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NANOTECHNOLOGIES
Principles, Applications,
Implications and
Hands-on Activities
A compendium for educators

Research and EUR 24957

Innovation
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EUROPEAN COMMISSION
Directorate-General for Research and Innovation
Industrial technologies (NMP)
Unit G.4 — Nano Sciences and Nano Technologies

E-mail: [email protected]

Contact: Matteo Bonazzi

European Commission
B-1049 Brussels
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EUROPEAN COMMISSION

NANOTECHNOLOGIES:

Principles, Applications,
Implications and Hands-on
Activities

A compendium for educators

Edited by the European Commission

Directorate-General for Research and Innovation
Industrial technologies (NMP) program
Authors:
Luisa Filipponi and Duncan Sutherland

Directorate-General for Research and Innovation

Industrial technologies (NMP)

two thousand and thirteen

EUR 24957
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Europe Direct is a service to help you find

answers to your questions about the European Union

Freephone number
(*): 00 800 6 7 8 9 10 11
(*) Certain mobile phone operators do not allow access to 00 800 numbers or these calls may be billed.

LEGAL NOTICE
Neither the European Commission nor any person acting on behalf of the Commission is responsible for the use which might be
made of the following information.

The views expressed in this publication are the sole responsibility of the authors and do not definitely reflect the views of the European
Commission.

More information on the European Union is available on the Internet (http://europa.eu).

Cataloging data and copyright information can be found at the end of this publication.

Luxembourg: Publications Office of the European Union, 2012

ISBN 978-92-79-21437-0
ISSN 1018-5593
doi:10.2777/76945

© European Union, 2012

Reproduction is authorized provided the source is acknowledged.

Printed in Luxembourg

Printed on elemental chlorine-free bleached paper (ECF)

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EXECUTIVE SUMMARY

This publication has been developed within the context of the research developed by the European
project NANOYOU, funded by the European Union's seventh framework program (FP7, grant
agreement n° 233433). It has been enriched by the authors with numerous and multifaceted inputs,
reflections and insights on societal issues, also provided by the European project TimeforNano.
(FP7, grant agreement n° 233481).

The results from all these efforts have been integrated and edited into an overall and fully referenced
book, showing how to address nanosciences and nanotechnologies concepts and applications.

It has been specially developed to present in a single, balanced compendium, much of the relevant and
valuable educational material that will help inform, motivate and inspire young people about nano
technologies and their applications. Theory, application and experiments in nanosciences and nanotech
nologies are organized in self-contained modules that offer increased flexibility throughout the
development ment of the course. Furthermore, a case study approach provides teachers with practical
applications and examples to discuss in class.

The program focuses on three application fields — information and communication technologies,
energy and environment, and medicine — and also addresses the associated ethical, societal, legal
and safety aspects to encourage further dialogue. Resources and training materials are available to
educators, supported, also, by online tutor web portals where young people and educators can actively
participate in virtual dialogues, experiments and games.

The lessons, discussions on applications and experiments presented in this book have been tested by
teachers, professors and educators from about one thousand schools (50 pilot schools and 906 ancil
lary schools) in 20 European countries from 2010 to 2011, reaching about 40,000 students. This expe
rience allowed for feedback and enriched this book with many comments and contributions, enabling to
produce the final and inclusive version.

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NOTE FROM THE EDITOR

The challenge of this book is to present in an understanding and attractive way nanosciences and
nanotechnologies to the educational community.

The first version was written as part of the NANOYOU project with the aim of providing school
teachers and educators of pupils aged 14-18 years with a comprehensive, yet easy to read and use,
compendium on nanotechnologies that fundamental concepts of nanosciences and nanotechnologies,
applications in three main application areas (medicine, environment and energy, information and
communication technologies), and experiments that can be safely carried out by the teacher in school
science laboratories. A key goal was to emphasize practical applications relevant to youngsters, and
to include topics of ethics, legal and societal aspects associated with selected applications. The
challenge was to provide school teachers and educators with a lasting tool they could use for their
school teaching to integrate nanosciences and nanotechnologies concepts in their activities. As such,
it should not be seen as a comprehensive scientific review (and for this reason some latest
developments, in say graphene, are not included): it is rather a compendium that can be used by
teachers, educators, or general readers interested in gain some fundamental understand of
nanotechnologies, their principles, applications but also implications, for individuals and society. After
its first version, the book has been further reviewed, selecting and integrating diverse inputs, reflections
and insights, also from other European projects: all these efforts have provided a very valuable and
integrated view of the science, technology and applications of the nano disciplines , simultaneously
offering innovative, inspiring and stimulating visions and understandings of the complexity and relevance they do repr

In this light, the aim and domain of this book is to illustrate the essence of nanotechnology. To this end,
the authors have succeeded in illustrating the new methods and materials, as well as explaining and
discussing the theory, applications and scientific experimentations on nanosciences and nanotechnologies.
In addition, the coverage of related ethics, legal, societal impact and safety complements the techno
scientific issues by raising awareness and stimulating debates on the benefits, challenges and risks
for that may be associated with the development of these and other emerging technologies.

We feel this work is particularly important: in fact, nanosciences and nanotechnologies are at the
forefront of today's science and technology, engineering both matter and living systems at the scale of
molecules and atoms. Their unique applications, products, markets and profitable revenue sources can
bring new benefits and challenges to both society and economy, as they are becoming increasingly
embedded in today's life. In fact, society at large needs to understand their pros and cons to make
responsible choices about new products and processes: research, innovation and education constitute
a living ecosystem, where education plays a key role.

Young Europeans might need to become more conscious and equipped on the fundamentals,
applications and prospects of nano disciplines to meet the new needs of research , economy and
industry. This will entail the necessity to enrich the educational systems with innovative tools, methods
and instruments to develop the new skills and understandings which are required to deliver responsible
innovation.

In this light, developing and disseminating appropriate learning and teaching materials could contribute
to shape a better informed ground for a more conscious, attentive and aware society, better equipped
to make fully responsible choices on nanotechnologies' potential impacts, opportunities, benefits,
uncertainties and drawbacks .

4 NANOTECHNOLOGIES: PRINCIPLES, APPLICATIONS, IMPLICATIONS AND HANDS-ON ACTIVITIES

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Nanotechnology is one of the very frontiers of science today. As a matter of fact, nanotechnology could
affect us all, beyond nanoparticles, critical length scales and nanotools: so, European citizens should be
able to see how all this science and technology could influence their lives ahead of the actual develop
ments. Beyond any spontaneous enthusiasm or mistrust any such highly innovative scientific develop
ment may bring, the fact that nanotechnology is becoming more and more deeply embedded in today's
life should warrant a meaningful, conscientious communication based on a continuous participation and
exchange between stakeholders and citizens.

So, developing appropriate communication, dialogue and education actions is crucial. Out of this
dialogue, desirable patterns could emerge. If the associated opportunities, risks and uncertainties were
properly addressed, all of us would certainly be closer to reaching consensus on which decisions and
choices to undertake. Every audience, be it young people, teachers, business, organizations or, more
broadly, the general public, could be called inclusive on to become involved at all levels, enabling policy
to promote good governance through. In this light, education is likely to be one key to communicate all
this to young people.

This compendium aims to address this challenge: as a matter of fact, it stems from the EC project
NANOYOU, and it has been enriched by the authors with numerous and multifaceted inputs, reflections
and insights on societal issues, also provided by the European project TimeforNano . So it represents a
valuable tool to support the educational communities on nanosciences and nanotechnologies. In fact, it
provides educators and teachers with a selection of relevant, accurate and up-to-date Theoretical and
experimental materials to help them inform, motivate and inspire young people about nanosciences,
nanotechnologies and their applications. The lessons, discussions on applications and experiments of this
compendium have been tested from 2010 to 2011 by hundreds of teachers, professors and edu cators
on tens of thousands of students from about one thousand schools in 20 countries in Europe and beyond
(Austria, Belgium, Cyprus , Czech Republic, Denmark, Finland, France, Germany, Greece, Hungary, Italy,
Latvia, Lithuania, Portugal, Romania, Slovakia, Sweden, Spain, Turkey, UK).

The educational materials are organized in three self-contained modules to offer increased flexibility
throughout the development of the course, addressing the fundamental concepts, the main application
areas and selected hands-on experiments. Furthermore, a case study approach provides educators and
teach ers with practical applications and examples to discuss in class. Background materials, literature
reviews, specific case studies and ideas are presented to show educators how to address nanosciences
and nano technologies concepts. Topics dealing with the ethical, societal and safety aspects of
nanotechnologies are also included to help educators encourage class debates, referenced with other
European projects and relevant webpages.

Overall, this experience has been very well received by about a thousand of participating educational
communities, which actively tested and enriched this book, enabling us to produce the inclusive, far
reaching and wide-ranging version you have in your hands: we are confident that the broadest possible
panoply of readers could appreciate this effort.

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6 NANOTECHNOLOGIES: PRINCIPLES, APPLICATIONS, IMPLICATIONS AND HANDS-ON ACTIVITIES

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CONTENTS

MODULE 1: FUNDAMENTALS ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ ÿ

Chapter 1: Introduction to nanoscience and nanotechnologies ÿÿÿÿÿÿ19

Definition of nanoscience and nanotechnologies ....................................................................... ................................. ............19

The nanometre scale ............................................................................ ................................. .............19

What is a nanomaterial? .............................. 20

What makes 'nano' special ....................... 22

From nanoscience to nanotechnologies ..................................................................... 23

Is it nanotechnology or nanotechnologies? ................................. ............................24

Bringing 'nano' into the classroom: Why and how? ................................. ................................. ...24

A cutting-edge science and technology ............................................................................ ................................. ............25

Hands-on nano! .............................. 25

'Nano' in the context of 'conventional' scientific disciplines ................................................................. ............25

Nanoscience in nature: a great starting point .................................................................. ................................. .26

Teaching challenges .............................................................................. ................................. ................................. 27

Talking about the 'bigger picture' ............................ 28

Talking about ELSA and safety in the classroom ............................................................ .................................29

Overview of ELSA issues in nanotechnologies ............................................................................ ................................................thirty first

thirty first
Privacy .......................................................................

Justice ........................... 32

Early diagnostics ....................................................................... 33

More than 'human'? .............................. 33

Nanotechnologies in consumer products ....................................................................... ................................. .......34

Safety of nanomaterials ....................................................................... ................................. .............35

APPENDIX ....................................................................................... ................................. ................................. .............39

Chapter 2: Nanoscience in nature ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ ÿÿÿÿÿÿÿÿÿÿÿ41

What is a natural nanomaterial? .............................. 41

Overview of natural nanomaterials ....................................................................... ................................. ............41

Learning from nature ....................................................................... 43

Detailed description of some natural nanomaterials ............................ ................................. .....44

Bones ....................................................................................... ................................. ................................. .............44

Lotus leaf ....................... forty six

How is this 'Nano'?............................ forty six

Gecko .......................................................................... 49

Morpho rhetenor ....................................................................... 51

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Chapter 3: History of nanotechnologies ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ

Feynman's speech ....................................................................... 55

Scanning tunneling microscope ....................................................................................... ................................. ............55 Colored

glass ................................ ................................. ................................. ................................. ..........56

Faraday's studies on gold colloids ............................................................ ................................. ............56

Miniaturized electronics.......................... 57

The GMR effect ....................................................................... 58

Advanced materials ....................................................................... 58

Fullerenes and carbon nanotubes .............................................................................. ................................. .................59

Liquid crystals ....................................................................................... 59

Chapter 4: Fundamental 'nano-effects' ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ ÿ63

What happens at the nanoscale? .............................. 63

A different kind of small................................................................................. sixty four

Physics at the nanoscale ....................................................................... sixty four

Chemistry at the nanoscale ............................................................................ ................................. ....................................66

Molecules as devices ....................................................................... sixty seven

Unique material properties at the nanoscale ............................................................................ ................................. ......................sixty seven

Surface properties ....................................................................... sixty seven

The importance of surface atoms ....................................................................................... ................................. .................69

Shape also matters ....................... 69

Surface energy ....................................................................... 70

Reactions where surface properties are very important ............................................................................ ............71

Catalysis ....................................................................................... 71

Detection .......................................................................... 72

Electrical properties ....................... 72

Quantum confinement and its effect on material electrical properties ................................................73

Nanomaterials with exceptional electrical properties ............................................................................ ............74

Optical properties ....................................................................... 74

Interaction of light with matter ................................................................................. ................................. ............74

Color generation from nanoparticles and nanostructures ............................................................ ............75 Color in metal colloids

(surface plasmons)................................ ................................. ............75

Color in semiconducting nanocrystals (quantum dots) .................................................................. ............77

From white to transparent materials ....................................................................... ................................. ...........77

Magnetic properties ....................................................................... 78

Mechanical properties ....................................................................... 80

Improving existing materials ....................................................................... ................................. ............80

Chapter 5: Overview of nanomaterials ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ ÿ83

Biomimetic nanomaterials ....................................................................... ................................. ................................. ........84

Gecko-inspired adhesive (or bio-rubber) ..................................................... ................................. ...........84

8 NANOTECHNOLOGIES: PRINCIPLES, APPLICATIONS, IMPLICATIONS AND HANDS-ON ACTIVITIES

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Self-healing adhesives ....................................................................... 85

Biomimetic membranes, capsules and bioreactors ............................................................ .................................85

Biomimetic energy nanomaterials ....................................................................... ................................. ............85

Self-assembled nanomaterials ....................................................... eighty six

Self-assembled monolayers (SAMs) ............................................................ ................................. .................86 Liquid

crystals ..................................................................... ............. 88

Liquid crystal self-assembly ............................................................................ ................................. ............89

Phases of liquid crystals and their properties................................................................................. .............90

Liquid crystal applications ....................................................................... 91

Nanostructured metals and alloys ....................................................................... 91

Metal nanoparticles ....................................................................... 92

Plasmonic structures ....................................................................................... 92

Reinforcements ....................................................................... 93

Environmental applications .............................................................................. ................................. ............................93

Nanocrystalline metals ....................................................................... ninety four

Ferrofluids ....................................................................................... ninety four

Shape-memory alloys ....................................................................... 95

Polymers ....................................................................................... 96

Conductive polymers ....................................................................... 96

Block copolymers ....................................................................... 97

Responsive 'smart' polymers ....................................................................... ................................. ............98

Biomedical applications ....................................................................................... ................................. .............98

Nanoreactors ....................................................................... 98

Artificial moving parts ....................................................................... 99

Other applications .......................................................................... 99

Polymeric nanofibres ....................................................................................... 99

Semiconductors ....................................................................... 101

Quantum dots .............................. 101

Semiconducting oxides ....................................................................... 102

Titanium Dioxide............................ 102

Zinc dioxide ....................................................................................... 103

Indium tin oxide ....................................................................................... 104

Photonic crystals ....................................................................................... ................................. ................................. ....104

Ceramic and glassy materials ....................................................................... 105

Porous alumina ....................................................................................... ................................. ................................. ........105

Zeolites ....................................................................................... 105

Aerogels ....................................................................................... 106

Carbon-based materials ....................................................................... 106

Carbon nanotubes ....................................................................... 108

Mechanical properties ....................................................................... 109

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Electrical and thermal properties ....................................................................... ................................. ..........110

Chemical reactivity ....................................................................... 110

Applications ....................................................................... 111

Composites.......... 112

Inorganic nanocomposites ....................................................................................... ................................. .................................112

Structural nanocomposites ....................................................................................... ................................. ............112

Nanocomposites with enhanced magnetic properties ....................................................................... ............113

Polymer nanocomposites ....................................................................... 114

Nanoparticle-polymer nanocomposites .................................................................................. ................................. .116

Carbon nanotubes printed polymer composites ....................................................................... ................................................................117

Polymer-clay nanocomposites ....................................................................................... ................................. .................117

Nanocoatings ....................................................................................... ................................. ................................. ................................................119

Tribological nanocoatings ....................................................................... 119

Responsive nanocoatings ....................................................................... 120

Superhydrophilic coatings ....................................................................... 121

Superhydrophobic coatings ....................................................................... 121

Chapter 6: Characterization methods ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ

Microcopy ....................................................................................... ................................. ................................. .............125

Scanning tunneling microscope ....................................................................................... ................................. ......................................126

Operational principle of the STM ..................................................... ................................. ............................126

How are images created? .............................. 128

Atomic force microscope ....................................................................................... 130

Spectroscopy methods ....................................................................................... 132

X-ray methods ....................................................................... 132

UV-visible plasmon absorption and emission ............................................................................ .................................................132

Plasmon resonance light scattering ....................................................................... ................................. ................133 Surface-

enhanced Raman scattering ................................................. ................................. ............133

Non-radiative and non-electron characterization methods ....................................................................... .............134

Chapter 7: Fabrication methods ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ ÿÿÿÿÿÿÿÿÿÿÿ 137 Top-

down ....................... ................................. ................................. ................................. .....137

Conventional lithography ....................................................................................... 137

Photolithography ....................................................................... 138

Scanning lithography ....................................................................... 138

E-beam lithography ....................................................................... 139

Soft lithography ....................................................................... 139

Nanocontact printing ....................................................................... 141

Nano-imprint lithography ....................................................................... 141

Nanosphere lithography ....................................................................................... 141

Colloidal lithography ....................................................................................... 143

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Scanning probe lithography ....................................................................... 144

Writing 'atom by atom' .............................. 144

Bottom-up ....................................................................... 146

Plasma arcing ....................................................................................... 146

Chemical vapour deposition ....................................................................... 146

Molecular beam epitaxial ............................................................................ 146

Sol-gel synthesis .............................................................................. ................................. ................................. ......147

Sol-gel process for making nanostructured surfaces ............................................................................ ............148

Functionalized silica glass surfaces ....................................................................... ................................. .........149

Molecular self-assembly ....................................................................... 149

DNA nanotechnology ....................................................................................... 151

MODULE 2: APPLICATIONS AND IMPLICATIONS ÿÿÿÿÿÿ155

Chapter 1: Medicine and healthcare ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ ÿÿÿÿ157

Diagnosis ................................................................................. ................................. ................................. .............157

Biosensors ....................................................................................... 158

Cantilever biosensor ....................................................................... 159

Plasmonic biosensors ....................................................................... 160

Artificial nose biosensor ....................................................................... 162

Microarrays ....................................................................... 163

Nanobarcodes ....................................................................... 163

Lab-on-a-chip ....................................................................... 163

Imaging ................................................................................. ................................. ................................. ................................................................164

Diagnostic imaging ....................................................................... 164

In situ diagnostic devices ....................................................................... 166

Therapy ............................ 166

Drug development and targeted drug delivery ....................................................................... ............................166

Drug design and screening .............................................................................. ................................. ............166

Targeted drug delivery ....................................................................... 167

siRNA drug delivery ....................................................................... 167

Stimuli-activated drug delivery ....................................................................... ................................. .................................169 Current

and future nano-drug carriers ................................................................. ................................. .................170

Externally activated therapies that use nanoparticles ............................................................ ............170

Theranostics ....................................................................................... 171

Regenerative medicine ....................................................................................... 171

Tissue and biomaterial engineering ....................................................................... ................................. ..........171

Nanoengineering bone regeneration ....................................................................................... ................................. .......173

Nanoengineering neuron regeneration ....................................................................................... ................................. ..174

Neuron tissue engineering ....................................................................... 174

Neuroprosthetics ....................................................................... 175

Neuronal stimulation, monitoring and pain management ............................................................................ ............176

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Non-invasive brain-machine interfaces ............................................................................ ................................. ............177

Chapter 2: Environment ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ 181

Remediation and mitigation ....................................................................... 182

Remediation using metal nanoparticles ....................................................................... ................................. ......182

Remediation using semiconducting nanoparticles ....................................................................... .................................................183

Remediation using dendrimers ............ ................................. ................................. .........184

Remediation using magnetic nanoparticles ....................................................................... .................................................184

Remediation using aerogels and solid absorbents ............................................................ .......................................185

Nanomembranes and nanofilters ....................................................................... ................................. ............185

Superhydrophilic filters ....................................................................................... ................................. ..............................186

Pollution prevention ....................................................................... 186

Materials ....................................................................... 187

Lotus effect® surfaces and textiles ....................................................................... ................................. ............187

Antimicrobial coatings, textiles and other products ................................................................. ............189

Other coatings ....................................................................... 191

Fertilisers and wood treatment products ....................................................................... .................................................191

Biomimetic water harvesting ....................................................................................... ................................. ............191

Nanocatalysis ....................................................................................... 192

Catalytic gold ....................................................................... 193

Recovery of catalytic materials ....................................................................... ................................. ............193

Green manufacturing ....................................................................... 194

Environment sensing ....................................................................... 195

Nanowire and nanotube-based sensors ....................................................................... ................................. ........196

Cantilever sensors ....................................................................... 197

Food packaging and monitoring ....................................................................... 197

Chapter 3: Energy ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ 201 Solar

energy ....... .............................. 202

Photovoltaics .............................. 203

Nanocrystals ....................................................................................... 204

Biomimetic approaches using nanotechnologies ....................................................................... .......................................204

Artificial photosynthesis ....................................................................... 204

Dye-sensitized solar cells ....................................................................... 205

Quantum-dot-sensitized solar cells................................................................................. ................................. ............206

Lotus-mimicing PV coatings ....................................................................... ................................. .................206

Solar energy storage ....................................................................... 207

Solar heating ....................................................................... 207

Hydrogen society ............................................................................ ................................. ................................. ............207

Hydrogen production ................................................................................. ................................. .................................208

Nanotechnologies for improving photoinduced water splitting .......................................................................... 209

twelfth NANOTECHNOLOGIES: PRINCIPLES, APPLICATIONS, IMPLICATIONS AND HANDS-ON ACTIVITIES

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Hydrogen storage ....................................................................... 210

Solid metallic nanostructured supports ................................................................................. ................................. .210

The hydrogen fuel cell ....................................................................... 212

Proton exchange membrane fuel cell ....................................................................................... ................................. .......212

Thermoelectricity ....................................................................... 214

Rechargeable batteries ....................................................................... 215

Nanotechnologies to impact energy capacity, battery power, charge rate and

lifetime ............ ................................. .....................................216

Nanomaterials as alternatives to conventional electrodes .................................................................. ...........216

'Paper battery' ....................... 217

Battery operation range, lifetime and safety ............................................................ ............................217

Supercapacitors ....................................................................... 218

Energy savings ......... 218

Catalysis ....................................................................................... 218

Advanced materials ....................................................................... 219

Insulators and 'smart' coatings ....................................................................... ................................. ............219

Energy-harvesting materials ....................................................................... ................................. ............220

Efficient lighting................................................................................................ 221

Efficient energy transport ....................................................................... 222

Chapter 4: Information and Communication Technologies ÿÿÿÿÿÿÿÿÿ225

Integrated circuits ....................................................................................... ................................. ................................. .............225

More Moore ....................................................................... 227

More than Moore ....................................................................................... 228

Beyond CMOS ....................................................................................... 228

New data storage and processing nanotechnologies ....................................................................... ............229

Data storage ....................................................................................... ................................. ................................. ..............................230

The concept of a universal memory ............................................................................ ................................. .................231

Nanotechnology developments in data storage ....................................................................... .................................231

MRAM .............................. 232

232
NRAMTM ....................................................................................... ................................. ............................

Phase-change memory ....................................................................... 233

Photonics ....................................................................................... ................................. ................................. .................................233

Photonic crystals ....................................................................................... ................................. ................................. ....233

Applications in communication ....................................................................................... ................................. ............234

Properties of photonic crystals................................................................................. ................................. ............234

Fabrication of photonic crystals ................................................................................. ................................. ..235

Displays ......... 236

OLEDs ....................................................................................... ................................. ................................. ............236

Applications of OLEDs ....................................................................................... ................................. ............................238

13
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Quantum dot light-emitting diodes (QD-LED) .............................. ................................. .239

Electronic paper (e-paper) ............................ 239

Nanotechnologies for e-paper ....................................................................... ................................. .................. 240

Information storage devices ....................... ................................. ................................. ............241

Nanotechnologies in tags............................................................................ 241

Wireless sensing and communication ....................................................................... ................................. .................................243

Wearable sensing textiles ....................................................................... 244

MODULE 3: EXPERIMENTS ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ ÿÿÿÿÿÿÿÿÿÿÿÿ 247

Experiment A: Natural nanomaterials ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ ÿÿÿÿÿÿÿÿÿÿÿÿÿ

TEACHER RESOURCES ....................................................................... 250

STUDENT BACKGROUND READING ................................................................................. ................................. ............ 263

STUDENT LABORATORY WORKSHEET ............................................................................ ................................. .........269

Experiment B: Liquid crystals ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ275

TEACHER RESOURCES ....................................................................... 276

STUDENT BACKGROUND READING ................................................................................. ................................. ............ 289

STUDENT SYNTHESIS PROCEDURE ................................................................................. ................................. ............294

STUDENT LABORATORY WORKSHEET ............................................................................ ................................. ......... 297

Experiment C: Colorimetric gold nanosensor 305

TEACHER RESOURCES ....................................................................... 306

STUDENT BACKGROUND READING ................................................................................. ................................. .................324

STUDENT SYNTHESIS PROCEDURE ................................................................................. ................................. ..........331

STUDENT LABORATORY WORKSHEET ............................................................................ ................................. .........334

Experiment D: Superhydrophobic materials ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ

TEACHER RESOURCES ....................................................................... 342

APPENDIX FOR TEACHERS ....................................................................... 361

STUDENT BACKGROUND READING ................................................................................. ................................. .................364

STUDENT LABORATORY WORKSHEET ............................................................................ ................................. ......... 373

Conclusions ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ

Acknowledgements ÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿ 389

BIBLIOGRAPHY AND Extra Reading for students and teachers ÿ391

14 NANOTECHNOLOGIES: PRINCIPLES, APPLICATIONS, IMPLICATIONS AND HANDS-ON ACTIVITIES

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In nova fert animus mutatas dicere formas corpora.

My mind inclines me to speak of forms changed into new bodies.

(Publius Ovidius Naso,

Metamorphoseon - Proemium)
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MODULE 1:
FUNDAMENTALS
Module addressing principles
and fundamental concepts
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CHAPTER 1:

INTRODUCTION TO NANOSCIENCE
AND NANOTECHNOLOGIES
This introductory chapter defines nanoscience, nanotechnologies and nanomaterials. It illustrates in
general terms what is 'special' about the 'nano-world' and why this new area of science and technology
is exciting and worth bringing into the classroom.

Definition of nanoscience

and nanotechnologies

The most common working definition of nanoscience is:

'Nanoscience is the study of phenomena and manipulation of materials at atomic, molecular and
macromolecular scales, where properties differ significantly from those at a larger scale' (1 ).

Bulk materials (the 'big' pieces of materials we see around us) possess continuous (macroscopic)
phys ical properties. The same applies to micron-sized materials (eg a grain of sand). But when
particles assume nanoscale dimensions, the principles of classic physics are no longer capable of
describing their behaviour (movement, energy, etc.): at these dimensions, the principles of quantum
mechanics principles. The same material (eg gold) at the nanoscale can have properties (eg opti
cal, mechanical and electrical) which are very different from (and even opposite to!) the
properties the material has at the macroscale (bulk). Nanotechnologies are defined thus:

'Nanotechnologies are the design, characterisation, production and application of structures, devices
and systems by controlling shape and size at the nanometre scale.'

In the next sections of this chapter we will discuss these definitions and their meaning, starting with
what is meant by the 'nanometre scale'.

The nanometer scale

The nanometre scale is conventionally defined as 1 to 100 nm. One nanometre is one billionth of a
meter (10-9 m). The size range is normally set to a minimum of 1 nm to avoid single atoms or very
small groups of atoms being designated as nano-objects (Figure 1). Therefore, nanoscience and
nanotechnologies deal with clusters of atoms of 1 nm in at least one dimension.

( ) Nanoscience and nanotechnologies: opportunities and uncertainties, report by The Royal Society and The Royal Academy of
first

Engineering 2004 (http://www.nanotec.org.uk/).

MODULE 1: FUNDAMENTALS 19
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The upper limit is normally 100 nm, but this is a 'fluid' limit: often objects with greater dimensions
(even 200 nm) are defined as nanomaterials.A valid question a student might ask is 'Why 100 nm
and not 150 nm?' , or even 'Why not 1 to 1 000 nm?' The reason why the '1 to 100 nm range' is
approximate is that the definition itself focuses on the effect that the dimension has on a
certain material — for example the insurgence of a quantum phenomenon — rather than at
what exact dimension this effect arises. Nanoscience is not just the science of the small, but
the science in which materials with small dimension shows new physical phenomena,
collectively called quantum effects, which are size-dependent and dramatically different from the
properties of macroscale materials.

Nanoscience is the study of materials that exhibit remarkable properties, functionality and
phenomena due to the influence of small dimensions.

Figure 1: Three and a half gold atoms placed in a row equal 1 nm (assum
ing a covalent radius of 0.144 nm each)

Image: L. Filipponi, iNANO, Aarhus University, Creative Commons ShareAlike 3.0

What is a nanomaterial?
A nanomaterial is an object that has at least one dimension in the nanometre scale (approximately 1 to
100 nm). Nanomaterials are categorised according to their dimensions as shown in Table 1.

Table 1: Nanomaterials are categorised according to their dimensions

Nanomaterial dimension Example

Nanoparticles, quantum dots, nanoshells, nanor

All three dimensions < 100 nm
ings, microcapsules

Two dimensions < 100 nm Nanotubes, fibres, nanowires

One dimension < 100 nm Thin films, layers and coatings

Nanomaterials can be of two types:

• 'non-intentionally-made nanomaterials', which refers to nano-sized particles or materials that

belong naturally to the environment (eg proteins, viruses, nanoparticles produced during volcanic
eruptions, etc.) or that are produced by human activity without intention ( eg nano particles
produced from diesel combustion);
• 'intentionally-made' nanomaterials, which refers to nanomaterials deliberately produced
through a defined fabrication process.

20 NANOTECHNOLOGIES: PRINCIPLES, APPLICATIONS, IMPLICATIONS AND HANDS-ON ACTIVITIES

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The definition of nanotechnologies does not generally include 'non-intentionally-made nanomaterials'

and is, therefore, limited to 'intentionally-made nanomaterials'.

A very important concept to bring in to the classroom is 'the smallness of nano'. Nanomaterials are
larger than single atoms but smaller than bacteria and cells. It is useful to use a scale such as the
one shown in Figure 2 where students can visualize the relationship between bulk materials, for
example a tennis ball, and nanomaterials.

Figure 2: From macro-materials to atoms: nanomaterials and nanodevices that are of interest in
nanotechnologies are at the lower end of the scale (1–100 nm)

Image: adapted from 'A snapshot of nanotechnology', National Cancer Institute

Some good examples to bring to the classroom:

•our fingernails grow at the rate of 1 nm per second;

•the head of a pin is about 1 000 000 nm in diameter; •a
human hair is about 80 000 nm in diameter; •a
DNA molecule is 1–2 nm wide; •the
transistor of a latest-generation Pentium Core Duo processor is 45 nm.

MODULE 1: FUNDAMENTALS 21
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A simple activity for youngsters is to measure their height in nano meters!

Details of the activity How tall are you in nanometers? can be found in the
timefornano NanoKIT — Activity 1 (http://www.timefornano. eu/nanokit#ac01).

What makes 'nano'

special

'Nano' means small, very small; But why is this special? There are various reasons why nanoscience
and nanotechnologies are compared promising in materials, engineering and related sciences. First,
at the nanometre scale, the properties of matter, such as energy, change. This is a direct consequence
of the small size of nanomaterials, physically explained as quantum effects. The consequence is that
a mater ial (eg a metal) when in a nano-sized form can assume properties which are very different
from those when the same material is in a bulk form. For instance, bulk silver is non-toxic, whereas
silver nanoparticles are capable of killing viruses upon contact. Properties like electrical conductivity,
colour, strength and weight change when the nanoscale level is reached: the same metal can
become a semiconductor or an insulator at the nanoscale level. The second exceptional property
of nanomaterials is that they can be fabricated atom by atom by a process called bottom up. The
information for this fabrication process is embedded in the material building blocks so that these can
self-assemble in the final product. These two fabrication methods are reviewed in Module 1, Chapter
7: Fabrication methods. Finally, nanomaterials has an increased surface-to-volume ratio compared
to bulk materials. This has important consequences for all those processes that occur at the surface
of a material, such as catalysis and detection. The properties that make nanomaterials 'special' are
further discussed in Module 1, Chapter 4: Fundamental 'nano-effects'.

Nanoscience and nanotechnologies depend on the exceptional properties of matter at the nanoscale
level. In this context, 'nano' doesn't only mean '1 000 times smaller than micro', and nanotechnol
ogies are not just an extension of microtechnologies to a smaller scale. It is an entirely new paradigm
that opens entirely new scientific opportunities.

The exceptional properties of matter at the nanoscale are the subject of Module 1, Chapter 4:
Fundamental 'nano-effects'.

22 NANOTECHNOLOGIES: PRINCIPLES, APPLICATIONS, IMPLICATIONS AND HANDS-ON ACTIVITIES

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From nanoscience to
nanotechnologies
Nanoscience is an 'interdisciplinary science', which means that it involves concepts of more than one
discipline, such as chemistry, physics, etc. There are other disciplines that are inherently interdisciplin
ary, such as materials science (and engineering), which cover, at the same time, concepts of chemistry
and physics. Nanoscience further expands the borders of material science by adding biology and bio
chemistry to the mix. Nanoscience is thus a 'horizontal-integrating interdisciplinary science that cuts
across all vertical sciences and engineering disciplines' (2 ) (Figure 3).

Figure 3: Nanoscience is a horizontal

integrating interdisciplinary science that
cuts across all vertical sciences and
engineering disciplines.

Image: L. Filipponi, iNANO, Aarhus University,

Creative Commons ShareAlike 3.0

Nanoscience offers educators the possibility to bring into the classroom the concept of 'interdisciplin
ary'. As will be discussed in the next chapters (Chapters 2 and 3), we have numerous examples of
nanoscience in nature, as well as in historic artefacts. The teacher, therefore, has an opportunity to
truly show how nanoscience integrates not only scientific disciplines (chemistry, physics, biology,
etc.) but also the humanities. Some practical ideas on how to exploit this opportunity are given
throughout this book.

The application of nanoscience to 'practical' devices is called nanotechnologies. Nanotechnologies are

based on the manipulation, control and integration of atoms and molecules to form materials, struct
tures, components, devices and systems at the nanoscale. Nanotechnologies are the application of
nanoscience especially to industrial and commercial objectives. All industrial sectors rely on materials
and devices made of atoms and molecules thus, in principle, all materials can be improved with nano
materials, and all industries can benefit from nanotechnologies. In reality, as with any new technology,
the 'cost versus added benefit' relationship will determine the industrial sectors that will mostly benefit
from nanotechnologies.

(2 ) Hornyak, GL et al., Introduction to Nanoscience, CRC Press, 2008.

MODULE 1: FUNDAMENTALS 23
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Figure 4: Nanotechnologies are

horizontal enabling convergent
technologies which cross all vertical industry
sectors. The different heights of the
industrial sectors in the graph are only
indicative and are intended to emphasize
the fact that the level of impact of
nanotechnologies will be different in
each industrial sector.

Image: L. Filipponi, iNANO, Aarhus University,

Creative Commons ShareAlike 3.0

Thus, nanotechnologies are horizontal-enabling convergent technologies (Figure 4). They are
'horizontal' because they cut across numerous industrial sectors; they are 'enabling' since they provide
the platform, the tools to realise certain products; and are 'convergent' because they bring together
sectors of science that were previously separated.

One example is DNA silicon chips, which are an example of convergence between semiconductor
science (inorganic chemistry) and biology, with applications in the medical industry.

Is it nanotechnology or nanotechnologies?
When the term was first used in 1959, it was used in the singular, 'nanotechnology'. In the last few
years, the field has evolved in few years. terms of science and technology Scientists have also started
to address the ethical, ethical and societal impact of 'nanotechnology'. In doing so, it has become
clear that this is not one technology, but that different nanotechnologies exist (which all share the
common concept of using the properties of matter at the nanoscale). There has even been a call
from a prominent scientist and expert in nanotechnologies to stop using the singular, and to use the
plural, precisely to communicate the variety of materials and methods involved in nanotech nologies.
Nowadays, the plural form is most used and it is the form that will be used in this Teachers Training
Kit.

Bringing 'nano' into the classroom:

Why and how?
There are numerous reports that emphasize the need to 'revitalise' science teaching in school, particu
larly at the highschool (14+) level. It is also often recommended in those reports that-based science
education (or problem-based learning) is encouraging, where teaching is conducted through an
inductive (rather than deductive) method. This should be combined with numerous 'hands-on' activities
to allow students to see science for themselves, and then learn and understand the theoretical
explanation of what they see. Nanoscience and nanotechnologies offer such opportunities!

24 NANOTECHNOLOGIES: PRINCIPLES, APPLICATIONS, IMPLICATIONS AND HANDS-ON ACTIVITIES

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A cutting-edge science and technology

Nanoscience and nanotechnologies offer teachers a new instrument to bring exciting science
and technology into the classroom. Nanotechnologies are now used in numerous devices with
which young students are very familiar, such as computers, mobile phones and iPods. Nanoscience
offers the possibility to improve numerous material properties and create new ones; in the future,
we will have more and more products that incorporate some form of 'nano' — either a nanomaterial,
or a nano-enabled technology. Bringing 'nano' into the classroom means bringing in the latest
cutting-edge science and technology and talking about very exciting future scientific developments.

Hands-on nano!

One of the peculiarities of nanoscience is that numerous 'nano-effects' can be seen in our 'macro
world'. The best example is a gold colloid (gold nanoparticles of about 15 nm dispersed in water)
which is red in colour. When some salt solution is added to the gold colloid, it turns blue! There are
many 'hands-on' activities and demonstrations that can be used to show the properties of
nanomaterials — effects that are visible! So even though the 'nano-world' is invisible, we can
appreciate its effects in materials with which youngsters are very familiar, such as gold. In this
Teachers Training Kit, these activities are described in an Experiment Module and throughout the
main text as simple demonstrations that a teacher can perform in the classroom.

'Nano' in the context of 'conventional' scientific disciplines

One of the challenges a science teacher might face is how to insert nanoscience into conventional sci
ence curricula. Where does this 'new' science fit into the 'conventional' scientific disciplines — chem
istry, physics or biology? The aim of this training kit is also to provide teachers with practical ideas on
how to integrate nanoscience and nanotechnologies into their science curriculum.

Nanoscience is not new per se, it is a name we now give to a number of fields of research that
share a common principle: the investigation of matter at a scale which is intermediate between
'bulk' matter, described by Newtonian physics, and atomic matter (ie atoms, electrons, etc.),
described by quantum physics. Nanoscience works in this 'size window' (approximately 1 to 100
nm) where matter shows some remarkable properties. A number of scientific fieldswith very old
origins are included in this window: for example, colloidal science (see also Module 1, Chapter 3:
History of nanotechnologies. In a sense, the study of atoms and molecules is the basis of
most natural science disciplines , such as chemistry, biochemistry and physics Nanomaterials
are not all new either: nanocrystals, nano-sized catalysts and magnetic nanoparticles have been
studied for many years now, for a variety of applications. instance, the Atomic Force Microscope
(AFM) and the Scanning Tunnelling Microscope (STM) techniques were first introduced to the
scientific community in the mid 1980s.

MODULE 1: FUNDAMENTALS 25
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So the question is: If it's not all new, why is it so special? In recent years, researchers have been
able to uncover the enormous potential of nanoscience and nanotechnologies thanks to a new set
of analytical and fabrication tools. At the same time, in recent years, new nanomaterials have
been reluctantly fabricated or discovered, novel nanotools have been developed and old ones
implemented, and novel properties of matter at the nanoscale level have been discovered.

All of this has allowed the systematic investigation of nanomaterials and the realisation that
the exceptional properties of matter at the nanoscale level can be used to build new
materials, systems and devices with properties, capabilities and functions that could not be
achieved if bulk materials were used . This is where the novelty lies, and the reason for being
excited about it! The exceptional properties of matter at the nanoscale have prompted to 'reinvent'
the way materials are engineered and produced, and are opening up exciting new opportunities in
many different fields.

Nanoscience is thus a 'work-in-progress science'. A 'work' that finds its roots in disciplines, such as
chemistry and physics, where much fundamental knowledge is well established, and that is progressing
towards fields where new knowledge is currently being created and collected.

For these reasons, we prefer to describe nanoscience as an evolution of more traditional scientific
disciplines. 'Nano' is not a revolution per se, but nanotechnologies might have some revolutionary
implications for our society in terms of the applications or tools that they will enable.

Nanoscience in nature: a great starting point

Even though nanoscience is often perceived as a science of the future, it is actually the basis for
all systems in our living and mineral world. We see hundreds of examples of nanoscience right in
front of our eyes every day — from geckos that can walk upside down on a ceiling, apparently
against gravity, butterflies to butterflies with iridescent colours, to fireflies that glow at night. In
nature, we encounter some outstanding solutions to complex problems in the form of fine
nanostructures with which precise functions are associated. In recent years, researchers have
had access to new analytical tools to see and study those structures and related functions in depth.
This has further stimulated research in the nanoscience area and has catalysed nanotechnologies.
So, in a sense, natural nanoscience is the basis and inspiration for nanotechnologies.

Natural nanomaterials offer a great starting point to bring nanoscience into the classroom. Images
from microscopes are a great resource, especially if used consequently in a 'zoom-in' fashion,
starting from a macro object (eg a plant leaf) and showing how zooming in with subsequent
magnifications reveals finer and finer structures. This becomes extremely effective if we start with
familiar, natural objects such as plants (Figure 5) and animals. Students will be fascinated to
discover how many natural nanomaterials are around us.

26 NANOTECHNOLOGIES: PRINCIPLES, APPLICATIONS, IMPLICATIONS AND HANDS-ON ACTIVITIES

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MACRO
MACRO(A) MICRO
MICRO(B) and (C) NANO (D)
NANO
Figure 5: Close-up views at progressive magnification of a nasturtium leaf revealing the presence
of surface nanocrystals (image on the far right)

Image: (A) A. Snyder, Exploratorium; (B, C) A. Marshall, Stanford University; (D) A. Otten and S. Herminghaus, Göttingen,
Germany; all images are material of the NISE Network, reprinted under NISE Network Terms and Conditions

Teaching challenges
The definition of nanoscience naturally calls for the definition of a nanometre, which is a billionth of
a meter. Although the are many examples that one can present of objects that have dimensions at
this level, such as the width of DNA (2 nm), mental visualization of these objects is impossible,
and many studies have reported how young people, especially children, lack the mental capacity
to actu ally imagine something this small because of lack of experience. Even for adults, mental
visualization of objects with sub-micron dimensions is extremely difficult (a result of the inherent
resolution of our visual ability, which is 2 µm).

One concept that can easily be shown is the fact that even if we cannot see
something, it doesn't mean is not there. A very simple way to show this is
by performing progressive dilutions of a scented colored liquid: at very high
dilutions, although the color can no longer be seen, we can still smell the
scent. Details of this activity, Dilution, can be found in the timefornano
NanoKIT — Activity 2 (http://www.timefornano.eu/ nanokit#ac02).

MODULE 1: FUNDAMENTALS 27
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However, as much as we can ask students to imagine something that is a thousand times smaller
than their hair, we need to ask if they can really understand the sense of the dimensionality we
are talking about. And, more important, if they can understand the difference between objects that
are at the nanoscale level and objects that are even smaller, such as atoms. For some people,
knowing that a rock is a million years old or a thousand million years old makes no difference: both
dimensions are just 'huge' and are confused in a 'time blur'. similarly, the nanoscale and the atomic
scale can be perceived as a 'scale blur', just too small to think of. Therefore, the challenge here is to
introduce the nanoscale and the concept of nanoscience in a meaningful way, one that grasps the
attention of the students but that also means something to them. In this sense, an enquiry-based
approach (based on student questions) together with hands-on activities can help. For example,
starting from a cube of a soft material and cutting it progressively until it can no longer be handled
(which will not lead to a nanometre-sized cube, but will give a sense of smallness); or using ratio
examples, such as how tall would a tower of single paper of sheets be, assuming each sheet is 1
nm. Images from microscopes are probably one of the best resources we have, especially if used
consequently in a 'zoom-in' fashion, as described in the previous section. But, what is also important
is showing the peculiarity of the nano meter scale, why objects at this level are 'special' and behave differently from t
Examples should be given so that instead of trying to imagine a nanometre, students perceive what
it means, for example, for a certain material to be 2 nm rather than 2 mm. Gold is a prime case, and
the classic example is a gold wedding ring compared with multicolored gold quantum dots (colloidal
gold). Whatever the example or the methodology chosen to communicate, it is important to remember
that young people will have great difficulty in conceiving nanoscale objects; so it is important not to
ask them to visualize how small a nanometre is but rather that they appreciate what it means to be
so small. NANOYOU has developed numerous tools (a memory game, puzzles and laboratory
exercises) precisely to overcome those difficulties.

One aspect that is often overlooked (or assumed) when introducing nanoscience and nanotechnology
is the actual nature of a 'nano-object' or 'nanomaterial'. It is possible to mistakenly give the impression
to the audience that these are free-standing objects or that these are aerosol-like particles that can
float in a medium. Although some nanoparticles are airborne, most of the nanomaterials under
research or used in commercial products are integrated or attached to another substrate.
Furthermore, nanoscience does not just deal with nano-objects but also nanostructures within larger
objects. For instance, a wire having the dimension of a hair (say, 2 µm) can be of molecules which
are orderly arranged in nanowires.

Talking about the 'big picture'

Nanotechnologies have progressed at a fast pace in the last few years, both in laboratories and in
the commercialisation of numerous products. The promise of nanotechnologies is great in many
applica tions and this has resulted in conspicuous investments both at research level and in industry.
Other emerging technologies in the past were presented to the scientific community (and industry)
as revo lutionary, with enormous potential for commercialisation, most notably the genetic engineering
of foodstuffs. Genetically modified organisms were expected to bring profit and advancement in the
food and medical industries. Due to a number of issues (one of the most important being very poor
commu nication between the scientific community and the popular media), GMOs were not received
favourably by the consumer community, and the result has actually been the opposite. In many
countries, these products have been banned or strongly regulated. Numerous ethical questions were also raised on

28 NANOTECHNOLOGIES: PRINCIPLES, APPLICATIONS, IMPLICATIONS AND HANDS-ON ACTIVITIES

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'who' would benefit from these products, and what implications they might have for people's long-
term health, as well as the life cycle of animals and plants. The GMO case is a clear example of an
emerging technology that did not go through a careful Ethical, Legal and Social Aspects (ELSA) analysis.
It is also a clear example of an innovative technology that suffered a backlash from consumers to the
point where research was stopped and entire research centers were closed. Consumers had a power
that scientists (and even the media) did not realise until it was too late.

With nanotechnologies, there is a general determination to 'do it differently' at all levels. Probably for
the first time in the history of scientific innovation, researchers, regulators, non-gov ernmental
organizations (NGOs), consumer organisations, trade unions and industry are all involved in
setting guidelines, action plans, protocols, codes of conduct, regulations, etc., to make sure that
nanotechnologies realise their potentials while protecting the safety of consumers and the
environment (in terms of pollution and impact on its life cycles), and are ethically sound. Clearly,
this is a massive effort and the work is complex and has only started.
While this Teachers Training Kit, we will indicate areas of nanotechnology applications that are raising
ELSA issues, and the actions that are currently being taken to address them.

For the teacher, bringing ELSA issues into the classroom is an opportunity to talk about science, tech
nology and innovation in a more complex, 'three-dimensional' fashion. It gives educators an opportunity
to stimulate discussions in class about which innovations students think are valuable (and which are
not), who will benefit from these, at what cost, etc. It is a chance to think and talk about the 'big ger
picture' of science and innovation and think about its implications not just for the single
individual, but for society.

Talking about ELSA and safety in the classroom

Questions of ethics, social impact, safety, etc., are rare part of a secondary science curriculum.
Depending on age and school curricula, some students might have undertaken some philosophy
courses, others probably not: therefore, ELSA issues are probably a new concept for most. The
question is then how to introduce those concepts without overloading students with information,
and how to respond adequately to questions raised in class. Otherwise, the result might be a feeling
that ELSA and safety questions are just too big to be even analyzed.

The aim of NANOYOU is also to provide teachers with resources to encourage class discussion
about ELSA topics related to nanotechnologies. To focus the discussion, teachers have access to a
number of tools (Table 2).

MODULE 1: FUNDAMENTALS 29
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Table 2: Tools available in this training kit

NANOYOU Tool description

NANOYOU Nano role-playing game This is a role-playing game with various
(http://www.nanoyou.eu) dilemma scenarios. For each dilemma, several
'roles' have been created: each student (or
group of students) is given one specific role
and a class debate is held on the dilemma.
The dilemmas relate to specific applications of
nanotechnologies; these dilemmas are discussed
in Module 2 of this Teachers Training Kit within
the various application areas (NANOYOU
dilemma, blue boxes).

NANOYOU NT Virtual dilemmas These are computerised animations where

(computerised animations) students enter a virtual world and are
(http://www.nanoyou.eu) by various dilemmas relating to
nanotechnology applications.

ELSA Topics in the NANOYOU Teachers In this kit, teachers will find ELSA boxes
Training Kit in Nanotechnologies throughout the chapters of Module 2 (ELSA
Topic, red boxes).

NANOYOU Video competition Youngsters aged 18+ have produced some

videos on the topic of Nanoelectronics and
societal impact. All videos can be found in the
NANOYOU Project YouTube channel
(http://www.youtube.com/user/NANOYOUproject).
Videos are cited throughout the document.

OTHER RESOURCES description

PlayDecide for TIME for Nano — Senior This game is a variant of the game Decide
(http://www.playdecide.eu). This version was
made especially for the timefornano NanoKIT.
Decide is a discussion game for young people in
which the ethical and social issues arising from
nanotechnologies are discussed. It works best
when played by four to eight people and it
takes about an hour and a half to play
(http://www.timefornano.eu/nanokit).

PlayDecide for TIME for Nano — Junior This is a simplified version for younger
players. On the back of the cards, there are
pictures that can be used to tell a story where
nanotechnologies are involved. The players are
free to choose as many cards as they wish and
put them in a line so as to tell a story as in a
comic book. They can tell their story to their
friends or write it down (http://www.timefornano.
eu/nanokit).

30 NANOTECHNOLOGIES: PRINCIPLES, APPLICATIONS, IMPLICATIONS AND HANDS-ON ACTIVITIES

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timefornano Videos A video contest among youngsters was

also run by timefornano. Videos can be found
in the timefornano YouTube channel
(http://www.youtube.com/user/timefornano)
or Vimeo channel (vimeo.com/channels/
timefornano). Videos of the timefornano
competition deal with some ELSA aspect of
nanotechnologies and are useful to bring those
topics into class … with fun and creativity!

In the next section, we provide an overview of ELSA topics which relate to nanotechnologies
and an overview of the safety of nanomaterials. In each section, the relevant NANOYOU tools
that have been developed to promote dialogue in class are highlighted.

When discussing ELSA and safety topics, it is useful to encourage students to reflect on other
innovative technologies that they are familiar with and that have had important ELSA and safety implications.
Some examples are provided in Appendix A.

Overview of ELSA issues in nanotechnologies

What follows is a short overview of crucial ELSA questions that are relevant to nanotechnologies. The list is
not exhaustive and aims to give teachers an idea of the vastness and complexity of these issues.
Most are open questions for which we don't provide answers —they are meant to spur debates in class
with students.

Privacy

We live in a world where our movement is often controlled by hidden cameras. Miniaturisation has
allowed these devices to be integrated into many objects, and nanotechnologies will most likely lead
to even smaller devices allow them to be integrated into textiles and other composite materials.
Nowadays, consumer choices are tracked by Internet purchases and other indirect means, but 'smart' labels
currently under development use a built-in tracking system called Radio Frequency Identification (RFID). These
labels do already exist, but are fairly large, for instance, in e-passports (see Module 2, Chapter 4: Information
and Communication Technologies for more information). The vision in the future is to miniaturise them to a
point that every commercial object will contain a 'smart' label, and be able to communicate its position. This
would ensure, for example, in the case of food packages, the product integrity, transport conditions, etc. RFID
technology could be the ultimate solution to theft and fraud. Opponents warn that such devices could be used
as 'spychips', even integrated into humans, and which could be used by governments, leading to an increased
loss of civil liberties. If, for instance, food companies were to use this type of chip on the products we consume,
they would have access to an incredible amount of private information.

Another vision of the ICT industry is the concept of ambient intelligence: computation and com munition
always available and ready to serve the user in an intelligent way (ie satisfying certain requirements). The
vision is to have electronic devices that work as a gateway between the user and the environment. This will
require ubiquitous sensing and computing: devices must be highly mini-aturized, integrated in the
environment, in soft materials like textiles, autonomous, robust, and require low power consumption.
Nanotechnologies have the conceptual capacity to realise this vision. The time frame from 'vision' to reality
could be decades but, if this was to come true, we would live in a world

MODULE 1: FUNDAMENTALS thirty first

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where we are even more connected, never 'alone', scrutinised. Clearly, this would add numerous
benefits to our current life but would also threaten our personal privacy even more.

NANOYOU
ROLE-PLAYING
DILEMMA MORE INFO…
GAMES and VIRTUAL
DIALOGUE TOPIC
GPS Jacket Should we buy a jacket with Module 2, Chapter 4:
built-in GPS? Information and
Communication Technologies

Internet for everything Do we want to live in a world Module 2, Chapter 4:

where everything is connected, Information and
monitored, observed and open Communication Technologies
to scrutiny?

More information, including videos, on the issue of Privacy implications of

nanotechnology is available on the timefornano project page (http://
www.timefornano.eu/privacy).

Justice

Who should benefit from nanotechnologies? Are nanotechnologies going to further increase the eco
nomic and social divide between 'north' and 'south' in the world? This is referred to as the 'nanodivide'.
Will medical devices, or therapies, developed diagnostic nanotechnologies, be available for anyone, and
distributed through the public health system, or will they be so expensive that only a limited sector of the
population will have access to them?

NANOYOU PPT Teachers can find a PowerPoint presentation, Benefits and risks for devel
oped and developing countries, which covers aspects of justice, the 'nanodivide', and the
responsible development of nanotechnologies under the 'About' section of the NANOYOU
website (http:/ /www.nanoyou.eu).

The questions of justice related to nanotechnologies are not unique, but rather relevant to many
technology advancements. The history of drug development, and the associate generation of patents
behind commercialized drugs, is definitely filled with questions of justice. Nanotechnologies are enabling
technologies with applications in many sectors, which promise to improve the quality of life of individuals
in numerous ways. For this reason, the questions of justice are even more important and vast.

32 NANOTECHNOLOGIES: PRINCIPLES, APPLICATIONS, IMPLICATIONS AND HANDS-ON ACTIVITIES

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More information, including videos, on the issue of Divide (Justice)

implications of nanotechnology is available on the timefornano project
page (http://www.timefornano.eu/divide).

Early diagnostics

Diagnostic nanosensors allow the early detection of various diseases, such as cancer, at the very onset of
the symptoms, before the disease is perceived by the patient (see Module 2, Chapter 1: Medicine and
healthcare. Early detection means a higher chance of successfully treating and overcoming the disease.
On the other hand, some worry that this will give doctors access to a large amount of personal information.
The question is: Where is this information going to be stored, and who will have access to it? Furthermore,
what if those devices are used not as a diagnostic tool but as a mean to assess a per son's medical
condition by other entities, such as insurance companies or job agencies? Clearly, these devices open
questions of privacy data use and possible misuse.

Some early diagnostic devices already exist, such as genetic screening devices. Nanotechnology is directly
involved in the development of more powerful diseases and precise genetic screening devices, which, at
present, are only available for a small range of common and are fairly imprecise. In genetic screening, the
doctor gathers information on the genetic predisposition a patient has to a certain disease. Scientists already
know that the evolution of a disease does not only depend on genetic pre disposition but also on the diet
followed by the patient, the lifestyle and the environment in which they live. So the question is: Does having
a predisposition to a disease make a person 'ill'? When does 'ilness' start? And even more: Do we want
to know this kind of information?

NANOYOU
ROLE-PLAYING
DILEMMA MORE INFO…
GAMES and VIRTUAL
DIALOGUE TOPIC
Nanosensors in medical Should nanosensors be used to diagnose Module 2, Chapter 1:
diagnostics medical conditions in the early stages Medicine and healthcare
when there are still no definite restrictions
in place to protect patients' privacy?

More information, including videos, on the issue of Health implications of

nanotechnology is available on the timefornano project page (http://
www.timefornano.eu/health).

More than 'human'?

Humans have always tried to their health status and lifestyle: nowadays, there are numerous drugs and
medical technologies that can treat conditions that only a few decades ago were deadly. But, medical
advancements have not just been limited to the treatment of disease: the reconstruction of injured body
parts is now possible though innovative biomaterials and implants, and tissue engineer ing is opening up
the possibility to recreate organs from cultures of stem cells. Nanotechnologies are already playing an
important part in modern medical diagnosis and treatment technologies, and are opening new venues for
future developments.

MODULE 1: FUNDAMENTALS 33
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Many technologies we have today allow doctors to restore a loss sustained as a consequence of an
injury or a congenital condition (eg vision or hearing impairment). Some would argue that this is already
'unnatural', in the sense that it gives humans a capacity that they would not otherwise have.
If you think about it, even glasses provide people who have poor vision a capacity they would not have
naturally. Today, we also have access to treatments that alter our natural appearance through plastic
surgery. In the future, researchers think it might be possible to create implants that allow humans to
have additional skills, such as being able to see in the dark, or have implants that can improve human
brain capacities. Neuroprosthetics are another example. Bioengineers and medical engineers say that
their role should be to compensate for a body's deficit (as result of an accident or a disease), not to
replace any existing function. It should not lead to the enhancement of human capabilities.
however, nanotechnologies are making these developments more feasible and affordable, obliging
researchers in the field, as well as regulators, ethicists and sociologists to reflect on the social, medical and
ethical consequences of these devices (see Module 2, Chapter 1: Medicine and healthcare ).

Nanotechnologies are involved in those medical advancements, as are genetic engineering and biotech
nology. So the question becomes: Are these developments leading to treatments that surpass being
'human'?

NANOYOU
ROLE-PLAYING
DILEMMA MORE INFO…
GAMES and VIRTUAL
DIALOGUE TOPIC
Want to be superhuman? Is it acceptable to use Module 2, Chapter 1:
processes developed for Medicine and healthcare
medical treatment to enhance
the human body?

Improving human brain Is it ethically acceptable to use Module 2, Chapter 1:

capacities technologies developed for Medicine and healthcare
specific medical treatments
for other purposes such as
improving human capabilities?

More information, including videos, on the issue of Enhancement

implications of nanotechnology is available on the timefornano project
page (http://www.timefornano.eu/enhancements).

Nanotechnologies in consumer products

In 2006, the Project on Emerging Nanotechnology (Woodrow Wilson International Center for Scholars)
started compiling a nanotechnology consumer products inventory with the intention of collecting,
archiving and sharing information on consumer products which producers claim to be nano. About 200
products were identified in March 2006: after little more than one year, this number had more than
doubled. At the time of writing (August 2010), the inventory has more than 1 100 products listed.

34 NANOTECHNOLOGIES: PRINCIPLES, APPLICATIONS, IMPLICATIONS AND HANDS-ON ACTIVITIES

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Products in this inventory are categorised on their (explicit) application, specifically: Appliances;
Automotive; Goods for Children; Electronics and Computers; Food and Beverages; Health and Fitness;
Home and Garden. Although the project aims at identifying true nano products, the inventory curators
clearly state 'we have made no attempt to verify manufacturers' claims about the use of nanotechnology
in these products, nor have we conducted any independent testing of the products'.
Therefore, the inventory contains products that claim to be enabled by nanotechnologies, but this is not
checked nor demonstrated. For this reason, one should be cautious when looking at this list, and
should also remember the following.

1. There are a large number of nanocharacteristics that could be included in a consumer product,
such as a coating (thin coatings and layers in the nanometre range, either applied to the
material or formed on use) or a nanomaterial (eg nanotubes, nanoparticles ). Furthermore,
nanotechnology could be used to produce the consumable without being responsible for its
final characteristics: in this case, nanotechnology is only the enabling technology for production.
2. Technical, detailed information regarding these consumer products is often limited due to
corporate security.

To date, the majority of products listed belong to the 'Health and Fitness' group, among which cosmetics
and textiles represent the majority of products.

Among the materials claimed to be responsible for the nanolabel, silver is the most common material mentioned,
followed by carbon (which includes fullerenes), zinc (including zinc oxide), silica, titanium (including titanium
dioxide) and gold.

Safety of nanomaterials
The safety of nanomaterials has become a crucial question in the last few years, especially as the number of
consumer products containing them has been rising every year.

The fact that nanomaterials, by definition, are materials that have a size comparable to biomolecules (eg
proteins, DNA) raises the question of their safety. Could nanomaterials interact with biomolecules in an adverse
manner, triggering a toxic effect? Could nanomaterials pass protection barriers in cells? In nanomedicine, as we
will see in Module 2, Chapter 1: Medicine and healthcare, nanomaterials are precisely used to target infected
cells and deliver agents locally. They are designed to pass though cell membranes, for instance. The question
of toxicity extends also to ecotoxicity: What happens when materials containing nanoparticles reach landfills and
degrade? Will nanomaterials be dispersed in the environment? In what dose? Could this cause harm to systems?

It would be incorrect to say that we know nothing about the toxicological properties of nanomaterials.
In the last years, a wealth of information has been collected and reported by authoritative research
groups. What it is not clear is how relevant these results are for humans, since tests have so far been
practiced in animal models or in vitro. Another problem is that different testing methods are used in
different laboratories, making it difficult to compare results. Research so far has mainly focused on two
groups of materials: carbon-based nanomaterials (carbon nanotubes and fullerenes) and metal or metal-
oxide nanoparticles (eg ultrafine titanium dioxide, TiO2 ). Several studies seem to indicate that some
forms of carbon nanotubes show pulmonary toxicity and that this depends on the production method
and the length and surface properties of the carbon tubes. similarly, TiO2 has been reported to cause
inflammation in the lungs when inhaled in high doses.

MODULE 1: FUNDAMENTALS 35
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Scientists recognize that before a full assessment of nanomaterial toxicity can proceed, some fundamental
issues need to be resolved.

• The need for a definition of nanomaterial is crucial. It is not just a matter of nomenclature; it
is, more important, a matter of defining what 'cut size' should be considered in nanotoxicology.
It is a common belief among toxicologists that the conventional scale 1–100 nm now used to
define a nanomaterial in nanotoxicology is not exhaustive, as nanomaterials often aggregate
or agglomerate in larger particles with dimensions ranging from hundreds of nanometres to
microns. • The reference materials must be defined. Scientists have reported how the same
nanoma terial (eg nano-sized TiO2 ) purchased from two different manufacturers can give
strikingly different toxicological results when tested. In order to define reference materials,
they need to be fully characterised, which means deciding what standard measuring
methods to use (or, possibly, developing new ones, if the existing ones prove inappropriate).
•
It is important to test materials pure and free from contaminations. For instance, carbon nanotubes
are commonly contaminated with iron due to their manufacturing process. Scientists report that the
removal of the iron from the carbon nanotube moiety significantly reduces the oxidant generation and
the cytotoxicity (ie toxicity to cells) of the material. The hypothesis is that it is the nano metal oxide —
rather than the carbon nanotube — that generates the reactive oxygen species 8, responsible for the
toxic effect.
• The medium used to disperse the nanomaterial during the toxicological testing is crucial. It has
been reported how fullerenes are best dispersed in calf serum, whereas they cannot be
dispersed at all in water. Lack of dispersion can lead to false results or confused toxicological
results: therefore, it is essential that dispersion media are defined for each nanomaterial to be
tested.

Overall, the scientific community agrees that progress has been made in the toxicological evaluation of
nanomaterials. There is still much research to be done, but some key matrices have been identi fied — for
example that surface area is a more important parameter than mass when dealing with engineered
nanoparticles, and some targets and common behaviors have been also identified. The question is now how
to make a risk assessment framework from these data, how to convert scattered numbers collected in
numerous laboratories around the world into a risk management strategy for the safe handling of nanomaterials.

Before a risk management for nanotechnologies can be developed and implemented, a funda
mental question needs to be answered: What is the real risk of nanotechnologies? Currently,
nanotechnology is an umbrella term that covers a very large number of materials, applications and
instrumentations. There is a need to classify nanotechnology applications and nanomaterials. This also
applies to the risk debate: the starting point for this debate is to identify the real safety concerns of
nanomaterials. Now, while there is, at times, hype in describing the benefits of nanotechnology, there
is also hype in the associated risk debate. The starting point should be to identify the safety concerns
that are peculiar to nanotechnologies and to identify the key safety needs in spe cific areas of
applications. This will allow us to move from a rather uncoordinated and scattered toxicological
assessment of nanomaterials to coordinated research and cooperation between different institutions.
Precisely for this reason, it is now preferred to use the plural (nanotechnologies) rather than the singular
(nanotechnology) in discussing these matters.

The second question to be answered is: How are engineered nanoparticles (ENPs) different
from non-intentionally-made nanoparticles (also called nanopollutionor ultrafine particles)?
Nanopollution is already a reality in many workplaces, from the welding industries to paint shops and bakeries.

36 NANOTECHNOLOGIES: PRINCIPLES, APPLICATIONS, IMPLICATIONS AND HANDS-ON ACTIVITIES

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Nanoparticles are produced by aeroplane and motor vehicle exhaust emissions, erosion of man-made
materials (eg tyres), as well as by natural erosion and volcanic activity. Humans are already
exposed to nanopollution in many ways and to different degrees. In the workplace, there are
already some effective protective measures for workers exposed to ultrafine particles (filters, textiles,
gloves). There is some evidence that established measures against ultrafine particles would also be
protective against ENPs, should these be classified as hazardous. So the question becomes: Are
ENPs new hazardous materials and, if so, do these pose a risk for humans and/or the
environment? Is this risk different to 'nanopollution', and, if so, how and what should be done to deal
with it? This is a complex question, one that will need time to be fully answered. Basically, at the
moment, there is not enough data to provide an exhaustive answer and more research is needed
(and being undertaken). But the risk associated with any material depends on the exposure route
and dose, so research is also focusing on developing some measuring tools capable of detecting
and distinguishing the presence of nanoparticles in the environment, regardless of their source.

Research into the potential toxic effects of nanomaterials is now a priority in most funding institutions and
agencies, as it is clear that the success of nanotechnologies will also depend on how the issue of safety is
handled.

As a priority, particular attention is given to silver, titanium dioxide and silica nanoparticles and carbon
nanotubes, since it appears that these are the nanomaterials mostly used in consumer products.
For more information on these nanomaterials, their properties and uses, see Module 1, Chapter 5:
Overview of nanomaterials.

NANOYOU
ROLE-PLAYING
DILEMMA MORE INFO…
GAMES and VIRTUAL
DIALOGUE TOPIC
Antibacterial socks Is it right to sell antibacterial Module 2, Chapter 2:
socks containing silver Environment
nanoparticles while it is not
known yet if these are entirely
safe for the environment?

Nano toothbrush Will the prolonged use of Module 2, Chapter 2:

the toothbrush cause the Environment
degradation of its material
and the accidental release of
nanoparticles into saliva, and
if this could have negative
health effects?

Nanotechnology in food Should nanoparticles be used Module 2, Chapter 2:

packaging in our food or pharmaceutical Environment
packaging to detect freshness
when we still do not know the
full ramifications of the using
them?

MODULE 1: FUNDAMENTALS 37
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Boat coating Nanoparticles in the coating Module 2, Chapter 2:

could break down and pollute Environment
the ocean waters.

Pioneering cancer therapy with Should gold-coated Module 2, Chapter 1:

nanoparticles nanoparticles be used to Medicine and healthcare
treat patients' bodies before
possible health risks have
been explored?

Sunscreens with nanoparticles Nanoparticles of TiO2 Module 1, Chapter 4:

contained in sunscreens could Fundamental 'nano-effects';
penetrate through the skin and Module 1, Chapter 5: Overview
produce detrimental health of nanomaterials
effects?

Revolution for the light bulb Quantum dots (QD) integrated Module 2, Chapter 2: Energy
in light-emitting devices
(QD-LEDs) could be toxic or
ecotoxic once these devices
are disposed.

Nano-based solar cells Nanomaterials inside Module 2, Chapter 2: Energy

photovoltaic cells could be
toxic or ecotoxic once these
devices are disposed of.

More information, including videos, on the issue of Environmental

implications of nanotechnology is available on the timefornano project
page (http://www.timefornano.eu/environment).

38 NANOTECHNOLOGIES: PRINCIPLES, APPLICATIONS, IMPLICATIONS AND HANDS-ON ACTIVITIES

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APPENDIX

In this Appendix, some ideas are provided for teachers to use to encourage students to reflect on
other innovative technologies with which they are familiar and that have had important ELSA and
safety implications.

• Automotive transportation: cars and motor vehicles have certainly improved our lives by giving
us the opportunity to move freely, save time in travel, and explore new places. However, pol
lution produced by fuel combustion is, in part, responsible for the global environmental issues
that we are facing now. In addition, transportation has mostly benefited industrialized nations:
poor countries lack the infrastructure (metalled roads) in most cases, and people cannot afford
these commodities. In our society, we have become extremely dependent on cars, especially
for short trips, when alternative transport solutions exist but are not so convenient and easy
(public transport, bicycles). In recent years, there has been a general call from health advisors
and environmental organizations to reconsider the way we use cars, and to favor other means
of transportation that pollute less and render us physically more active.
• Synthetic plastics: about 100 years ago synthetic plastics like Nylon® where created. Plas tics
have revolutionized fabrication processes and enabled a massive production of affordable
consumable goods. Nowadays, nearly all tools we use and have around us are made of plas
tic: laptops, iPods, packages, shoes, cars, etc. Being artificial, these polymers do not degrade
naturally (as opposed to the biopolymers used in biodegradable plastics). The consequence is
that they pose a tremendous challenge when it comes to disposal. Indeed, plastics are one of
the most important pollution agents in the water and on land. The problem of plastic toxicity is
widespread and also involves humans: research is now showing that numerous chemicals used
in plastics are toxic to humans and possibly carcinogenic. however, the world as we know it
would not exist without plastics.
• The Internet: our society has been enormously changed with the advent of the Internet. This tool
was invented to allow research centers around the world to communicate and exchange
information easily. Today, the Internet is an unlimited source of information for everyone and,
more recently, it has become a new form of social communication and networking. Imagine what
would happen if the Internet were to shut down This tool…also plays an important role politically:
bloggers in war areas are able to communicate what is really happening. Socially, the Internet is
reshaping the way people communicate, some even say too much. Experts are concerned that
youngsters use the Web as their primary communication channel, and that per sonal, face-to-
face communication is progressively being lost. There are concerns that an abuse of this form
of communication could deprive youngsters of personal encounters, considered essential for
personality development.

MODULE 1: FUNDAMENTALS 39
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CHAPTER 2:

NANOSCIENCE IN NATURE
This chapter introduces the concept of 'natural nanomaterials' and illustrates in some detail a few examples that can be
introduced in the classroom.

What is a
natural nanomaterials?
All materials can, in principle, be described at the nanoscale. In this text, by 'natural nanomaterials' we
mean materials that belong to the natural world (animal and mineral), without human modification or
processing, and that have remarkable properties because of their inherent nanostructure.

The chemical identity and properties of a substance depend upon its molecular structure. The nano
structure of a biological material is due to its supramolecular organization — the arrangement of tens
to hundreds of molecules into shapes and forms in the nanoscale range. The interaction of light, water
and other materials with these nanostructures gives the natural materials some remarkable properties
which can be appreciated at the macroscale.

Natural nanomaterials provides an inspiring way of bringing nanoscience into the classroom.
Many natural materials, with which students will be very familiar, owe their properties to nanostructures in their composition.
It can be really enlightening to discover that common, natural materials, such as feathers and spider silk, or materials that
we use every day, such as paper and clay, have properties that depend not only on their chemistry but also on their
nanostructure.

Overview of natural nanomaterials

We see hundreds of examples of nanoscience under our eyes daily, from geckos that walk upside
down on a ceiling, apparently against gravity, to butterflies with iridescent colours, to fireflies that glow
at night. In nature, we encounter some outstanding solutions to complex problems in the form of
fine nanostructures with which precise functions are associated.

A short list of some natural nanomaterials follows: it is not exhaustive, but the interested teacher can
find more information in the bibliography at the end of this module.

• Nanoparticles from natural erosion and volcanic activity: nanoparticles are part of our mineral
world since they are naturally produced during erosion and volcanic explosions. •
Minerals, such as clays, are nanostructured: clays are a type of layered silicate characterised by
a fine 2D crystal structure. Among clays, mica has been the most studied. Mica is made up of
large sheets of silicate held together by relatively strong bonds. Smectic clays, such as
montmorillonite, have relatively weak bonds between layers. Each layer consists of two sheets
of silica held together by cations such as Li+ , Na+, K+ and Ca2+. The presence of the cations is

MODULE 1: FUNDAMENTALS 41
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necessary to compensate for the overall negative charge of the single layers. The layers are 20–
200 nm in diameter laterally and form into aggregates called tactoids, which can be about 1 nm
or more thick. Naturally occurring clays include montmorillonite (MMT) and herite. The fine
nanostructure of clays determines their properties. When water is added, the clay swells, but
the volume change is rather unusual — it is several times the original volume due to the
'opening' up of the layered structure by the water molecules that replace the cations. Clay
swelling is a significant factor in soil stability and must be taken into account when building
roads etc.
• Natural colloids, such as milk and blood (liquid colloids), fog (aerosol type), gelatin (gel type): in
these materials, nanoparticles are dispersed in the medium (liquid or gas) but do not form a
solution, rather a colloids. All these materials have the characteristic of scattering light and
often their color (as in the case of blood and milk) is due to the scattering of light by the
nanoparticles that make them up.

EXPERIMENT A in the NANOYOU Experiment Module investigates nat

ural colloids (milk and gelatin) and how their properties are connected to
their nanostructure. A gold colloid is the subject of EXPERIMENT C in
the NANOYOU Experiment Module.

• Mineralised natural materials, such as shells, corals and bones: many of these materials are
formed by calcium carbonate crystals that self-assemble together with other natural materials,
such as polymers, to form fascinating three-dimensional architectures. For instance, a shell is
grown by a layer of cells that first lays down a coating of protein supported by a polysaccharide
polymer like chitin. The proteins act like a nano-assembly mechanism to control the growth of
carbon carbonate crystals. Around each crystal remains a honeycomb-like matrix of protein
and chitin. This relatively 'flexible envelope' is fundamental for the mechanical properties of the
shell and mitigates cracking. The size of each crystal is around 100 nm. The result is that the
nacre of mollusc shells has extraordinary physical properties (strength, resistance to
compression, etc.). • Materials like skin, claws, beaks, feathers, horns, hair: these materials
are made significantly of very flexible proteins like keratin, elastin and collagen. Keratins have
a large glycine and alanine content. This leads to ÿ-sheets that can bond strongly one with
another in an aligned fashion. Fibrous keratin molecules can twist around each other to form helical intermedia
filaments. similarly, collagen (not related to keratin in terms of primary structure) has a high
percentage of glycine and forms flexible triple-helix structures. In addition to intra and inter
molecular bonds, keratins have numerous cysteines that can form stable disulphide bonds. The
amount of cysteines in the protein determines the strength and rigidity of the material: keratin in
human hair, for instance, contains about 14% cysteines. Materials like nails, hooves and claws
have a higher percentage of cysteines.
• Paper and cotton: both are made mainly of cellulose. The high strength, durability and
absorbency of cotton are due to the nanoscale arrangement of the fibres.
• Insect wings and opals: the colors seen in opals and butterflies are directly related to their fine
structure, which reveals packed nanostructures that act like a diffraction grid and induce
iridescence. In the case of opals, this is due to packed silica spheres in the nanometre range,
uniform in size and arranged in layers. Butterflies often owe the color of their wings to pig
ments that absorb specific colours; in some species, such as the beautiful Morpho rhetenor,
colors are due to the presence in the wings of nanostructures which are photonic crystals. This
example is discussed in more detail in the next section of this chapter.

42 NANOTECHNOLOGIES: PRINCIPLES, APPLICATIONS, IMPLICATIONS AND HANDS-ON ACTIVITIES

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• Spider silk: silk is the material with the greatest known strength — about five times that of steel of
the same weight. The extraordinary properties of spider silk are due to the proteins that make up
the silk (mainly fibroin) and its supramolecular organization which is at the nanoscale level.

• Lotus leaves and similar (nasturtium): the nanostructure of the leaves of these plants is
responsible for their exceptional surface properties and their ability to 'self-clean'. This example
is discussed in more detail in the next section of this chapter. • Geckos'
feet: the structure of the gecko foot is an amazing example of the relationship between function
and nanostructure. The ability of geckos to walk upside down, against gravity, even on wet or
dirty surfaces, is intimately connected to the nanostructure of their feet. This example is also
discussed in more detail in the next section of this chapter.

Learning from nature

Natural nanomaterials are of interest not only to understand (and appreciate) the amazing proper
ties of biological materials but also to gather inspiration for the design and engineering of new
materials with advanced properties.

The physical origins of the remarkable properties of many biological materials are due to complex,
often hierarchical structures ( 3). They are characterised by a surprising level of adaptability and
multifunctionality. These materials can provide a model for designing radically improved artificial
materials for many applications, such as solar cells, fuel cells, textiles, drug delivery systems, etc.

What is even more inspiring is the notion that in nature, some very simple laws apply.

1. Nature runs on sunlight and uses only the energy it needs. Natural nanomaterials are extremely
energy efficient!
2. Nature fits form to function and recycles everything — waste products are minimised in nature!
3. Nature rewards cooperation although it promotes diversity and local expertise.

The field of materials engineering devoted to trying to fabricate artificial materials that mimic natural ones
is conventionally called biomimetics. Nanoscience is a fundamental component of biomimetics.

Natural nanomaterials are inspirational for the engineering of new mater

ials with advanced functionalities. In Module 1, Chapter 5: Overview of
nanomaterials, some examples are given. A short list of biomimetic
materials inspired by natural ones follows.

(3 ) Hierarchical structures are those structures that are synthesized at different levels of complexity by alternating growth
conditions.

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Biomimetic materials … … inspired from

Polymers Substructure of nacre

Structural elements Wood, ligaments and bone

Electrical conduction Eels and nervous system

Photoemission Deep-sea fish and glow-worms

Photonic crystals Butterfly and bird wings

Hydrophobic surfaces Lotus leaves and human skin

Adhesives Geckos' feet

High tensile strength fibre Spider silk

Artificial intelligence and computing Human brain

Detailed description of some natural nanomaterials

Now, a few fascinating natural nanostructures are described in some detail and how their natural nanostructure is responsible
for their properties (adhesiveness, strength, flexibility, colour, etc.) is explained.

Bone
Thinking about it, the unique properties of bone are a list of apparent contradictions: rigid, but flex ible; lightweight, but solid
enough to support tissue growth; mechanically strong, but porous. Bone can withstand weight without breaking. Its compressive
strength is about twice its tensional strength.
These outstanding properties are the result of bone's complex hierarchical structure and composition: bone material is made
of a composite of collagen (mainly Type I collagen) fibrils reinforced with calcium phosphate particles (hydroxyapatite) (
4 ).

From a mechanical point of view, many bones such as the femoral head can be described as a 'sand wich' structure with a
dense external shell (cortical bone) and a spongy interior (cancellous bone). In cancellous bone, only about 20% of the volume
is filled with bone material, the rest is made of bone marrow. Cortical bone is made of fibrils regularly arranged (Figure 1).

The fibrils consist of an assembly of collagen molecules 300 nm thick which are long by the
osteoblasts (bone-forming cells) into the extracellular space and self-assembled into fibrils. Adjacent
fibrils molecules are staggered along the axial direction by about D = 67 nm (Figure 2), generating
a characteristic pattern of gap zones of length 35 nm and overlap zones of length 32 nm within the
fibril.

(4 ) Hydroxiapatite: Ca5(PO4 ) 3OH.

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Figure 1: (a) Section through a femoral head

showing the shell of cortical bone (C) and the
spongious bone (S) inside; (b) enlargement of the
cortical bone region revealing several osteons (O)
respectively to blood vessels surrounded by con
centric layers of bone material; (c) picture of a
sin gle trabeculum from the spongious bone
region; (d) further enlargement showing the
lamellar and fibrillar material texture around an
osteocyte lacuna (OC) as visible in scanning
electron micros copy (white arrow). The lamellae
are formed by bundles of mineralized collagen fibrils (insert).

Image: Fratzl et al., Journal of Material Chemistry, 2004,

14:2115–23, reprinted with the permission of the Royal
Society of Chemistry

Figure 2: Self-assembly of collagen fibrils: (a) procollagen

molecule after excretion from the cell; (b) collagen after
cleavage of the propeptide ends; (c) parallel self-assembly
with a staggering period of D; (d) periodic density variation
along the fibril axis, resulting from the staggering. In the
stripes labeled O, there is an overlap of all molecules. In
the stripes labeled G (gap region), one molecule in five is
missing and the density is accordingly less.

Image: Fratzl et al., Progress in Materials Science, 2007, 52(8):1263–

334, reprinted with the permission of Elsevier

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Collagen fibrils are filled and coated by tiny mineral crystals of hydroxiapatite. These are mainly
flat plates mostly arranged parallel to each other and parallel to the fibril main axis. Crystals occur at
regular intervals along the fibrils, with an approximate repeat distance of 67 nm. In mammalian
species, bone mineral crystals have a thickness of 2–4 nm (Figure 3).

Figure 3: Sketch of the arrangement

of mineral particles in collagen fibrils.
Mineral particles are typically very
thin objects (2–4 nm) and aligned with
the collagen matrix.

Image: Fratzl et al., Journal of Material Chemistry, 2004, 14:2115–23, reprinted with the permission of the Royal Society
of Chemistry

To summarise, bone is formed from a soft organic matrix (collagen) reinforced by an anisotropic stiff
inor ganic component (crystals of hydroxiapatite). These two components are assembled in a hierarchic
struct ture which is organized at the nanoscale level. It is this nanoscale hierarchic organization that
allows bone to tolerate small microfractures that arise from normal activity and dissolved energy without
propagation of the crack. Hydroxiapatite is a rigid material which is not capable of dissipating much
energy; therefore, collagen is believed to have a major role in the structural properties of bone (elastic
and plastic deformation). Figure 4 illustrates the role of collagen during bone deformation. Older bone,
which is more mineralized and thus has a larger percentage of hydroxiapatite, is stiffer and breaks more easily.

Bone is a 'perfect' nanocomposite and is used as a model for polymer com posites
reinforced with nanomaterials such as carbon nanotubes. Poly mer composites and
their applications are covered in Module 1, Chapter 5: Overview of nanomaterials.

Lotus leaf
The lotus plant (Nelumbo nucifera) is a native Asian plant which has the distinct property of being able
to maintain its leaves particularly clean even if its natural habitat is muddy. For this reason, this plant is
considered sacred in some cultures and a sign of purity. The leaves of the lotus plant have the
outstanding characteristic of totally repelling water because they are superhydrophobic (Figure 5).
The consequence is that water droplet roll off the leaf surface and, in doing so, drag dirt away from it, as shown in Figure
7. This effect, 'self-cleaning', renders the lotus leaf clean and resistant to dirt. The same effect is found in other leaves
such as those of nasturtium (Tropaeolum) and some Cannas, and
in some animals such as the water strider.

How is this 'Nano'?

The surface properties of the lotus leaf were first evaluated by Wilhelm Barthlott. In 1997, he pub
lished an important paper where he described for the first time the 'Lotus effect' (a term that he later
copyrighted) responsible for the self-cleaning properties of the lotus leaves. In his original paper,
Barthlott showed that the self-cleaning properties of the lotus plant are produced by a combination of

forty six
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Figure 4: Schematic model for bone deformation in response to external tensile load at three
levels in the structural hierarchy: at the tissue level (left), fibril array level (centre), and mineralized
col lagen fibrils (right). The stiff mineralized fibrils deform in tension and transfer the stress
between adjacent fibrils by shearing in the thin layers of extra-fibrillar matrix (the white dotted lines
in the center plot show the direction of shear in the extra-fibrillar matrix). The fibrils are covered
with extra-fibrillar mineral particles, shown only over a selected part of the fibrils (red hexagons)
so as not to obscure the internal structure of the mineralised fibril. With each mineralized fibril, the
stiff mineral platelets deform in tension and transfer the stress between adjacent platelets through
shear in the interparticle collagen matrix (red dashed lines indicate shearing qualitatively and do
not imply homogeneous deformation).

Image: Fratzl et al., Progress in Materials Science, 2007, 52(8), 1263–334, reprinted with the permission of Elsevier

Figure 5: Left to right: Lotus leaf; Tropaeolum (nasturtium) leaves; water droplet resting on the
surface of a nasturtium leaf

Image: (left to right) iNANO, Aarhus University, Creative Commons ShareAlike 3.0; Wiki Commons, Creative Commons
ShareAlike 3.0; A. Otten and S. Herminghaus, Göttingen, Germany, NISE Network, reprinted under NISE Network Terms
and Conditions

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the microstructure of the leaves and the epidermal cells on their rough surfaces, which are
covered with wax crystals (Figure 6). These crystals provide a water-repellent layer, which is
enhanced by the roughness of the surface, making it a superhydrophobic surface, with a contact
angle of about 150°. The consequence is that water droplet on the surface tend to minimise the
contact between the surface and the drop, forming a nearlyspherical droplet. Figure 6 shows the
progressive magnification of a nasturtium leaf. In the last image on the right, nanocrystals a few
tens of nanometres in size are shown.

A B C EASY

Figure 6: Close-up views at progressive magnifications of a nasturtium leaf revealing the presence
of surface nanocrystals (image on the far right)

Image: (A) A. Snyder, Exploratorium; (B, C) A. Marshall, Stanford University; (D) A. Otten and S. Herminghaus, Göttingen,
Germany; all images are material of the NISE Network, reprinted under NISE Network Terms and Conditions

The consequence is that water droplet roll off the leaf surface and, in doing so, drag dirt away from it,
as shown in Figure 7. This effect, 'self-cleaning', renders the lotus leaf clean and resistant to dirt.

Contaminants on the surface (generally larger than the cellular structure of the leaves) rest on the tips
of the rough surface and when a water droplet rolls over the contaminant, the droplet removes the
particle from the surface of the leaf (Figure 8).

Figure 7: Diagram summarizing the connection between

roughening and self-cleaning: while on smooth surfaces, the
particles are mainly redistributed by water (bottom); on rough
surfaces, they adhere to the droplet surfaces and are removed
from the leaves when the droplet roll off (right).

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Figure 8: Graphical representation of water droplets on a lotus leaf

Image: William Thielicke, Creative Commons Attribution ShareAlike 3.0

The Lotus effect® has been an inspiration for several innovative

materials, mainly involving self-cleaning properties to reduce the amount
of cleaning needed, with an obvious environmental benefit. This also
includes textiles and is discussed in Module 2, Chapter 2: Environment.
The Lotus effect® is also used in new solarcell covers to increase their
efficiency: this is explored in Module 2, Chapter 3: Energy.

EXPERIMENT D in the NANOYOU Experiment Module investigates the

Lotus effect® in real plants and in innovative materials such as Nano-Tex®
fabric and nanoporous silicon.

A simple hands-on activity to show the superhydrophobic effect involves

magic sand — a product that creates a superhydrophobic assembly in
water. Details of the Magic Sand activity can be found in the timefornano
NanoKIT — Activity 6 (http://www.timefornano.eu/nanokit#ac07).

Gecko

A gecko can cling to virtually any surface at any orientation; walk on smooth or rough surfaces, even
upside down on a glass surface; and walk on a dirty or wet surface maintain full contact and adhe sion
to it. As it walks, a gecko does not secrete any sticky substance, and its feet do not have any suction-
like features (even at microscopic sizes). The reason for the gecko's amazing properties lies in the
nanostructures that are present on its feet.

The gecko foot has a series of small ridges called scanners which contain numerous projections
called setae. Each seta is about 100 µm long and has a diameter of about 5 µm. There are about half
a million of these setae on the foot of a gecko. Each seta is further subdivided into about a thousand
200 nm-wide projections called spatulae (Figure 9). As a result, the total surface area of the
gecko's feet is enormous. The gecko spatulae are very flexible, so they essentially mold themselves
into the molecular structure of any surface. The result is a strong adhesion which is entirely due to
van der Waals forces. A single seta can resist a force of 200 µN, or approximately 10 atmospheres of
stress. The gecko case is thus a very good example of the effect of large surface area on small forces.

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Figure 9: Structural hierarchy of the gecko adhesive system: (A) macrostructure: ventral view of a
Tokay Gecko (Gekko gecko) climbing vertical glass; (B) mesostructure: ventral view of the foot,
with adhesive lamellae (scansors) visible as overlapping pads (note the clean appearance of the
adhesive surface); (C) microstructure: proximal portion of a single lamella, with individual setae in
an array visible; (D and E) nanostructure: single seta with branched structure at upper right,
terminating in hundreds of spatular tips.

Image: (A) Hansen et al., Proceedings of the National Academy of Sciences, 2005, 102(2), 386–9, reprinted with the permission
of the National Academy of Science, USA, © 2005

Another very interesting property of geckos is that their feet don't get dirty as they walk, even if
they walk on a surface covered with sand, dirt, water, etc. Their feet stay clean even on dirty
surfaces and full adhesion is maintained. The phenomenon has been evaluated and it was found
that the feet remain clean because it is more energetically favourable for particles to be on the
surface than to remain adherent to the gecko spatulae. If a gecko walks over a dirty surface, it
takes only a few steps for its feet to be totally clean again, and adhesion is not compromised.

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This self-cleaning property of the gecko foot is now being evaluated

with a view to designing new materials that stay clean and/or can self-
clean, such as 'bio-rubbers'. This is discussed in Module 1, Chapter 5:
Overview of nanomaterials.

Morpho rhetenor
The wings of butterflies often display extraordinary colours, a consequence of the wing surface and its
interaction with light. The wings also exhibit iridescence: the shift in color of an object when observed at
different angles. The effect can easily be seen by observing a music CD.

Iridescence is a 'physical color' and it results from the interaction of light with the physical structure of
the surface. To interact with visible light, those structures must be nano-sized (the visible spectrum
corresponds to wavelengths between 380 and 750 nm). The interaction of light with this nano-rough
surface can lead to constructive or destructive interference. The colour, intensity and angles of
iridescence depend on the thickness and refractive index of the substrate, and on the incident angle
and frequency of the incident light.

In materials like opals, natural iridescence is observed, due to packed silica spheres in the nanometre
range, uniform in size and arranged in layers. This provides appropriate conditions for interference.

In the case of butterflies and moths, the iridescence is produced in a peculiar way. Scientists have stud
ied the structure of the wings of Morpho rhetenor in detail and have found that these are formed by rows
of scales arranged like tiles on a roof. Each scale is about 70 x 200 µm and has a smaller struct ture
on its surface, a very intricate and highly ordered nanometre organization of ridges. Each ridge is about
800 µm wide. The spaces between them form a natural photonic crystal that can generate constructive
and destructive interference. The SEM analysis of the cross-section of the ridges on the wings shows
and an even more intricate structure that looks like fir trees (last image in Figure 10).

Figure 10: Close-up views at progressive magnifications of Morpho rhetenor showing the scales,
which magnified show photonic crystal structures, which in turn show a cross-section displaying
setae that look like fir trees

Image: (far left): Wiki Commons, Creative Commons Attribution ShareAlike 3.0; (all other images): S. Yoshioka, Osaka
University, NISE Network, reprinted under NISE Network Terms and Conditions

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These are called setae, are about 400 nm long, and are responsible for producing constructive
interference in the blue wavelengths which generate the strong blue color (Figure 11).

Figure 11: The blue color of the wings is due to the con
structive interference of light generated by the photonic
crystal in the wings structure

Image: F. Nijhout, Duke University, NISE Network, reprinted under NISE

Network Terms and Conditions

A photonic crystal is a periodic nanostructure that can modify the passage of light. The refractive
indices of the materials that make up the crystal, and the presence of cavities or other defects
determine which frequencies of light can propagate well.

In computing, propagation of light (rather than electrons) is being investi

gated as an alternative to current integrated circuits. Photonics and
photonic crystals in particular are described Module 2, Chapter 4:
Information and Communication Technologies.

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CHAPTER 3:

HISTORY OF NANOTECHNOLOGIES
This chapter provides some historical background to nanotechnologies. A very valid question that
students might bring up in class, and that we attempt to answer, is 'When was nanotechnology
invented?' As discussed in Chapter 1, nanotechnologies are an evolution of other materials engineering
disciplines (eg thin-film technology). The term is really an 'umbrella' term that covers disciplines that
have very old historic roots. What is even more fascinating is that now scientists have the tools to study
ancient artefacts, they have found that, in many cases, these were made using nanoparticles!
Nanotechnologies are around us in nature (Chapter 2) and in history!

Feynman's speech

The concept of nanotechnology is attributed to Nobel Prize winner Richard Feynman who gave a very
famous, visionary speech in 1959 (published in 1960) during one of his lectures, saying: “The principles
of physics, as far as I can see, do not speak against the possibility of manoeuvring things atom by
atom”. At the time, Feynman's words were received as pure science fiction. Today, we have instruments
(see the following section) that allow precisely what Feynman had predicted: creating structures by
moving atoms individually.

Scanning tunneling microscope

The development of nanotechnologies has been enabled by the invention of two analytic tools that have
revolutionized the imaging (and manipulation) of surfaces at the nanoscale. These are the Scanning
Tunnelling Microscope (STM) and the Atomic Force Microscope (AFM). The STM and the AFM are
capable of imaging surfaces with atomic resolution.

The operation principle of the STM and AFM and their use for surface
imaging and surface manipulation are described in Module 1, Chapter 6:
Characterisation methods.

Both instruments were invented by Binning and his co-workers at IBM Zürich. Binning, Rohrer and
Ruska (all at IBM Zürich) were awarded the Nobel Prize in Physics in 1986 for the invention of
these amaz ing tools, which, practically, opened the doors of the nano-world to science. With the
advent of the STM, scientists were given the tool not only to image surfaces with atomic resolution,
but also to move individual atoms. The STM is the first step in realising Feynman's vision of atom-by-
atom fabrication.

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Colored glass
Metal colloids (metal nanoparticles dispersed in a medium) are the best example of nanotechnology
throughout ancient, medieval and modern times. In Chapter 4, it was seen how metal nanoparticles
possess optical properties (ie different colours) that are related to surface plasmons. The size and
shape of the metal nanoparticles influence their visible colours! There are numerous artefacts that have
notable color effects precisely because they are made with metal colloids.

• One of the most fascinating is a piece of Roman glasswork, the Lycurgus cup, dating from
the fifth century. This magnificent cup, housed at the British Museum, depicts King Lycurgus
dragged into the underworld by Ambrosia. When illuminated from the outside, the cup appears
green. When illuminated from the inside, the cup appears ruby-red except for the King, who
looks purple. The reason for this dichroism was unknown until detailed SEM analysis of the
cup was performed in 1990. It was found that it was due to the presence of nano-sized
particles of silver (66.2 %), gold (31.2 %) and copper (2.6 %), up to 100 nm in size, embedded in the glass.
Light absorption and scattering by these nanoparticles determine the different colours. •
The beautiful stained glass windows produced in medieval times, and visible in numer ous
churches, are made of a composite of glass and nano-sized metal particles. The 'ruby-red'
glasses are often seen are a mixture of glass with ultrafine (nano-sized) gold powder. The
'purple of Cassius' is a colloidal mixture of gold nanoparticles and tin dioxide in glass.
• Chinese art history is also filled with examples of nanotechnology. For instance, the Chinese
known as family rose contains gold porcelain nanoparticles 20–60 nm in size.

Faraday's studies on gold colloids

If we look into the history of science, gold colloids have been the subject of research since the mid 19th
century! It was actually Michael Faraday who was the first to conduct systematic studies on the
properties of metal colloids, in particular gold. In 1857, during his lecture at the Royal Society of
London, Faraday presented a purple-colored slide, reduced that it contained 'gold in exceedingly fine
particles, which became diffused, produce a ruby-red fluid … the various preparations of gold, whether
ruby, green, violet or blue … consist of that substance in a metallic divided state'.

Faraday postulated correctly about the physical state of colloids; he also describes how a gold
colloid would change color (to blue) when salt is added.

This effect is shown in Experiment C in the NANOYOU Experiment Module.

Teachers have an opportunity to link this experiment with some concepts of
science history.

In the early 20th century, Gustav Mie presented the Mie theory, a mathematical treatment (to which
we still refer) of light scattering that describes the relationship between colloid-sized metals and the
optical properties of solutions containing them.

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Miniaturized electronics

Youngsters are surrounded by electronic devices — computers, mobile phones, portable electronic
games, etc. It is really amusing to see their reaction when we show them pictures of the first mobile
phones introduced in the 1980s! We (and, even more, they) take for granted the miniaturisation of
electronic devices, and are used to expecting even more every year or so. The evolution of this
miniaturisation has been brought about by the tremendous advances in the semiconductor industry and
the ability to produce smaller and smaller integrated circuits (ICs). The 'core' of ICs is the transistor —
every chip is made of numerous transistors that act like gates for the flow of electrons: they can be in the open or closed
Just to paint to picture, in 1965, 30 transistors populated a chip; in 1971, there were 2 000; and, today,
there are about… 40 million! This exponential growth was actually predicted in 1965 by Gordon E. Moore
(co-founder of Intel Corporation). Moore predicted that the 'complexity of integrated chips' would double
every 18 months. At the time he was a visionary … but, indeed, Moore's law proved to be right. The data
density of computer chips has increased in the last years at the predicted pace doubling every 18 months.

TIP FOR TEACHERS: Ask your students to go home and collect information on old computers or
laptops owned by their parents, friends or relatives. Ask them to record when they were purchased
(approximate date of production), and what was the data storage capacity (hard disc capacity). Make
an overall table with the information collected by all the class. Is Moore's law confirmed?

The history of integrated chips is, in a sense, the history of nanotechnology. The first transistor
invented in 1947 was a bulk, macro object (Figure 1). To keep up with the demand for miniaturisa
tion, the dimensions of the transistor have been reduced considerably over the last 20 years. In 2002,
the nano-size was reached and a single transistor was 90 nm. As of today (end of 2009), a single
transistor in an Intel® Core™ 2 Quad processor is 45 nm.

Figure 1: Replica of the first bipolar transistor, this replica was

photographed at the Nixdorf-Museum, Paderborn, Germany.

Image: Wiki Commons, Creative Commons Attribution ShareAlike 3.0

If they were to keep pace with Moore's law, transistors would have to be as small as 9 nm by
2016. This dimension is below the fabrication capabilities of the latest-generation tools used in the
microelectronics industry. Moreover, at this dimension, electrons would be able to 'jump' the gate
just with their own thermal energy. Numerous novel approaches are under investigation to realise
work able transistors of this size. These include molecular electronics and quantum computing —
both are examples of true nanotechnologies.

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The fabrication techniques used in the microelectronics industry are

reviewed in this Module, Chapter 7: Fabrication methods. The future
evolution of computing and the impact of nanotechnologies are discussed
in Module 2, Chapter 4: Information and Communication Technologies.

The GMR effect

Numerous popular electronic products, such as the iPod, have components that use an effect called
giant magnetoresistance (GMR). In simple terms, the electrical resistance of structures made of
very thin layers of magnetic and non-magnetic metals can change by an unexpected large
amount in the presence of an applied magnetic field. The effect was discovered independently by
Albert Fert and Peter Grunberg in 1988 and, for its discovery, they shared the 2007 Nobel Prize in Physics.
When the prize was announced, the Swedish Academy of Science wrote: 'GMR technology may also
be regarded as one of the first major applications of the nanotechnology that is now so popular in a very
diverse range of fields.'

The GMR effect is a true nano-effect! GMR is used in the latest-generation

memory devices like the MRAM. The details of the GMR effect are
described in Module 2, Chapter 4: Information and Communication Technologies.

Advanced materials

The history of materials engineering is full of examples of nanomaterials! Often, these were pro
duced inadvertently and not characterised at the nanoscale as many of the analytic tools used today
were not yet available. For instance, the process of anodising was first patented in the early 1930s.
This represents one of the most important processes used in industry to protect aluminum from cor
rosion. It consists of depositing a thin oxide protective layer on the aluminum surface. The inventors of
this technique were not aware that the protective layer is actually a nanomaterial — the anodic layer
is composed of hexagonally close-packed channels with diameters ranging from 10 to 250 nm or greater.

Other familiar examples are: nanoparticles that are found in the rubber component of car tyres; titanium
ium dioxide pigment found in some of the latest-generation sunscreens; components in computer chips;
numerous synthetic molecules used in current drug compositions; thin, hard coatings used in industry.

There are many nanomaterials that have a long history: not all can be reviewed here, so the discussion
will be limited to two examples.

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Fullerenes and carbon nanotubes

In 1985, RE Smalley, HW Kroto and RF Curl discovered a new form of the element carbon: the
buckyball, a molecule consisting of 60 atoms of carbon (C60) assembled in a form similar to a football
(Figure 2). The researchers were then able to develop a method to synthesise and characterise this
new nanomaterial. The existence of C60 had actually been predicted by Eiji Osawa of Toyohashi Uni
versity of Technology in a Japanese magazine in 1970. This new allotrope of carbon was officially
named Buckminsterfullerene in honor of Buckminster Fuller, an architect famous for his geodesic dome
design. shortly after the discovery in 1985, various others fullerenes were discovered.

Figure 2: Left to right: a geodesic dome designed by architect Buckminster Fuller, the structure of
C60 and a football.

Image: Wiki Commons Images, Creative Commons Attribution ShareAlike 3.0

In 1996, Kroto, Curl, and Smalley were awarded the 1996 Nobel Prize in Chemistry for their roles in
the discovery of this class of compounds.

The properties and applications of fullerenes and their parent nanomaterial

carbon nanotubes are described in detail in Module 1, Chapter 5: Overview
of nanomaterials.

Liquid crystals
Liquid crystals were first accidently discovered in 1888 by Friedrich Reinitzer, a botanical physiologist
who was working in the Institute of Plant Physiology at the University of Prague. Reinitzer was
conducting experiments on a cholesterol-based substance (cholesteryl benzoate) and trying to
determine the correct formula and molecular weight of cholesterol. When he tried to precisely determine
the melting point, which is an important indicator of the purity of a substance, he was struck by the fact
that this substance seemed to have two melting points. He found a first melting point at 145.5 °C, where
the solid crystal melted into a cloudy liquid. This 'cloudy intermediate' existed up to 178.5 °C where the
cloudiness suddenly disappeared, giving way to a clear transparent liquid. At first, Reinitzer thought that
this might be a sign of impurities in the material, but further purification did not show any changes

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in this behaviour. He concluded that the material had two melting points, but asked his colleague Otto
Lehmann, a German physicist who was an expert in crystal optics, for help in understanding this unex
pected behaviour. They isolated and analyzed the 'cloudy intermediate' and reported seeing crystallites.
Lehmann then conducted a systematic study of cholesteryl benzoate and other solids that displayed the
double melting behaviour. He became convinced that the cloudy liquid had a unique kind of order. It
could sustain flow like a liquid but under the microscope appeared like a solid. In contrast, the transpar
ent liquid at higher temperature had the characteristic disordered state of all common liquids. Eventu
ally, he realised that the cloudy liquid was a new state of matter and coined the name 'liquid crystal,' to
emphasize that it was something between a liquid and a solid, sharing important properties of both.
Not just a liquid, where molecules are randomly distributed, and not just a solid, where molecules are
ordered in organized structures.

TIP FOR TEACHERS: The discovery of liquid crystals is a good example of how science often proceeds
(ie with a discovery made by mistake that is then further evaluated (rather than just dismissed as an
error)). In fact, many major scientific discoveries were made this way. An educator may take this
opportunity to demonstrate to the class other scientific discoveries that were the result of an accidental
discovery, followed by the studies of long-sighted scientists who pursued the scientific meaning of the
'accident' (another great example is the discovery of penicillin).

The scientific community challenged the conclusions of Reinitzer and Lehmann since, at that time,
scientists knew only three states of matter: gas, liquid and solid. The general idea was that all matter
normally had one melting point (where it turns from solid to liquid) and a boiling point (where it turns
from liquid to gas).

however, the work done by Lehmann was continued at the beginning of the 20th century, but liquid
crystals were treated by the scientific community as a pure scientific curiosity. Only later did scientists
realise that these materials were indeed a fourth state of matter and could actually have commercial
use. In 1969, Hans Kelker succeeded in synthesizing a substance that had a nematic phase at room
temperature, the N-(4-methoxybenzylidene)-4-butylaniline (MBBA) molecule. Later, other chemically
stable substances (cyanobiphenyls) with low melting temperatures were synthesised: these materials
opened the doors to the use of liquid crystals in practical applications such as displays. Since these dis
coveries, research on these materials has increased and in 1991 Pierre-Gilles de Gennes received
the Nobel Prize in Physics 'for discovering that methods developed for studying order phenomena in
simple systems can be generalized to more complex forms of matter, in particular to liquid crystals and
polymer'.

Now it is known that the peculiar properties of a liquid crystal depend on how external factors, such as
electric field or temperature, change its phase results in a rearrangement of its supramolecular
nanostructure.

Nowadays, liquid crystals are used for many applications, mainly in the ICT
sector, such as in mobile phone displays. Liquid crystals are described in
detail in Module 1, Chapter 5: Overview of nanomaterials and their
applications are discussed in Module 2, Chapter 4: Information and
Communication Technologies.

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In EXPERIMENT B of the NANOYOU Experiment Module, students

prepare different types of liquid crystals that change phase with temperature
and, as a consequence, change colour. Students can make a room
thermometer with four different types of liquid crystals.

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CHAPTER 4:

FUNDAMENTAL 'NANO-EFFECTS'
Nanoscience is often referred to as 'the science of small'. The question we address in this chapter is:
Why does size matter? What is so special about nano-sized materials? How are their properties
different from those of 'conventional' bulk materials? Here, a complete review of the topic, which would
involve an in-depth review of quantum physics, cannot be provided, but some fundamental aspects of
nanosci ence that are essential to understanding the exceptional properties of nanomaterials are highlighted.
Rather than focusing on the theory behind these effects, the focus is on the implications that
these effects have on the properties of materials.

What happens at the nanoscale?

The macroscopic physical properties of a substance (melting point, boiling point, conductivity, etc.) are
determined by studying a pure sample in quantities big enough to be measured under normal labora
tory conditions . One mole of any material contains 6,022 x 1023 molecules; one mole of water, for
instance, weights 18 g. Therefore, when the boiling point of one mole of water is determined, in reality
the value which is obtained an average value based on the behavior of billions and billions of molecules
of water; we assume that the result should be true for any size of group of water mol ecules. This is
not correct for many materials: as the size of the material is reduced, and the nanoscale level is
reached, it is possible that the same material will display totally different properties (different melting
point, conductivity, etc.). This is because matter at the nanoscale no longer follows Newtonian physics
but rather quantum mechanics.

In other words, the properties of materials can be size-dependent. This might be a rather new
concept to bring into the classroom as, conventionally, the properties of a substance (solid, liquid or
gas) are related to the atoms and molecules that make up the substance and the way they are
connected to one another ( chemical bonds). Size is not normally mentioned as a key factor. Students
will probably expect a piece of gold to be golden in color however big or small it is. This is correct at
the macro and micro-scale level: but at the nanoscale, things start to change dramatically due to
quantum effects. In fact, gold can be used as a prime example: a colloid of gold nanoparticles is no
longer 'golden' but ruby-red in color (Figure 1).

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Figure 1: The color of gold

depends on its size

Image: L. Filipponi, iNANO,

Aarhus University, Creative Commons
ShareAlike 3.0

TIP FOR TEACHERS: The concept that a material can have properties that are size-dependent can be
illustrated through 'macro' analogies. For instance, a glass half-filled with water makes a different sound
to a glass totally filled with water. In this analogy, the quantity (volume) of the water determines the sound
that is emitted. similarly, a guitar string under more or less tension will also make a different sound.

A different kind of small

Materials that belong to the 'nanoscale' are made of at least clusters of atoms and molecules, not just
single atoms: for example, 3.5 atoms of gold or eight hydrogen atoms lined up in a row are one nanometre
long. A glucose molecule is about 1 nm in size.

Nanomaterials represent a 'different kind of small' compared to other 'small' objects that a student
might be familiar with. Nanomaterials are not as small as electrons or single atoms, and are bigger
than other 'very small objects', such as a cell or bacterium, that a student can probably think of. Nano
structures are at the confluence of the smallest human-made objects (eg latest-generation transis
tors) and the largest molecules of living things (eg DNA, proteins). Nanomaterials are intermediate
in size between isolated atoms and molecules, and bulk materials. At this scale, matter shows
exceptional properties.

Thanks to their unique properties, nanomaterials offer two exciting possibilities:

• nanomaterials can be used to improve current materials or create new ones that have exceptional
properties;
• as nanomaterials have dimensions in the range of the largest molecules found in the natural world, it is possible to
integrate them and interact actively with them in a device.

The fabrication and utility of a range of nanomaterials are further discussed in Module 1, Chapter 5:
Overview of nanomaterials.

Physics at the nanoscale

Nanomaterials are closer in size to single atoms and molecules than to bulk materials, and to explain their behaviour, it is
necessary to use quantum mechanics. Quantum mechanics is a scientific model that was developed for describing the
motion and energy of atoms and electrons. As quantum mechan ics concepts are normally included in a secondary
science (physics or chemistry) school curriculum, they are not described here in detail. Here, just a brief summary of the
most salient quantum effects, together with other physical properties that are relevant at the nanoscale is provided.

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• Due to the smallness of nanomaterials, their mass is extremely small and gravitational forces
become. Instead, electromagnetic forces are dominant in determining the behavior of
atoms and molecules.
• Wave-corpuscle duality of matter: for objects of very small mass, such as the electron, wavelike
nature has a more pronounced effect. Thus, the electrons exhibit wave behavior and their
position is represented by a wave (probability) function.
• One of the consequences is a phenomenon called tunneling. Classic physics states that a body
can pass a barrier (potential barrier) only if it has enough energy to 'jump' over it. Therefore, if
the object has lower energy than that needed to jump over the energy barrier (the 'obstacle'), in
classic physics, the probability of finding the object on the other side of the barrier is zero. In
quantum physics, a particle with energy less than that required to jump the barrier has a finite
probability of being found on the other side of the barrier. Figuratively, one can imagine that
the particle passes into a 'virtual tunnel' through the barrier (Figure 2). It should be noted that
in order to have a tunnel effect, the 'thickness' of the barrier (ie energy potential) must be
comparable to the wavelength of the particle and, therefore, this effect is observed only at
nanometre level. So, in simple terms, electron (or quantum) tunnelling is (when a par ticle
electron) with lower kinetic energy is able to exist on the other side of an energy barrier with
higher potential energy, thus defying a fundamental law of classic mechanics. Tunnelling is
the penetration of an electron into an energy region that is classically forbidden.

Tunnelling is a fundamental quantum effect and it is the basis of a very important instrument for
imaging nanostructured surfaces called the Scanning Tunnelling Microscope (STM). The same
instrument can be used as a nanofabrication tool (movement of single atoms). The operation
principle and capabilities of the STM are discussed in Module 1, Chapter 6: Characterisation methods.

Figure 2: Schematic representation of tunneling

Image: ©Max Planck Institute for Quantum Optics

• Quantum confinement: in a nanomaterial, such as a metal, electrons are confined in space

rather than free to move in the bulk of the material.
• Quantization of energy: electrons can only exist at discrete energy levels. Quantum dots
are nanomaterials that display the effect of quantisation of energy.
• Random molecular motion: molecules move due to their kinetic energy assumption (the sample
is above absolute zero). This is called random molecular motion and is always present. At the
macroscale, this motion is very small compared to the sizes of the objects and thus is not influ
ential on how the object moves. At the nanoscale, however, these motions can be of the same
scale as the size of the particles and thus have an important influence on how they behave.
One example of a random kinetic motion is Brownian motion.

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• Increased surface-to-volume ratio: one of the distinguishing properties of nanomaterials is

that they have an increased surface area. This is characteristic described in more depth in
the next section.

Chemistry at the nanoscale

It has already been stated that a nanomaterial is formed of at least a cluster of atoms, often a cluster
ter of molecules. It follows that all types of bonding that are important in chemistry are also
important in nanoscience. They are generally classified as:

• intramolecular bonding (chemical interactions): these are bondings that involve changes in
the chemical structure of the molecules and include ionic, covalent and metallic bonds;
• intermolecular bonding (physical interaction): these are bondings that do not involve changes in
the chemical structure of the molecules and include ion-ion and ion-dipole interactions; van der
Waals interactions; hydrogen bonds; hydrophobic interactions; repulsive forces (such as steric
repulsions).

It is assumed that the description of chemical and physical bonds is part of the secondary science
school curriculum, so here some chemical and physical interactions that often used to describe the
properties of nanomaterials are highlighted.

Nanomaterials often arise from a number of molecules held together or large molecules that assume
specific three-dimensional structures through intermolecular bonding (macromolecules). Therefore,
nanoscience also deals with supramolecular chemistry (ie the chemistry that deals with inter
actions among molecules), which is just a sub-area of the general field called 'chemistry'. In these
macromolecules, intermolecular bonding often plays a crucial role.

• Intermolecular bondings, such as hydrogen bonding and van der Waals bonding are weak
interactions but in a large number they can have a total energy that can be quite significant.
Consider, for instance, the structure of DNA (which has a cross-section of 2 nm): the two helixes
are held together by numerous hydrogen bonds. This point becomes particularly relevant in
nanoscience, where materials can have very large surface areas and, consequently, small
forces can be applied to very large areas.

HANDS-ON ACTIVITY a very simple demonstration to show how small forces become important
on large surfaces is to take two big books made of thin paper (such as a phonebook or Yellow
Pages) and fought one page of the first book over a page of the second book alternately.
When only a few pages are overlapped, it is very easy to take the two books apart: you just need
to pull. As the number of connected pages increases, it becomes harder to pull the two books
apart. After a certain number of pages, it is no longer possible to separate the two books by hand!
The interaction between the pages is due to weak forces (electrostatic and van der Waals). When
the surface area is big, these weak forces result in a very strong interaction!

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• Intermolecular bondings often hold macromolecules (such as proteins) together in specific three-dimensional
structures with which precise biological functions are associated. Disrup tion of these interactions in a protein
irreversibly affects its 3D structure (quaternary structure) and leads to a total loss of function (protein denaturation).

• One type of intermolecular bonding particularly significant in nanoscience is the hydrophobic effect. This is a
process driven by entropy and which has a major role in biological materials. In simple terms, it is the property by
which non-polar molecules (eg oil) tends to form aggregates of like molecules in water.

TIP FOR TEACHERS: Students will be familiar with the hydrophobic effect. A simple example is oil
drops in water.

Molecules as devices

In nanoscience, macromolecules are often considered as 'devices' that, for instance, can trap or
release a specific ion under certain environmental conditions (pH etc.). A biological example of such
a macro molecule is ferritin. Therefore, in nanoscience and nanotechnologies, where molecules can
themselves be devices, bonds may also be device components. One area of study is, for example,
the use of molecules as molecular switches, actuators and electronic wires. This is further
discussed in Module 2, Chapter 4: Information and Communication Technologies.

Unique material properties

at the nanoscale

Surface properties
Regardless of whether we consider a bulk material or a nanoscale material, its physical and chemical properties depend
on many of its surface properties. Surfaces perform numerous functions: they keep things in or out; they allow the flow
of a material or energy across an interface; they can initiate or terminate a chemical reaction, as in the case of catalysts.
The branch of science that deals with the chemical, physical and biological properties of surfaces is called surface science.
In this context, the term interface, rather than surface, is often used, to emphasize the fact that it is a boundary between
two phases: the material and the surrounding environment (liquid, solid or gas).

If a bulk material is subdivided into an ensemble of individual nanomaterials, the total volume remains
the same, but the collective surface area is greatly increased. This is shown schematically in
Figure 3.

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Figure 3: Schematic drawing showing how surface to volume increases as size is decreased (image not to
scale)

Image: L. Filipponi, iNANO, Aarhus University, Creative Commons ShareAlike 3.0

The consequence is that the surface-to-volume ratio of the material — compared to that of the parent
bulk material — is increased.

TIP FOR TEACHERS: A very simple example to mention in class is granular sugar and caster sugar.
Caster sugar is finer, stickier (more surface absorption) and dissolves faster in water.

How would the total surface area increase if a cube of 1 m3 were progressively cut into smaller and smaller
cubes, until it is composed of 1 nm3 cubes? Table 1 summarizes the results.

Collective
Size of cube side Number of cubes
surface area
1m first 6 m2
0.1 m 1 000 won 60 m2
0.01 m = 1 cm 106 = 1 million 600 m2
0.001 m = 1 mm 109 = 1 billion 6 000 m2
10-9 m = 1 nm 1027 6 x 109 = 6 000 km2

USEFUL VIDEO No 1 CUTTING CHEESE — a simple and fun video to watch that shows the
increase in surface area as a material is cut into progressively smaller cubes can be watched
online (http://community.acs.org/nanotation/NanoTubePlayer/tabid /131/VideoId/101/Small-Can
Be-Big-A-French-Cheesy-Perspective.aspx).

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The importance of surface atoms

In surface science, the chemical groups that are at the material interface determine its properties.
Properties like catalytic reactivity, electrical resistivity, adhesion, gas storage and chemical reactivity
depend on the nature of the interface. Nanomaterials has a significant proportion of atoms existing
at the surface. This has a profound effect on reactions that occurs at the surface such as such as
catalysis reactions, detection reactions, and reactions that, to be initiated, require the physical
adsorption of certain species at the material's surface.

USEFUL VIDEO 2 MENTOS IN DIET COKE® — this video shows the effect of putting a mint
Mentos into a bottle of Diet Coke®. The effect is linked to the surface roughness of the Mentos
and to the chemistry of its coating. Even if this effect is not definitely a 'nano-effect', the video
illustrates the connection between surface properties and physical behaviour. The effect only
occurs with a mint Mentos and not using a glazed (fruit) Mentos, a sign that the effect is due to
surface chemistry/topography (http://dsc.discovery.com/videos/mythbusters-diet-coke-and -mentos.html).

The fact that in a nanomaterial a fraction of the atoms is at the larger surface influences some phys
ical properties such as the melting point. Given the same material, its melting point will be lower if it is
nano-sized. Surface atoms are more easily removed than bulk atoms, so the total energy needed to
overcome the intermolecular forces that hold the atom 'fixed' is less, thus the melting point is lower.

Shape also matters

Given the same volume, the extent of the surface area depends on the shape of the material.
A simple example is a sphere and a cube having the same volume. The cube has a larger surface area
than the sphere. For this reason, in nanoscience, not only the size of a nanomaterial is important, but
also its shape. Figure 4 illustrates this concept. In the section on catalysis, an example is given of a
nanomaterial whose properties are determined not only by size but also by shape.

Figure 4: The ratio between the

height (h) and the diameter (d)
determines whether a shape is like
a wire or a disc: shape influences
surface area.

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Surface energy
Atoms and molecules that exist at the surface or at an interface are different from the same atoms or
molecules that exist in the interior of a material. This is true for any material. Atoms and molecules at
the interface have enhanced reactivity and a greater tendency to agglomerate: surface atoms and
molecules are unstable, they have high surface energy.

TIP FOR TEACHERS: A simple example to use in class to demonstrate the concept of 'high surface
energy' is to coat some ping pong balls with Velcro (putting the two sides on different balls). If you
place the balls in a plastic bag and shake, the balls will stick together. If normal balls are used, no
attachment occurs.

As mentioned in the previous section, nanomaterials have a very large fraction of their atoms and
mol ecules on their surface. On the other hand, a fundamental chemical principle is that 'systems of
high energy will strive to attain a state of lower energy, by whatever means possible'. So how is it
possible to have nanomaterials? Nanomaterials are abundant in nature (proteins, DNA, etc.).
Nanomaterials are inherently unstable, therefore there are various methods that nanomaterials
adopt to minimise their inherent high surface energy.

One of the ways of reducing the surface energy innanoparticles is agglomeration. Surface energy is
an additive quantity. The surface of 10 identical nanoparticles is equal to the sum of the surface energy
of each individual nanoparticle. If these were to agglomerate, and become one large particle, the over
all surface energy would be reduced. The concept is illustrated in Figure 5. If a generic surface energy
value ÿ is associated with each lateral surface of cube A, than its total surface energy is 6ÿ. The same
applies to cube B. Therefore, the total surface energy of both cubes, A and B, separated, is 2 x 6ÿ = 12ÿ.
The total surface energy of the parallelepiped C, on the other hand, is 10ÿ.

Figure 5: The surface energy of two separate cubes is higher than the surface energy of the two
cubes agglomerated.

Nanoparticles have a strong intrinsic tendency to agglomerate. To avoid this, surfactants can be used.
This also explains why when nanoparticles are used in research and industry they are often immobilised
on a solid support or mixed within a matrix. Even in commercial products that claim to contain
nanoparticles (such as sunscreens) microscope images show that they are actually present in the form
of agglomerates of > 100 nm dimensions.

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Reactions where surface properties are very important

In this last section, two reactions are briefly reviewed: catalysis and detection, where the surface
properties of the material are particularly important, and what nanoscience can do to improve their
outcome is highlighted.

Catalysis

A catalyst is a that increases a chemical reaction rate without being consumed or chemically altered.
Nature's catalysts are called enzymes and are able to assemble specific endproducts, always finding
pathways by which reactions take place with minimum energy consumption. Man-made cata lysts
are not so energy efficient: they are often made of metal particles fixed on an oxide surface, working
on a hot reactant stream (to reduce the phenomenon, 'catalyst poisoning', which occurs when species
dispersed in the atmosphere, such as CO, occupy the active sites of the catalysts is used). One of
the most important properties of a catalyst is its active surface where the reaction takes place.
The 'active surface' increases when the size of the catalysts is decreased: the smaller the catalyst
particles, the greater the surface-to-volume ratio (Figure 5). The higher the catalysts' active surface,
the greater the surface reactivity. Research has shown that the spatial organization of the active
sites in a catalyst is also important. Both properties (nanoparticle size and molecular structure/
distribution) can be controlled using nanotechnology. Hence, this technology has great potential to
expand catalyst design with benefits for the chemical, petroleum, automotive, pharmaceutical and
food industries. The use of nanoparticles that have catalytic properties allows a drastic
reduction in the amount of material used, with resulting economic and environmental benefits.

Catalysis and its importance in environmental and energy applications are discussed in Module 2,
Chapter 2: Environment and Chapter 3: Energy. Figure 6 illustrates the effect of nanostructuring
on a catalyst surface.

Figure 6: Schematic representation of the increased

active surface of a nano-sized catalyst (right)
compared to a bulk catalyst

Image: L. Filipponi, iNANO, Aarhus University, Creative Commons

ShareAlike 3.0

A good example of how nanoscience can impact the development of catalytic materials is that of gold.
Bulk gold is a noble metal: it is stable, non-toxic, and resistant to oxidation and chemical attack. For
these reasons, it is widely used in jewelry. On the other hand, nanoscale gold particles can cata
lyse chemical reactions. It has been found that finely dispersed gold nanoparticles on oxide supports
are catalytically very active. In many cases, the catalytic activity and selectivity of dispersed gold
nanoparticles exceed those of the commonly used transition metal catalysts such as platinum, rhodium

MODULE 1: FUNDAMENTALS 71
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and palladium. This is an exciting result metals because like platinum and palladium (commonly used in
catalysis such as car catalytic converters) are toxic and are also very rare metals, therefore very expensive.

Detection

The detection of a specific chemical or biological compound within a mixture represents the basis for
the operation of numerous devices, such as chemical sensors, biosensors and microarrays. These
devices will be described in more detail in Module 2, Chapter 1: Medicine and healthcare. As with
catalysis, a detection reaction occurs at the material interface. The rate, specificity and accuracy of
this reaction can be improved using nanomaterials rather than bulk materials in the detection area.
The higher surface-to-volume ratio of nanomaterials increases the surface area available for detection
with a positive effect on the rate and on the limit of detection of the reaction. In addition, nanomaterials
can be designed to have specific surface properties (chemical or biochemical), tailored at a molecular
level. This way, the active sites on the material surface can act as 'locks' to detect specific molecules (the 'keys').
Figure 7 illustrates this concept. Scaling down using nanomaterials allows more detection sites to
be packed into the same device, thus allowing the detection of multiple analysis.

Figure 7: Schematic representation

showing the specific detection of
an analyte within a mixture by
'receptor' sites in a nanomaterial

Image: L. Filipponi, iNANO, Aarhus

University, Creative Commons ShareAlike 3.0

This scaling-down capability, together with the high specificity of the detection sites obtainable using
nanomaterials, will allow the fabrication of super-small 'multiplex detection devices' (ie devices that
can test and detect more than one analyte at the time).

Electrical properties

There are three categories of materials based on their electrical properties: (a) conductors; (b)
semiconductors; and (c) insulators. The energy separation between the valence band and the
conduction band is called Eg (band gap). The ability to fill the conduction band with electrons and the
energy of the band gap determines whether a material is a conductor, a semiconductor or an insulator.
In conducting materials like metals, the valence band and the conducting band overlap, so the value
of Egg is small: thermal energy is enough to stimulate electrons to move to the conduction band. In
semiconductors, the band gap is a few electron volts. If an applied voltage exceeds the band gap
energy, electrons jump from the valence band to the conduction band, thus forming electron-hole pairs called excit
Insulators have large bandgaps that require an enormous amount of voltage to overcome the threshold.
This is why these materials do not conduct electricity (Figure 8).

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Figure 8: Schematic illustration of

the valence and conduction
bands in materials based on their
electrical properties: insulator,
semiconductor and conductor

Image: L. Filipponi, iNANO, Aarhus

University, Creative Commons ShareAlike 3.0

Quantum confinement and its effect on material electrical

properties
Quantum confinement causes the energy of the band gap to increase as illustrated in Figure 9.
Furthermore, at very small dimensions when the energy levels are quantified, the band overlap
present in metals disappears and is actually transformed into a band gap. This explains why some
metals become semiconductors as their size is decreased.

Figure 9: The image compares the

energy of the band gap (arrow) in a
bulk semiconductor, a quantum dot
and an atom. As more energy states
are lost due to the shrinking size, the
energy band gap increases.

Image: L. Filipponi, iNANO, Aarhus University,

Creative Commons ShareAlike 3.0

The increase in band gap energy due to quantum confinement means that more energy will be needed
in order to be absorbed by the band gap of the material. Higher energy means shorter wavelength
(blue shift). The same applies to the wavelength of the fluorescent light emitted from the nano-sized
material, which will be higher, so the same blue shift will occur. Thus, a method of tuning the optical
absorption and emission properties of a nano-sized semiconductor over a range of wavelengths
by controlling its crystallite size is provided. The optical properties of nano-sized metals and
semiconductors (quantum dots) are described in the section of this chapter on optical properties.

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Nanomaterials with exceptional electrical properties

Some nanomaterials exhibit electrical properties that are absolutely exceptional. Their electrical prop
erties are related to their unique structure. Two of these are fullerenes and carbon nanotubes. For
instance, carbon nanotubes can be conductors or semiconductors depending on their nanostructure.
These materials are discussed in Module 1, Chapter 5: Overview of nanomaterials. Another example
is that of supercapacitors — materials in which there is effectively no resistance and which do not
obey Ohm's law.

Optical properties

Some nanomaterials display very different optical properties, such as color and transparency, com
pared to bulk materials. In this section, the reason for this behavior is discussed and some examples
provided. Before going into detail, some fundamentals are reviewed.

Interaction of light with matter

The 'color' of a material is a function of the interaction between the light and the object. If a material
absorbs light of certain wavelengths, an observer will not see these colors in the reflected light. Only
reflected wavelengths reach our eyes and this makes an object appear a certain colour. For example,
leaves appear green because chlorophyll, which is a pigment, absorb the blue and red colors of the
spectrum and reflect the green.

In general light (I) incident on a material can be transmitted (T), absorbed (A) or reflected (R):

I = T+A+R

As the size of the materials is reduced, scattering (S) of light can also contribute to its color (or
transparency). A short summary of each process follows.

• Reflection (R) occurs when lightstrikes a smooth surface and the incident wave is directed back
into the original medium. The reflected wave has the same geometrical structure as the incident
wave.
• Absorption (A) is a process that involves energy transformation. The energy levels of a sub
stance determine the wavelengths of light that can be absorbed. It is a molecular phenomenon,
dependent on the chemical identity and structure of the substance (not on the size of the mol
ecules or clusters), and involves electronic transitions, vibrations and rotations. Chromophores
and fluorephores are examples of organic materials that have specific electronic transitions. •
Transmission (T) is the ability of light to pass through a material: it is complementary to absorption.
Transmission of light is what is left after reflection, scattering and absorption has occurred.

• Scattering (S) is the phenomenon that occurs when radiation hits a structure with dimen
sions comparable to the incident wavelength. Therefore, it is a physical process that depends
on cluster size, the refractive index of the cluster and the refractive index of the suspension
medium. It is a physical interaction only — no energy transformations occurs during scattering
(as opposed to absorption), energy is simply changed in many directions. The wavelength of

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the incoming light and that of the outgoing light are the same. After the light hits the clusters in the
colloid and is redirected once, it can encounter another cluster and be redirected again. This
phenomenon is called multiple scattering. At the 'macro' level, the overall effect can be that light is
sent back the way it came (back scattering) or moves forward in the same direction it was moving
initially (front scattering). Maximum scattering occurs for wavelengths twice as large as the cluster
size. Therefore, if the cluster is about 200 nm, maximum scattering is observed at 400 nm, which lies
within the range of the visible spectrum.

The formula indicated above still holds if scattering occurs. Scattering simply contributes to the 'reflect
tion' (back scattering) and 'transmission' (front scattering) parts of the equation. Light that has been absorbed
cannot be scattered.

Color generation from nanoparticles and nanostructures

Nanomaterials in general can have peculiar optical properties as a result of the way light interacts with their
fine nanostructure. An overview follows.

Color due to … Example of nanomaterials

Interference: The color is based on the Butterfly wings (photonic crystals) — this
constructive interference of light wavelengths as example is described in Module 1, Chapter 2:
they interact with the nanomaterial. Nanoscience in nature
Liquid crystals (eg soap) — the colors of
liquid crystals are explained in detail in
Module 3, Experiment RED

Scattering: Colors arise because different Colloids (milk)

particle sizes scatter different wavelengths.

Surface plasmons: This is a peculiar effect Metal colloids (nano-gold)

found in metal nanoparticles (see the next
section) responsible for the vivid colors of metal
colloids.

Quantum fluorescence: The quantum Semiconductor quantum dots (QDs)

confinement in nano-sized semiconductors leads to
discrete energy levels from which energy can
be emitted (fluorescence) after it has been
absorbed by the semiconductor.

Color in metal colloids (surface plasmons)

One of the distinguishing properties of metal nanoparticles in general is their optical properties, which are
different from those of their bulk counterpart. This is due to an effect called localized sur face plasmon
resonance. In simple terms, when light hits a metal surface (of any size) some of the light wave propagates
along the metal surface giving rise to a surface plasmon — a group of surface conduction electrons that
propagate in a direction parallel to the metal/dielectric ( or metal/vacuum) interface. When a plasmon is
generated in a conventional bulk metal, electrons can move freely in the material and no effect is registered. In
the case of nanoparticles, the surface plasmon is localized in space, so it oscillates back and forth in a
synchronised way in a small space, and the effect is called Localized Surface Plasmon Resonance (LSPR).
When the frequency of this oscillation is the same as the

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frequency of the light that it generated it (ie the incident light), the plasmon is said to be in resonance
with the incident light.

LSPR energy is sensitive to the dielectric function of the material and the surroundings, and to
the shape and size of the nanoparticle. This means that if a ligand, such a protein, attaches to the
surface of the metal nanoparticle, its LSPR energy changes. similarly, the LSPR effect is sensitive to
other variations such as the distance between the nanoparticles, which can be changed by the
presence of surfactants or ions. The LSPR effect has been observed not only on metal nanoparticles
but also in nanorings, voids in metal films and other nanostructures (Figure 10).

Figure 10: Transmission electron micrographs and UV-Visible spectra of gold nanoparticle colloids
with various geometries: (top) spheres, (middle) decahedra and (bottom) rods

Image: Borja Sepúlveda et al., 'LSPR-based Nanobiosensors', Nano Today, 2009, 4(3), 244–251, reprinted with the
permission of Elsevier

One of the consequences of the LSPR effect in metal nanoparticles is that they have very strong
vis ible absorption due to the resonant coherent oscillation of the plasmons. As a result, colloids
of metal nanoparticles such as gold or silver can display colors which are not found in their bulk
form, such as red, purple or orange, depending on the shape, size and surrounding media of thenanoparticles.
An example has already been illustrated in Figure 1, which shows that a colloid of gold nanoparticles
about 15 nm in size is ruby-red! The properties of metal nanoparticles make them useful in sensing.

The applications of metal nanoparticles are discussed in Module 1,

Chapter 5: Overview of nanomaterials and Module 2, Chapter 4:
Medicine and healthcare.

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Color in semiconducting nanocrystals (quantum dots)

As already mentioned, nano-sized semiconductors have quantised energy states; therefore, the
conduction and the valence bands split and become discrete. Charge transfer occurs between
these discrete levels, so only wavelengths of a certain dimension are absorbed: as a consequence,
emission is monochromatic. Quantum confinement causes the energy of the band gap to increase:
therefore, more energy is needed in order to be absorbed by the band gap of the material. Higher
energy means shorter wavelength (blue shift). The same applies to the wavelength of the fluorescent
light emitted from the nano-sized material, which will be higher, so the same blue shift will occur.
Tuning the size of the semiconductor nanocrystal is a means of tuning the band gap and, therefore,
the wavelength absorbed/emitted by the crystal. As a result, the same material (eg CdSe) emits
different colors depending on its size (Figure 11).

Figure 11: Ten distinguishable emission

colors of ZnS-capped CdSe QDs excited
with a near-UV lamp

Image: Nature Biotechnology, 2001, 19:631–

5, reprinted with the permission of Macmillan Publishers
Ltd, © 2001

QDs are currently used as an alternative to conventional dyes in fluorescence microscopy and in
other methods where dyes are used (eg dye-sensitized solar cells). QDs are also being studied as
alternative light-emitting sources.

The applications of semiconducting nanoparticles (quantum dots) are

discussed in Module 1, Chapter 5: Overview of nanomaterials and
Module 2, Chapter 3: Energy and Module 2, Chapter 4: Information and
Communication Technologies.

From white to transparent materials

The scattering of visible light is responsible for the white appearance of high-protection sun
screens. Students will be familiar with these thick, white paste-like sunscreens that are often used on
children and on adults with sensitive skin. These sunscreens contain ZnO and TiO2 clusters of about
200 nm. Visible light interacts with these clusters and all of its wavelengths are scattered. The
combination of the visible spectrum is white: therefore, the sunscreen appears white (as illustrated in
the curve shown in Figure 12).

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If the dimensions of the cluster are reduced, for instance from 200 to 100 nm, maximum scat
tering occurs around 200 nm and the curve is shifted towards shorter wavelengths, which are no
longer in the visible spectrum: the effect is that the same material ( eg ZnO), now in smaller size (100
nm), no longer appears white but transparent (Figure 12).

Figure 12: Scattering curves for 100 nm and

200 nm ZnO clusters

Image: reprinted from the NanoSense Curriculum Series

'Clear Sunscreen', © SRI International, 2005–08, Creative
Commons Attribution ShareAlike 3.0

The different light scattering of bulk and nano-sized ZnO and TiO2 is
exploited in the latest-generation sunscreens which appear trans
parent rather than white. This and other applications, including coatings
for solar panels, are discussed in this module, Chapter 5: Overview of
nanomaterials.

Magnetic properties

The magnetic properties of a magnet are described by its magnetisation curve. In general terms, the
magnetisation curve of a ferromagnetic material is a plot of the total magnetisation of the sample
versus the applied DC field with strength H, as illustrated in Figure 13.

Initially, as H increases, M increases until a saturation point Ms is reached. When H is decreased

from the saturation point, M does not decrease to the same value it had before: rather, it is higher on
the curve of the decreasing field. This is called hysteresis. When the applied field H is returned to
zero, the magnet still has a magnetisation, referred to as remnant magnetisation In order
Mr . to remove the
remnant magnetisation, a field Hc has to be applied in the direction opposite to the field applied the
first time. This field is called the coercive field.

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Figure 13: Magnetisation hyster

esis loop showing the coercive field
Hc , the remnant magnetisation Mr ,
and the saturation point Ms

Image: L. Filipponi, iNANO, Aarhus

University, Creative Commons
ShareAlike 3.0

The diverse applications of magnets require the magnetisation curves to have different proper
ties. In general, for soft magnetic materials (eg those used in transformers and rotating elec
trical machinery), which are subject to rapidly alternating AC magnetic fields (so that they repeat
the magnetisation curve many times), small or zero coercive fields are required to minimise the
energy loss (in the form of heating) during operation. In the case of permanent magnets (hard
magnets) used as part of high-field systems, large coercive fields are required and large hysteresis
loops are sought, as well as high saturation magnetisations.

Nanostructuring of bulk magnetic materials can be used to design the magnetisation curve of
the material, leading to soft or hard magnets with improved properties.

In general, the magnetic behavior of a material depends on the structure of the material and on its
temperature. In order to 'feel' a magnetic field, a material must have a non-zero net spin (transition
metals). The typical size of expected magnetic domains is around 1 µm. When the size of a mag
net is reduced, the number of surface atoms becomes an important fraction of the total number of
atoms, surface effects become important, and quantum effects start to prevail. When the size of
these domains reaches the nanoscale, these materials show new properties due to quantum
confine ment, for example the giant magnetoresistance effect (GMR). This is a fundamental
nano-effect which is now being used in modern data storage devices. The effect of nanostructuring
on magnetic materials in discussed in detail in this module, Chapter 5: Overview of nanomaterials.

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The GMR effect and its application to the data storage devices are discussed
in Module 2, Chapter 4: Information and Communication Technologies.

Mechanical properties

Some nanomaterials have inherent exceptional mechanical properties which are connected to
their structure. One such material is carbon nanotubes: these are extremely small tubes having the
same honeycomb structure of graphite, but with different properties compared to graphite. They can
be single-walled or multi-walled, as illustrated in Figure 14. Carbon nanotubes are 100 times stronger
than steel but six times lighter!! The different structures, properties and potential applications of
carbon nanotubes are reviewed in the next chapter of this module, Chapter 5: Overview of nanomaterials.

Figure 14: Types of carbon nanotubes

Image: Mstroeck on en.wikipedia, Creative Commons

Attribution ShareAlike 3.0

Improving existing materials

Nanomaterials can also be used to improve the mechanical properties of existing materials. In
this case, nanocomposites are formed.

One example is nanocrystalline materials, which are polycrystalline (ie made of many crystals which
are identical but connected without orientation) and defined as materials with grain sizes from a few
nanometres up to 100 nm. In contrast, the grain size in industrial metallic materials is about 10 000 nm
or greater. These materials generally show improved mechanical properties (toughness, hardness,
etc.).

Why is this so? A polycrystalline material (illustrated in Figure 15) has large pockets of regularity
(crystals) in a 'sea' of atoms that are not ordered (amorphous region).

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Figure 15: (A) structure of NaCl, where the vast majority of sodium and chlorine atoms are organ
ised at a fixed distance from each other and always alternately (example of a single crystal);
(B) structure of a polycrystalline material such as iron — large pockets of regularity are seen in a
'sea' of atoms that are not ordered (the blue atoms are organized in tiny single crystals, whereas
the 'sea' consists of the red atoms where there is no crystal lattice); (C) SiO2 crystal (quartz) which
has the typical fracture surface of single crystals

Image: reprinted from 'Nanoteknologi– 12 historier om den nyeste danske nanoforskning', © iNANO, Aarhus University

Within the crystalline structures, there can be defects (cracks or dislocations). If subjected to mechan
ical stress, the polycrystalline materials can fracture because these defects allow the crack to propa
gate. To impede the movement of cracks and dislocations tiny particles (nanoparticles) of another
material can be added in the lattice. Nanocrystalline materials can have vastly improved mechanical,
magnetic, electrical, and catalytic properties and greater corrosion resistance compared to conventional
materials with large grains.

What can these materials be used for? Nanocrystalline materials are

already used in the form of hard coatings to protect tools in industry, such
as cutting tools, where they are making a great impact in improving tool
performance and lifespan. Nanoparticles added to a ceramic, such as
alumina, also increases its mechanical properties, and the same applies
to the addition of nanomaterials (such as carbon nanotubes) to poly
mers. The possibility of using nanomaterials for improving the mechan
ical properties of materials involves both intangible and organic (polymeric)
composites. Both these types of nanocomposites are discussed in detail
in this module, Chapter 5: Overview of nanomaterials. These mater
ials have a very broad spectrum of utility, ranging from improved metals to
improved plastics.

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CHAPTER 5:

OVERVIEW OF NANOMATERIALS
Nanoscience will impact the design and fabrication of new materials with innovative properties and
functions. Contributions to this field are very widespread, and include enhancing the properties of plas
tics, ceramics, coatings, composites, fibers and many more. Nanoscience also introduces an entirely
new concept in material design, the bottom-up approach of material self-assembly, which is directly
inspired from how organic and intangible materials are created in nature. As a matter of fact, as shown
in the first section, nature is a great source of inspiration to materials engineers, since many natural
nanomaterials perform extraordinary functions as a result of their inner nanostructure.

This chapter provides an overview of nanomaterials, their properties and functions. The application
areas of the cited nanomaterials are also mentioned. The second module of this Teachers Training Kit
is devoted to applications of nanotechnologies.

The question: What is a'nanostructured material'? must be considered before discussing examples
of various functional nanomaterials. Nanostructured materials are solids or semi-solids (eg hydro gels,
liquid crystals) characterised by a nano-sized inner structure. They vary differ from crystalline,
microstructured and amorphous solids because of the scale order. In crystalline solids, the atoms are
neatly arranged in a grid where the distance between neighboring atoms is well defined, and this order
extends to macroscopic dimensions. In contrast, microstructured materials show structural variation
only on a micron scale, whereas amorphous materials exhibit short-range order only. In nanostructured
materials, the spatial order is at the nanoscale, which lies between the microscopic and the atomic
scale.

The size of the nanostructures and the scale order within them in the solid affects the properties of
a material. Nanostructured materials differ from conventional polycrystalline mater ials in the size of the
structural units of which they are composed. They can exhibit properties that are different from those of
conventional materials, and this is often a direct consequence of the large fraction of grain boundaries (ie
the space between the nanostructures) in the bulk material.
This means that in a nanostructured material there is a large proportion of surface atoms (ie
atoms that are located at or near a surface). Due to the large surface area, bulk properties become
controlled by surface properties. This surface — also called an interface — can form a border with
the embedding matrix, a nanoparticle, air or vacuum in the case of a pore or defect.

Examples of nanostructured materials are nanoporous, nanocrystalline, nanocomposite and hybrid

materials: nanoporous materials have nano-sized pores; a nanocrystalline material consists of many
nano-sized crystalline domains; a nanocomposite material contains two or more phase separated
components with morphology of spheres, cylinders or networks with nano-sized dimensions (further
divided into intangible and polymer nanocomposites); and hybrid materials are made of a
combination of organic and inorganic components connected at a molecular level (eg block copolymers).
The materials within this chapter were categorised based on the function they serve, and for this reason,
throughout the text, they are often cross-referenced: a nanocoating can be a nanocomposite but,
because of its specific function, is described in a separate group .

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One of the distinguishing features of nanostructured materials is that they can have properties
that differ significantly from those displayed in bulk. This means that scientists have the
opportunity to design new materials with specific functions by exploiting the intrinsic properties of
nanomaterials. As a result, coatings, plastics and metals with new properties can be made to
fulfil specific functions. As discussed in this chapter, numerous new materials are being developed
with exciting properties. Although much research is still needed in this field, numerous commercial
realities already exist and exciting new materials should be expected in the future. These mater ials
have numerous applications that extend from the medical sector (eg antibacterial coatings) to
improved cutting tools.

Biomimetic nanomaterials

The first class of engineered nanomaterials to be reviewed is biomimetic materials. As mentioned in

Module 1, Chapter 2: Nanoscience in nature, nature is the best nanotechnology platform.
Over thousands of years of evolution, nature has developed an enormous array of materials, ranging
from feathers to shells, wood, bone and many more that have intricate hierarchical structures at the
nano, micron and macro levels which confer specific properties on the material, such as strength,
lightweight, permeability, colour. Natural materials provide an amazing platform and inspire materials
to fabricate advanced materials that possess specific functions. As a matter of fact, numerous 'macro'
materials we use today were developed after inspiration from natural materials. One example is
Velcro, which was developed in 1948 by a Swiss engineer named George de Mistral who was
inspired by the mechanism that enables cockleburs to cling to dog hair and fabric. Nanostructures in
natural materials often play a crucial role, inspiring scientists to mimic them starting from a molecular
level (molecular biomimetics). This is also called biomimetic nanotechnology. Now, some examples
of these biomimetic nanomaterials are provided.

Gecko-inspired adhesive (or bio-rubber)

In Chapter 2, the adhesive properties of the gecko foot were discussed and, specifically, how these
are not related to a glue in the foot, but rather to van der Waals and capillary forces exerted by
millions of nanostructures (called setae) that make up the foot. This allows the animal to walk upside
down, against gravity and on many different surfaces, including those which are wet. Moreover, a
gecko can walk on a dirty surface without losing adherence, since its feet are also self-cleaning. A
truly amazing material! Scientists have been inspired by this animal to design and fabricate adhesives
for numerous applications. For instance, a group of researchers at the University of California,
Berkeley, has developed adhesive gecko-foot-like surfaces for use in climbing robots. The adhesive
is made of patches of microfibre arrays with 42 million polypropylene microfibre per square centimeter.
The patches can support up to 9 N cm-2: a 2 cm2 patch can support a load of 400 g. This result is
very close to the loads supported by a gecko, which are about 10 N cm-2. This gecko-like adhesive
is very similar in functionality to the natural gecko foot, but not as good—yet. Researchers still have
to make it topography-independent (capable of attaching to any surface) and self-cleaning. At another
university, a biomimetic gecko tape has been produced using polymer surfaces covered with carbon
nanotube hairs, which can stick and unstick on a variety of surfaces, including Teflon®.

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Other gecko-inspired nanomaterials are under development for medical

applications, which will be covered in Module 2, Chapter 1: Medicine and
healthcare.

Self-healing adhesives
Diatoms are a type of algae with nanostructured amorphous silica surfaces. Some diatom species have
evolved strong self-healing underwater adhesives. Some are free-floating, others have adhesive
properties in water: for instance, diatoms in the Antarctic seas can attach to ice. Others secrete viscous
mucilage which binds colonies together while protecting the silica shells from wear as they rub against
each other. Molluscs are another species that have adhesive properties under water. Both diatoms
and molluscs have strong underwater glues that can also resist stress and self-heal if necessary. For
these reasons, they serve as a biomimetic model for self-healing materials. Researchers have studied
these natural adhesives and found that their self-healing properties are due to the properties of the
proteins contained in them. These proteins have 'sacrificial' bonds that allow the molecule to be revers
ibly stretched by breaking and re-bonding. This sacrificial bond behavior has been observed in many
other materials, such as wool. The detailed analysis of these natural materials is inspiring new nano
adhesives with self-healing properties.

Biomimetic membranes, capsules and bioreactors

The bilipid membrane has served as a biomimetic model for decades. A simple example is liposomes
(lipid vesicles) which are easily formed by shaking oil vigorously in water. Planar-supported bilayers are
also inspired by the lipid membrane and are formed by simply 'dipping' a suitable substrate inside an
organic aqueous phase.

Inside the cell, there are numerous self-assembled structures that encapsulate
specific biomolecules and release them as a consequence of molecular
signaling. These structures are inspiring a wide range of nanocapsules for
application in drug delivery. In some cases, bacteria or viruses are used
as templates for fabricating these nanocapsules. These nanomaterials are
described in more detail in Module 2, Chapter 1: Medicine and healthcare.

Biomimetic energy nanomaterials

Many challenges that we are now facing in the energy area (improvements needed in solar panels,
hydrogen fuel cells, rechargeable batteries, etc.) can be solved through the use of nano-engineered
materials. Some of these materials have been developed following direct inspiration from nature, such
as the new types of solar photovoltaic cells, which try to imitate the natural nanomachinery of
photosynthesis. Another interesting example is that of using battery electrodes with self-assembling
nanostructures grown by genetic engineered viruses.

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Both examples will be described in more detail in Module 2, Chapter 3;

Energy.

NANOYOU GAME Nature-inspired nanomaterials are used in one of the NANOYOU jigsaw
puzzle games (http://nanoyou.eu/en/play-nano.html) — students must match the nanomaterial
to its application, connecting it to a specific need.

Self-assembled nanomaterials

The concept of self-assembly derives from the observation that, in natural biological processes, mol ecules self-assemble to create
complex structures with nanoscale precision. Examples are the formation of the DNA double helix or the formation of the membrane
cell from phospholipids. In self assembly, sub-units spontaneously organise and aggregate into stable, well-defined structures through
non-covalent interaction. This process is guided by information that is coded into the characteristics of the sub-units and the final
structure is reached by equilibrating to the form of the lowest free energy.

An external factor, such as a change in temperature or a change in pH, can disrupt this organisation.
For instance, a protein self-assembles into a specific structure but, if exposed to conditions such as
high heat or high acidity, it can denature, which means that its structure is damaged, and the protein
unfolds. This means that the protein loses its function as its structure is damaged. So, in nature, self-
organised structures have specific functions.

Molecules in nature change conformation and move from one self-organised structure into another as they bind to certain ions or
atoms. Many examples are available, such as hemoglobin (which captures and releases an iron ion), or the potassium-sodium pump,
chlorophyll, etc.

The use of self-assembly to create new materials is a bottom-up approach to nanofabrication, and
is thus an essential tool in nanotechnology (see Module 1, Chapter 7: Fabrication methods).
Instead of carving nanostructures out of larger materials (which is the typical top-down approach,
such as micromachining and microlithography, used to fabricate integrated electronic circuits),
nanostructures are created from the bottom, from atomic building blocks that self-assemble into larger
structures . In the laboratory, scientists can make use of this self-organization of matter as a way of
programming the building of novel structures with specific functions. Examples of self-assembled
nanomaterials include dendrimers, DNA nanostructures, cyclodextrins, self-assembled monolayers (SAMs), liquid cry

Self-assembled monolayers (SAMs)

Some organic molecules, when exposed from solution or vapour to a suitable substrate, self-assemble
to produce homogeneous, densely packed layers of monomolecular thickness. These organic molecules
have long chains with two different end groups. The monolayer is formed when one of the two end
groups of the organic molecule reacts with a particular surface forming a chemical bond. The surface
properties of the substrate are then defined by the exposed functional groups of the monolayer. For
example, alkyl-silane or alkane thiol molecules exposed to a silica or metal surface assemble into

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organized layers. SAM-forming materials may be physisorbed layers, such as Langmuir-Blodgett films, or chemisorbed layers,
such as organosilanes bonded to silica or organothiols bonded to gold. Films of mixed SAMs with tailored surface properties
can be fabricated by mixing two (or more) precursor molecules and photosensitive SAM layers can be produced by molecularly
engineering the precursor to include a photoreactive species. Whitesides and his co-workers from Harvard University have
intro duced the use of mixed SAMs of alkanethiols on gold surfaces to control protein and cell adhesion.

SAMs of alkanethiol on gold are formed when a gold surface is exposed to a solution or to the vapour of
an alkanethiol. The sulphur atoms of the alkanethiols coordinate with the gold surface, while the alkyl
chains are closely pack and tilted to 30° from the surface normal. The terminal end group of a ÿ-
substituted alkanethiol determines the surface properties of the monolayer.

Figure 1: Schematic representation

depicting the formation of a self
assembled monolayer on a surface

Reprinted from: http://www.mtl.kyoto-u.ac.jp/

english/laboratory/nanoscopic/nanoscopic.htm

Surfaces with micron and nanopatterns of SAMs are interesting since they allow the creation of metal lic 'hybrid' circuits
where biomolecules can be selectively attached (and released) to patterns of gold.
Different methods exist for creating micro and nanopatterns of SAMs, such as microcontact printing (µCP), nanocontact
printing (nCP), conventional lithography and Dip Pen Nanolithography®. The details of these fabrication methods are discussed
in Module 1, Chapter 7: Fabrication methods.

SAMs are extremely useful in thin-film technology since they provide a

simple, versatile and relatively inexpensive way of producing coatings with
specific functionalities. Thin coatings are used in many applications, for
example to control surface wetting and adhesion properties; to provide
chemical resistance or specific biocompatibility; to confer antibacterial
properties; and for sensors (see also: Nanocoatings in this chapter and
Module 2, Chapter 2: Environment). SAMs are particularly interesting for
developing DNA and protein micro and nanoarrays for medical screening
(see Module 2, Chapter 1: Medicine and healthcare) and for future
electronic components in computer chips and other ICT developments (see
Module 2, Chapter 4: Information and Communication Technologies.

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Liquid crystals
A liquid crystal is a fourth state of matter: it has properties between those of a conventional liquid
and those of a solid crystal. Like a liquid, it flows, and, like a crystal, it can display long-range
molecu lar order (Figure 2). In terms of classifications, liquid crystals (together with polymers and
colloids), are often classified as 'soft matter' (Figure 3) and treated under the branch of physical
chemistry of condensed matter.

Figure 2: The liquid crystal phase is in between a solid and a liquid phase

Image: L. Filipponi, iNANO, Aarhus University, Creative Commons Attribution ShareAlike 3.0

Figure 3: Diagram showing where the branch of 'liquid crystals' fits into the classification of physical
chemistry of condensed matter

A fascinating and characteristic feature of liquid-crystalline systems is that they change their molecu
lar and supermolecular organization as a result of very small external disturbances: the molecules
in liquid crystal displays, for instance, are reoriented by relatively weak electrical fields. If a small
amount of chiral molecules are dissolved in an achiral liquid-crystalline host phase, remark able
macroscopic chirality effects occur, ranging from helical superstructures to the appearance of
ferroelectricity.

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Liquid crystal self-assembly

Liquid crystals are partly ordered materials, somewhere between their solid and liquid phases. This
means that liquid crystals combine the fluidity of ordinary liquids with the interesting electrical and
optical properties of crystalline solids.

Molecules of liquid crystals are often shaped like rods or plates or some other form that encourages them
to align together along a certain direction (Figure 4).

Figure 4: Example of the self-organization of anisometric (ie with asymmetrical parts) molecules in
liquid-crystalline phases

Left: Rod-like molecules form a nematic liquid, in which the longitudinal axes of the molecules are
aligned parallel to a common preferred direction (director).

Right: Disc-like (discotic) molecules arrange to molecule-stacks (columns), in which the longitudinal
axes are also aligned parallel to the director. As a result of their orientational order, liquid crystals
exhibit anisotropic physical properties, just like crystals.

Image: http://www.ipc.uni-stuttgart.de/~giesselm/AG_Giesselmann/Forschung/Fluessigkristalle/Fluessigkristalle.html

Liquid crystals are temperature sensitive since they turn to solid if it is too cold and to liquid if it is too
hot. This phenomenon can, for example, be observed on laptop screens when it is very hot or very
cold.

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Phases of liquid crystals and their properties

A liquid crystal is formed by the self-assembly of molecules into ordered structures, or phases. An
external disturbance, such as a change in temperature or magnetic field, even very small, can induce
the liquid crystal to assume a different phase. Different phases can be distinguished by their different
optical properties (Figure 5).

Figure 5: Schematic representation of

molecules in a solid (left, molecules
are well organised), in a liquid crystal
(center, molecules have a long range
distance order) and in a liquid (right,
molecules are not ordered)

Image: © IPSE Educational Resources,

University of Wisconsin-Madison

Liquid crystals are divided into three groups:

• thermotropic liquid crystals consist of organic molecules, typically having coupled double
bonds, and exhibit a phase transition as temperature is changed (Figure 5, left);
• lyotropic liquid crystals consist of organic molecules, typically amphiphilic (water-loving) and
exhibit a phase transition as a function of both temperature and concentration of the liquid
crystal molecules in a solvent (typically water) (Figure 5, right, and Figure 6 ) );
• metallotropic liquid crystals are composed of both organic and inorganic molecules, and their
liquid crystal transition depends not only on temperature and concentration but also on the
organic-inorganic composition ratio.

Figure 6: (left) Chemical structure of N (4-methoxybenzylidene)-4-butylaniline (MBBA); (right)

structure of a lyotropic liquid crystal: (1) is a bilayer and (2) is a micelle (the red heads of the
surfactant molecules are in contact with water, whereas the tails are immersed in oil (blue).

Image: Wiki Commons, Creative Commons Attribution ShareAlike 3.0

Lyotropic liquid-crystalline phases are abundant in living systems, such as biological membranes,
cell membranes, many proteins (such as the protein solution extruded by a spider to generate silk),
as well as tobacco mosaic virus. Soap is another well-known material which is in fact a lyotropic liquid
crystal. The thickness of the soap bubbles determines the colors of light they reflect.

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Liquid crystal applications

The order of liquid crystals can be manipulated with mechanical, magnetic or electric forces. What is
interesting is that this change of order can be obtained with very small variations of these forces. The
properties of liquid crystals are useful in many applications. The color of some liquid crystals depends
on the orientation of its molecules, so any influence that disturbs this orientation (eg a difference in
magnetic or electric field, temperature, or the presence of certain chemicals) can be detected with a
color change.

EXPERIMENT B in the NANOYOU Experiment Module deals with syn

thesising and testing different temperature sensitive liquid crystals. In this
experiment, students test how different liquid crystals are sensitive to
different temperature ranges and build an liquid crystal thermometer.

The details of how a thermotropic liquid crystal works are described in the
background document for EXPERIMENT B in the NANOYOU Experiment
Module.

Liquid crystals are routine used in displays for cell phones, cameras, laptop computers and other
electronics. In these displays, an electric field changes the orientation of the molecules in the liquid
crystal, and affects the polarization of light passing through them. Because of their sensitivity to
temperature, and the property of changing colour, they are also used in thermometers. In miniaturized
sensors, liquid crystals can detect certain chemicals, electric fields and changes in temperature.

Liquid crystal displays (LCDs) are discussed in Module 2, Chapter 4:

information and Communication Technologies.

In the future, liquid crystals might have very interesting applications. Recently, it has been found that
the inclusion of specific molecules, often in the order of nanometres, in the liquid crystal can lead to
inherent new electrical and optical properties. For example, liquid crystal materials have been modified
to induce new photonic functions and for application in waveguides and optical storage (ICT application area).
Another class of liquid crystals under development is photoconductive liquid crystals, which aim to use
new materials in photovoltaic cells and light-emitting diodes (Energy application area). Another area of
study is the modification of liquid crystals in such ways that allow them to be used in stimuli-responsive
materials and as templates for nanoporous polymers (potential nanomedicine application area).

Nanostructured metals and alloys

This section covers metal nanoparticles — nanocrystalline materials consists of a single metal or of
alloy made of two or more metals and nanostructured metal surfaces.

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Metal nanoparticles
Metal nanoparticles are a clear example of how the properties of matter can change at the nanometre
scale. For instance, metal gold is notably yellow in color and used for jewelry. As the noblest of all
metals, gold is very stable (eg it does not react with oxygen or sulfur). However, if gold is shrunk to
a nanoparticle, it changes colour, becoming red if it is spherical (Figure 7) and even colorless if
it is shaped in a ring. Furthermore, gold nanoparticles become very reactive and can be used as
new catalysts (this is discussed in Module 2, Chapter 2: Environment).

Figure 7: Gold colloid is ruby-red, not golden!

Image: L. Filipponi, iNANO, Aarhus University, Creative Commons

Attribution ShareAlike 3.0

Plasmonic structures

Noble metal nanoparticles, meaning gold, silver, platinum and palladium nanoparticles, show localized
surface plasmon-resonances (LSPR), an effect that was described in Module 2, Chapter 4: Funda
mental 'nano-effects'. The energy of the LSPR depends on the particle shape, size, compos
ition, inter-particle spacing and dielectric environment. The surface of the nanoparticles can be
functionalized with numerous chemical and biochemical molecules enabling specific binding of organic
molecules such as antibodies, making them useful in sensors.

For this reason, they are of special interest for optical detection and sensing in analytical chemistry and
molecular biology. The refractive index can be used as the sensing parameter: changes in the local
dielectric environment, induced by the sensing process, are used to detect the binding of molecules in
the particle nano-environment. The change in aggregation between the nanoparticles as a result of
analyte attachment affects the LSPR energy, so this effect can be used for highly miniaturized sensors.
Figure 8 schematically illustrates these two LSPR-based detection methods.

Figure 8: Top: LSPR sensor based on a change in

refractive index induced by analyte attachment to a
functionalized surface; bottom: LSPR sensor based
on a change in nanoparticle aggregation induced by
attachment to functionalised nanoparticles

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Localized surface plasmons have been evaluated in a range of nanoparticle shapes such as disks, triangles,
spheres and stars. More complex structures have also been studied, such as holes in thin metal films,
nanoshells and nanorings. Based on nanostructured metallic surfaces, a variety of optical applications are
possible. An important feature of plasmonic structures is that they allow label-free detection, which is important
in optical sensing. Currently, plasmonic components are being evaluated with respect to future applications in
cancer therapy, solar cells, waveguides, optical interconnection, camera LEDs, OLEDs and more.

The application of metal nanoparticles in medical diagnostics and targeted

healthcare treatment is discussed in detail in Module 2, Chapter 1: Medicine
and targeted healthcare.

Reinforcements

Metal nanoparticles are used as reinforcement in alloys for applications in lightweight con struction
within the aerospace sector and, increasingly, the automotive sector. The method is used, for example, to
harden steel. For instance, titanium nanoparticles are used as an alloy compound in steel, and the resulting
material shows improved properties with respect to robustness, ductility, corrosion and temperature resistance.
Particles of iron carbide are also precipitated in steel to make it harder.
The nanoparticles block the movement of the dislocations in the crystalline material (this effect was
described in detail in Module 1, Chapter 4: Fundamental 'nano-effects') increasing the hardness.
The trade-off between steel strength and ductility is an important issue, since modern construction requires
high strength whereas safety and stress redistribution require high ductility. The presence of hard nanoparticles
in the steel matrix could lead to a material with a combination of these properties, effectively matching high
strength with exceptional ductility.

Environmental applications

Some forms of metal nanoparticles have important environment applications.

• Zero-valent (Fe0) iron nanoparticles are under investigation for the remediation of contam
inated groundwater and soil. Iron, when exposed to air, oxidises easily to rust; however, when
it oxidises around contaminants such as trichlorethylene (TCE), carbon tetrachloride, dioxins,
or PCBs, these organic molecules are broken down into simple, far less toxic carbon compounds.
Iron nanoparticles are more effective than conventional 'iron powder', which is already used to clean
up industrial wastes. Iron nanoparticles are 10 to 1 000 times more reactive than commonly used iron
powders.
• Silver nanoparticles have a strong antibacterial capacity. They are used in numerous products
to prevent or reduce the adherence of bacteria to surfaces.

Metal nanoparticles and their use in environment applications are covered

in Module 2, Chapter 2: Applications of nanotechnologies —
Environment.

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Nanocrystalline metals
Nanocrystalline metals are classic metals and alloys that have an ultra-fine crystalline structure below 100 nm. They
exhibit exceptional mechanical and physical properties which make them inter esting for many applications.
Examples of nanocrystalline metal materials are aluminum, magnesium, and Al-Mg alloys which offer high strength
and are lightweight. Other examples are titanium and Ti-Al alloys.

Some crystalline metals offer exceptional magnetic properties. An example is the Finemet®
nanocrystalline soft magnetic alloys, which consists of melt-spun Fe-Si-B alloys containing small
amounts of niobium and copper.

The application of nanomaterials in the field of magnetic materials is very important and promising, with applications
in magnetic recording, giant magnetoresistance, magnetic cooling and magnetic sensing. These novel materials are
composed of magnetic nanoparticles dispersed in a magnetic or non-magnetic matrix (particle-dispersed
nanocomposites) or of stacked magnetic thin films (magnetic multilayer nanocomposites).

Applications of nanostructured magnetic materials for memory storage

are discussed in Module 2, Chapter 4: Information and Communication
Technologies.

Ferrofluids
Ferrofluids are colloidal mixtures composed of ferromagnetic or ferrimagnetic nanoparticles (such as magnetite)
suspended in a carrier fluid, usually an organic solvent or water. The ferromagnetic nanoparticles are coated with a
surfactant to prevent agglomeration (due to van der Waals and mag netic forces). Although the name may suggest
otherwise, ferrofluids do not display ferromagnetism, since they do not retain magnetisation in the absence of an
externally applied field. Rather, they display bulk-like paramagnetism, and are often referred to as 'superparamagnetic'
materials due to their large magnetic conductivity. When a paramagnetic fluid is subjected to a adequate strong
vertical mag net field, the surface spontaneously forms a regular pattern of corrugations; this effect is known as the
normal-field instability (Figure 9).

Figure 9: Ferrofluid with a magnet underneath

Image: G. F. Maxwell, Wiki Commons, GNU Free documentation

license

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Students can see the fascinating properties of a ferrofluid through the

Ferrofluid activity — Activity 5 in the timefornano NanoKIT (http://www.
timefornano.eu/nanokit#ac06).

Ferrofluids have numerous applications: in mechanical engineering, particularly for vehicle

suspension and breaking systems, due to their low-friction properties; in the ICT area, as liquid seals
(ferrofluidic seals) around the spinning drive shafts in hard disks; and in the biomedical sector as drug carriers.

Ferrofluids are also fascinating to artists. An excellent video produced by

two Japanese artists for the timefornano video competition is available
online (http://www.youtube.com/user/timefornano#p/c/ B69761C355310861/0/
me5Zzm2TXh4), an example of 'Nano and Art' .

Shape-memory alloys
Most metals are very hard and take a lot of effort to deform, but once they have been molded into
shape, they will stay like that until another force changes them. Memory metals, or 'shape-memory
alloys' (SMAs) are different. They can be 'programmed' to remember a specific shape and if the metal
is bent or deformed, it quickly returns to its original configuration. This is because memory metal has
two distinct crystal structures at the nanoscale and can be made to flip between them. Both are
regular lattices. The so-called parent phase (or austenite phase) occurs when the metal is at higher
temperatures (Figure 10). When shaped at high temperatures the metal will 'remember' this shape.
As the metal cools, its crystal structure changes to the second (martensite) phase. Gentle heating of
the metal makes it return to its original parent shape.

TIP FOR TEACHERS: An analogy can be made between thermotropic liquid crystals (LCs) and
shape memory alloys: in both materials there is a change in nanostructure as its temperature is
changed, with a 'macroscopic' effect visible (ie a change in color in) the case of the liquid crystals,
and a physical deformation in the shape-memory). The two materials differ significantly in the type of
nanostructure involved: a 'soft' structure in the case of the liquid cystals (see 'Liquid crystals' in this
chapter) and a crystalline structure in the case of the memory-alloy.

Glasses made of memory metal take advantage of the phenomenon 'pseudo elasticity'. In this instance,
the metal is in its austenite phase at room temperature and the martensitic phase is brought about by
applying a stress, rather than cooling. When the stress is removed, the metal reverts to its austenite
phase and its associated shape. Nitinol is used in orthodontics for braces. Once the Nitinol is placed in
the mouth, its temperature rises to ambient body temperature causes it to contract back to its original
shape. This results in a constant force being applied to the teeth. Nitinol wires do not need retightening
as often as they can contract as the teeth move, unlike conventional stainless steel wires.

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Figure 10: Left: Crystal structures of the two phases in a memory-shape alloy; right: schematic
showing how the crystal lattice changes with temperature, 'remembering' its structure

Image: 'Memory Metal', Exploring the Nanoworld, University of Wisconsin-Madison (http://mrsec.wisc.edu/Edetc/back

ground/memmetal/index.html), Creative Commons Nano-Commercial Attribution ShareAlike 3.0

Students can see the properties of a memory-shape alloy through the

Memory Metal Activity — Activity 6 in the timefornano NanoKIT (http://
www.timefornano.eu/nanokit#ac10.TXh4).

Polymers
A polymer is a large molecule made of a chain of individual basic units called monomers joined together
in sequence. A copolymer is a macromolecule containing two or more types of monomers. When the
polymer is a good conductor of electricity, it is referred to as conductive polymer (or organic metal). In
this section, nanostructuring of polymers and the effect this can have on the properties of polymers are
described. The focus is on copolymers since these are extremely useful in nanotechnologies.

Conductive polymers
Polymers that are good conductors of electricity are called conductive polymers and include polyacetyl
ene, polyaniline, polypyrrole, polythiophene — many more have also been synthesized. These
polymers are characterised by their alternating double-single chemical bonds, so they are ÿ-conjugated.
The ÿ-conjugation of the carbon bonds along the oriented polymer chains provides a pathway for the
flow of conduction electrons and is thus responsible for the good electrical conduction properties
of the material. A detailed SEM analysis of conductive polymers has revealed that these are made of
aa sequence of metallic nanoparticles about 10 nm in diameter. The high conductivity of poly
mers such as polyacetylene and polyaniline is related to the nanostructure of the polymer.
Polyaniline and its analogues change color when a suitable voltage is applied, or when reacting

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with specific chemicals (electrochromic and chemochromic). For this reason, they are promising for use
in light-emitting diodes (LEDs). Other applications are the surface finish of printed-circuit boards,
corrosion protection of metal surfaces, semi-transparent antistatic coatings for electronic products,
polymeric batteries and electromagnetic shielding.

Block copolymers
A copolymer is a macromolecule containing two or more types of monomers and a block copolymer
composed of these basic units or monomer types together in long individual sequences called blocks.
An example is the diblock polymer (A)m(B)n, which is made of a linear sequence of m monomers of
type A joined together to a linear sequence of n monomers of type B. A transition section joints the two
blocks:

[end group]-[polyA]m-[transition member]-[polyB]n-[end group]

Often, block copolymers are made of a hydrophilic (water-attractive) block, and a hydrophobic
(water-repellent) block. In general, macromolecules having hydrophilic and hydrophobic regions, such
as lipids, self-assemble in ordered structures when in water: the hydrophobic region packs together,
avoid the water molecules, leaving the hydrophilic molecules to the exterior of the struc ture. In the
same way, block copolymers made of hydrophilic and hydrophobic blocks when mixed in a selective
solvent, such as water, can self-assemble into ordered architectures at the nanoscale level.

The geometry and degree of order of these structures depends on the concentration and the volume
ratio between insoluble and soluble blocks. Depending on these parameters, the block copolymer can
form spherical micelles (nanospheres), cylindrical micelles and membranes. Both cylindrical and
spherical micelles consist of a non-soluble (hydrophobic) core surrounded by a soluble corona.
Membranes are made up of two monolayers of block copolymer aligned to form a sandwich-like mem
brane: soluble block-insoluble block-soluble block. Molecules that, at low concentration, form spherical
aggregates will assemble into cylindrical and eventually membrane-like structures as the concentration
is increased (Figure 11).

Figure 11: Different geom

etries formed by block copoly
mers in selective solvent
conditions

Image: adapted from Smart et

al., Nano Today, 2008, 3:3–4, 38–
45, reprinted with the permission of
Elsevier, © 2008

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Among spherical micelles, if the lengths of the projections formed by the hydrophilic corona are short
compared to the sphere diameter, the nanostructure is called a 'hairy nanosphere', whereas if the
sphere is small and the projections long, it is called a 'star polymer' (Figure 12).

Figure 12: Sketch of a star polymer and a

hairy polymer

Image: L. Filipponi, iNANO, Aarhus University,

Creative Commons Attribution ShareAlike 3.0

Responsive 'smart' polymers

Block copolymers form nanostructures that are very sensitive to external fields. For example,
moderate electrical fields or shear stimulation can trigger macroscopic rearrangements in specific
directions. This is a versatile property for making materials that respond and change on demand.
The intrinsic macromolecular nature of these copolymers leads to very slow and kinetically controlled
phase transitions. Thus, metastable or intermediate phases have longer lifetimes, which is desirable in
applications that want to exploit the phase transition properties of these materials.

Biomedical applications

The ability of block copolymers to form nanoparticles and nanostructures in aqueous solutions makes
them particularly useful for biomedical applications, such as therapeutics delivery, tissue engineering
and medical imaging. In the field of therapeutic delivery, materials that can encapsulate and release
drugs are needed. Hydrogels are very useful for the controlled release of drugs and block copolymer
hydrogels are particularly advantageous for the possibility of conferring some stimuli-activated prop
erties, such as temperature-sensitivity. Block copolymers form nanostructures with both hydrophilic
and hydrophobic areas, so they can form vesicles that can encapsulate and carry both hydrophobic
and hydrophilic therapeutic agents. Micelles formed using block copolymers have a hydrophilic corona
that makes them more resistant to the interaction of proteins, in particular plasma proteins; therefore,
these types of micelles exhibit long circulation times in vivo. Insoluble domains can also be engineered
to exploit the sensitivity of specific hydrophobic polymers to external stimuli such as pH, oxidative
species, temperature and hydrolytic degradation.

Block copolymers are also of interest for preparing scaffolds in tissue engineering — for instance,
very long micelles that mimic the natural extracellular have recently been prepared exploiting the self
assembly properties of a peptide copolymer.

Nanoreactors

The ability to generate compartmentalised volumes at the nanometre level is one of the
fundamental mechanisms used by cells in synthesising biomolecules and performing the biochemical

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processes necessary for their functions. This motif is now reassembled using block copolymer micelles
and vesicles as nanoreactors. This approach has been employed incarrying enzymatic reactions in
nano-sized compartments.

It has been shown that this approach can also be extended into a non-aqueous solvent. For instance,
a recent work reports block polymer nanostructures in ionic liquid and the ability of micelles to shuttle
from an aqueous solvent to an ionic liquid as a function of temperature: this opens the way to using
block copolymer technology in more sophisticated synthesis routes.

Artificial moving parts

Block copolymers structures can also be used to mimic the ability of biomolecules to convert chemical
energy into mechanical energy, for instance by using a pH-sensitive block copolymer whose micelles
swell according to pH variation. Thus, these materials are being evaluated to create artificial muscles
or moving nanostructures.

Other applications

The application of block copolymers is not limited to the biomedical field. They can be used in
conjunctive with other materials to form block copolymer nanocomposites. For instance, star polymers
are used in industry to improve metal strength.

Finally, block copolymers can form nanoporous membranes for applications in filtering systems and
fuel cell technology.

Polymeric nanofibres
Nanostructured fibrous materials, or nanofibres, are an important class of nanomaterials, now readily
available due to recent developments in electrospinning and related fabrication technologies. In
contrast to conventional woven fabrics, they have the typical structure illustrated in Figure 13.

Figure 13: Typical sample of electrospun polystyrene

Image: T. Uyar, Interdisciplinary Nanoscience Center (iNANO),

Aarhus University, © 2008

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Nanofibres have some unique properties: they are highly porous (ie they have a large intercon
nected void volume in the range of 50% or even greater than 90% and possess a very high surface
to-volume ratio). It is possible to increase the mechanical stability of nanofibrous structures by
anneal ing the fabric so to join together the crossing points of those fibres. These properties make
nanofibrous scaffolds useful for many biomedical and industrial applications.

In addition, researchers have succeeded in making coaxial nanofibres composed on two different
polymers or composite coaxial fibres. Researchers are also trying to make aligned nanofibres.
These types of materials, especially if made of conducting polymers, could have important
applications for electronic and medical devices.

Nanofibres has a broad spectrum of applications as schematised in Figure 14.

Figure 14: Overview of polymer nanofibre applications

The two areas that have so far received most attention are the medical
field (eg wound healing membranes) and filtration applications. These
will be covered in Module 2, Chapter 1: Medicine and healthcare and
Module 2, Chapter 2: Environment). Nanofibres are also being
considered for composite material reinforcement. As nanofibres are a
relatively recent type of nanomaterial, it is expected that many more
applications will be explored in the future.

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Semiconductors
Semiconductors, unlike metals, have a band gap. The band gap is between the valence band and the
conduction band. In intrinsic semiconductors which possess no impurities (eg boron, germanium,
indium, silicon), there are no electronic states in the band gap. The properties of semiconductors, in
par ticular the band gap, are manipulated by the addition of dopants — impurities able to donate charge
carriers in the form of electrons (n-type) or holes (p-type).

As with metals, the reduction in the size of the semiconductor triggers the insurgence of novel physical
properties. The most obvious example is that of quantum dots.

Quantum dots
Quantum dots are made of semiconductor materials, such as CdSe, ZnSe and CdTe, about 10 nm in size.
As in the case of metal nanoparticles, electrons in quantum dots are localized in space.

A quantum dot (QD) has a discrete quantised energy spectrum, so it can absorb a specific wavelength
and emit a monochromatic colour. Depending on their size, QDs emit different colours, as shown
in Figure 15. The reason for this was explained in Module 2, Chapter 4: Fundamental 'nano-
effects': the width of the band gap is related to the size of the semiconductor , smaller sizes lead to
a blue shift in the emission spectra.

Figure 15: Ten distinguishable emission col

ours of ZnS-capped CdSe quantum dots
excited with a near-UV lamp: from left to right
(blue to red), the emission maxima are located
at 443, 473, 481, 500, 518, 543 , 565, 587,
610, and 655 nm

Image: Nature Biotechnology, 2001, 19:631–35, reprinted with the permission of Macmillan Publishers Ltd, © 2001

Quantum dots, like metal nanoparticles, hold great promise for nano
enhanced imaging which will bring progress to fields such as environmental
monitoring, medical diagnostics and treatment. Quantum dots are also
evaluated as novel light sources to improve LED technology and in solar
cell technology. These applications of QDs in the energy and ICT sectors
will be reviewed in Module 2, Chapter 3: Energy and Module 2, Chapter
4: Information and Communication Technologies.

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Semiconducting oxides
Semiconducting oxides like TiO2 and ZnO in bulk (macro) form are widely used in industry in many
products. When they are in a nanoscale form, they display interesting physical properties that allow
the design of new materials and the improvement of old. A short description of these properties follows.

Titanium dioxide

Titanium dioxide (TiO2 ) is a mineral mainly found in two forms: rutile and anatase. Titanium dioxide is
the most widely used white pigment because of its brightness (white colour) and very high refractive
index (n = 2.4). It is used in paints, plastics, toothpastes, papers, ink, foods and medicines. In sun
screens with a physical blocker, titanium dioxide is used both because of its high refractive index and
its resistance to discoloration under ultraviolet light. This is because TiO2 is a UV filter: it absorbs UV light.
Titanium dioxide, particularly in the anatase form, can be employed also as a photocatalyst under UV
light. It oxidises water to create hydroxyl (OH) radicals and it can also oxidise oxygen or organic mater
ials directly. For this reason, TiO2 is added to confer sterilising, deodorising and antifouling properties
to paints, cements, windows and tiles.

Titanium nanoparticles (30–50 nm, often referred to as nano-TiO2) are at the center of much
attention due to their optical and catalytic properties: they retain the ability to absorb UV light but light
scattering is dramatically reduced, so that TiO2 from appearing white to transparent (a detailed
explanation of this effect is given in Module 1, Chapter 4: Fundamental 'nano-effects'. Nano-TiO2
is thus suitable for transparent coatings, and for new-generation sunscreens, which are characterised
by a high protective factor but transparent appearance. The catalytic properties of TiO2 when nano
sized are also greatly enhanced by the large surface-to-volume ratio. This property is increasingly
used for chemical catalysis applications such as photocatalytic purification of water and air to
decompose organic pollutants (solar photocatalytic remediation) Thin films of TiO2 are used on
windows to confer self-cleaning properties on the glass (this application of nano-TiO2 nanoparticles
is reviewed in the section on nanocoatings).

ELSA and SAFETY TOPIC The use of nanoparticles in sunscreens is under much attention
because some environmental organizations, such as Friends of the Earth Australia, have sug
gested that the nanoparticles used in these products can pass through the skin barrier and enter
the blood, causing unnecessary harm. To support this statement, they refer to research published
on the toxicity of nano-titanium and nano-zinc oxide. These studies, though, often use amounts
and exposure conditions (eg injection or inhalation) which are very different from what consumers
of these sunscreens would be exposed to (cream rubbed on skin, amount and frequency of use,
skin washed after some time, sun exposures, etc.). Manufacturers claim that the nanoparticles
used in the sunscreen formula are agglomerated: therefore, they have dimensions that don't
allow for skin-penetration. Research seems to support this statement. Opponents reply that long-
term studies must be performed before this can be demonstrated, and that skin types vary from
person to person, not to mention cases of damaged skin, so generalizations are not possible yet
(studies are mainly done in vitro using healthy skin ). Overall, more research is called for by all
stakeholders, including regulators, to establish the safety of these products.

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Another important application of nano-TiO2 is in organic solar cells,

such as the Grätzel solar cell, where nano-TiO2 is used as acatalyst to
promote light-induced electrical charge separation. The use of titanium
dioxide in this type of solar cells is covered in more detail in Module 2,
Chapter 2: Environment.

One limitation of using TiO2 as a photocatalyst is that this material only absorbs UV light, which
represents about 5 % of the solar spectrum. In this context, nanotechnology could bring an improvement
in the form of nanoparticles with surfaces modified with organic or inorganic dyes to expand the
photoresponse window of TiO2 from UV to visible light.

NANOYOU DILEMMA The example of titanium dioxide in sunscreens is used in one of the NT
Virtual Dialogue debates (http://www.nanoyou.eu/en/decide). In this dilemma, students con sider
the case of sunscreens with nanoparticles and reflect on their advantages and possible
disadvantages.

Zinc dioxide

Zinc oxide (ZnO) has some similar properties to TiO2 (ie its nanoparticles scatter light so it can be used
for transparent UV filters, in creams or coatings). Like TiO2, it is used for solar photocatalytic remediation
but, compared to TiO2, it has a weaker photocatalytic effect. Zinc oxide also suffers from the same
limitation of absorbing only a fraction of the solar spectrum so research is underway to increase its photoresponse.

A peculiarity of ZnO is that it has a tendency to grow in self-organised nanostructures. By control

ling crystal growth conditions, a variety of crystal shapes are possible. Researchers have been able to
grow nanoscale wires, rods, rings, etc. (Figure 16). Zinc oxide nanocolumns are of particular interest
since low-temperature photoluminescence measurements have revealed intense and detailed ultra
violet light emission near the optical band gap of ZnO at 3.37 eV. Thus, ZnO can act as an optical
amplification medium and as a laser resonator.

Zinc oxide wires arrayed on a surface are also being evaluated as piezoelectric elements for mini-
aturized power sources. This would allow the creation of flexible, portable power sources that could
be included in textiles so that energy from body motion, light wind, air flow, etc., could be scavenged.

Figure 16: Patterned ZnO grown as

vertical pillars in an arrayed format

Image: Xu et al., Journal of the American Chemical Society, 2008, 130:14958–14959, reprinted with the permission of
the American Chemical Society, © 2008

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The use of ZnO for the development of miniaturized power sources is

described in detail in Module 2, Chapter 3: Energy.

Indium tin oxide

Indium tin oxide (ITO) is a semiconducting material whose main feature is the combination of elec
trical conductivity and optical transparency. ITO is typically around 90% indium(III)-oxide (In2O3 )
and 10 % tin(V)-oxide (SnO2 ). It is widely used in its thin-film form as transparent electrodes in liquid
crystal displays, touch screens, LEDs, thin-film solar cells, semiconducting sensors, etc. ITO is an
infra red absorber and is currently used as a thermal insulation coating on window glass. Its anti-
static properties make it additionally useful in applications such as the packaging and storage of
electronic equipment. Since the material is very expensive, alternative materials, such as fluorescent
tin oxides and aluminum zinc oxides are being considered. The use of ITO in 'smart coatings' is
further discussed in the section on nanocoatings.

Photonic crystals
A photonic crystal consists of a lattice of periodic dielectric or metal-dielectric nanostructures that
affects the propagation of electromagnetic waves. Essentially, photonic crystals contain regularly
repeating internal regions of high and low dielectric constant. Photons (behaving as waves) propagate
through this structure — or not — depending on their wavelength. The periodicity of the photonic crys
tal structure has to be of the same length-scale as half the wavelength of the electromagnetic waves
(ie approximately 200 nm (blue) to 350 nm (red) for photonic crystals operating in the visible part of the
spectrum ). Such crystals have to be artificially fabricated by methods such as electron-beam
lithography and X-ray lithography.

Photonic crystals exist in nature. For instance, in Module 1, Chapter 2: Nanoscience in nature it was
shown how the beautiful blue wings of some butterflies owe their color to their internal nanostructure,
which is in fact a photonic crystal structure.

Photonic crystals are receiving much attention at present because of their

potential, in particular in the optical communication industry. Research
ers are considering using light and photonic crystals (as an alternative to
electrons traveling in wires) for the new-generation integrated circuits. Light
can travel much faster in a dielectric medium than an electron in a wire, and
it can carry a larger amount of information per second. Given the greater
impact that semiconductor materials have had on every sector of society,
photonic crystals could play an even role in the 21st century. Photonics and
their impact in the ICT sector are analyzed in Module 2, Chapter 4:
Information and Communication Technologies.

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Ceramic and glassy materials

Ceramic materials by definition are ionically bound; they are hard materials, both electrically and the
mally very stable. Included in this category are, for example, Al2O3, Si3N4, MgO, SiO2, Na2O, CaO
and ZrO2. Ceramics are characterised by being hard yet brittle, therefore, in many cases, they are
used as composites where they are mixed with other materials (eg metals) to increase their
mechanical performance. Composite hard nanocoatings are particularly important for cutting tools
(see the section on intangible composites).

Ceramics exist both in a crystalline and non-crystalline form (eg the broad family of 'glass'). Nano
structures within the material have important consequences for their properties, as discussed in the
next sections.

Porous alumina
Porous alumina membranes produced by anodic aluminum oxidation are characterised by having hexa
gonally close-packed channels with diameters ranging from 10 to 250 nm or greater. This material is often
used as a template for the synthesis of other materials.

Zeolites
Zeolites are natural crystalline materials with pores having regular arrangements (Figure 17). They
are also often used in the template synthesis of nanomaterial. They can also be used to prepare
organ ised structures of a certain material to confer new optical properties on it. For instance,
selenium can be incorporated into the channels of mordenite, a natural zeolite. The difference
between a mordenite selenium crystal and a natural selenium crystal is noticeable: the optical
absorption spectrum is significantly shifted to higher energies for the mordenite-selenium crystal.

Figure 17: A schematic representation of a zeolite

Image: Wikimedia Commons, image for public domain

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Aerogels

Silicon dioxide (SiO2 ) is the main component of quartz. It is chemically robust and finds widespread
applications. In commercial products, it appears as an additive in rubber products for vehicle tyres but
it is also the component of new types of aerogels. Generally, an airgel is considered as a solid with up
to 95 % of the volume consisting of nanoscale pores. Aerogels are manufactured with a sol-gel
technique and can be made of carbon, metal oxide, polymers or silicates.

Due to their high porosity, aerogels have an extremely high surface area and very low thermal
con ductivity. Thus they are suitable for thermal insulation and as filter materials (Figure 18).
Another prominent property is their low specific weight, making them interesting for lightweight
construction . Aerogels are also interesting for their optical properties, specifically high optical transparencies.
Silica aerogels are made of pores of about 10 nm arranged in distances between 10 and 100 nm. They
are resistant and chemically inert to liquid metals, heat resistant up to 1 200 °C and non-toxic, thus
they have also biomedical applications, such as substrates for cell growth and analysis. One of the
problems of SiO2 aerogels that needs to be addressed is that this material has to be expensively pro
tected against humidity, since it is not water-resistant and suffers from a loss of stability and thermal
conductivity once it gets wet.

Figure 18: The thermal insulating properties of a silica airgel

Image: Wikimedia Commons, image for public domain

Carbon-based materials

In nature, there are some pure materials that have strikingly different properties even though they
are made up of the same atoms. For instance, graphite and diamond (Figure 19): two very popular
materials, one conventionally in pencils and the other in jewelry. These two materials could not be
more different: graphite is soft, light, flexible, and conducts electricity while diamond is extremely
strong, hard and does not conduct electricity. Both materials are made of carbon atoms linked
through strong bonds (covalent): in graphite, each carbon atom uses three out of its four electrons to
form single bonds with its neighbours, forming a linear sheet, whereas, in diamond, each carbon
atom uses all its four electrons to form four single bonds, resulting in a 3D structure. The different
properties of graphite and diamond are a consequence of the different way the carbon atoms in the
materials are bonded together.

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Figure 19: The two allotropes of carbon and

their respective chemical structure: (left, top
and bottom) diamond; (right, top and bottom)
graphite

Image: Wiki Commons, Creative Commons Attribution

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Graphite and diamond are two pure forms (allotropes) of carbon. In 1985, a new allotrope of carbon
was discovered of 60 atoms of carbons linked together through single covalent bonds arranged in a
highly symmetrical, closed shell that resembles a football. This material was officially named
Buckminsterfullerene and is often referred to as buckyball, fullerene or simply C60. Since its discovery,
fullerenes with 70, 80 and even more carbon atoms have been discovered.

In the early 1990s, an incredible new carbon form was discovered: carbon nanotubes. These appear
to be like graphite sheets rolled up with fullerene-type end caps, but have totally different properties
compared to graphite. Figure 20 shows different forms of carbon allotropes (images (d) and (h) are
structures of C60 and a nanotube, respectively).

Figure 20: Eight allotropes of carbon: (a)

diamond; (b) graphite; (c) lonsdaleite;
(d) C60; (e) C540; (f) C70; (g) amorphous
carbon; and (h) a carbon nanotube

Image: Michael Ströc, GNU Free Documentation

License

It is now known that fullerenes and carbon nanotubes form naturally in common places like
flames (produced by burning methane, ethylene and benzene) and in soot. Scientists have now
developed methods to synthesize these nanomaterials with control over their final properties.

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Another exciting carbon-based nanomaterial is graphene which is the basic constituent of graphite
(the material used in the lead of a pencil). Graphene is a layer of carbon atoms, just one-atom thick;
although the thinnest material ever made, graphene is the strongest material ever measured, some
200 times stronger than steel and it is also the most conductive. This material was isolated in 2004
by Andre Geim and Konstantin Novoselov (University of Manchester) who used adhesive tape to
repeatedly peel apart shavings of graphite until the pieces were just one atom. The scientists
evaluated the amazing properties of graphene and were awarded the Nobel Prize in Physics in 2010 for their studies
Scientists believe in the future graphene could be used to make super-fast transistors and incorporated
into plastics to make transparent electronics for flat panels and mobile phones.

Carbon nanotubes
Carbon nanotubes can appear as single-wall nanotubes (SWNTs), with a diameter of approximately 1.4
nm, or multi-wall nanotubes (MWNTs), consisting of 2–30 concentric tubes with an outer diameter of
30–50 nm. The structure of an SWNT can be conceptualised by wrapping a one-atom-thick layer of
graphite sheet (grapheme) into a cylinder. To complete the nanotube, imagine adding two half fullerenes
on each end of the nanotube.

Carbon nanotubes can range in length from a few tens of nanometres to several micrometres, and can
have metallic properties (comparable to, or even better than, copper) or can be semiconductors (such
as silicon in transistors), on their structure. These nanomaterials are truly amazing and have great
potential in numerous fields as illustrated in Figure 21.

Figure 21: Overview of application areas of carbon nanotubes

Image: M. A. H. Hyder, Master Thesis, Technical University of Hamburg-Harburg, Germany, reprinted with the permission
of the author, © M. A. H. Hyder, 2003

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The application of CNTs in the energy, environment, medicine and ICT sectors
are covered in the respective chapters in Module 2.

Mechanical properties

The chemical bonding of nanotubes is composed entirely of sp2 bonds (carbon double bonds) similar
to those of graphite (whereas, in diamonds, all bonds are sp3 ). This bonding structure, which is
stronger than the sp3 bonds found in diamonds, provides the molecules with their unique strength.
Nanotubes naturally align themselves into 'ropes' held together by van der Waals forces.

Theoretical predictions say that carbon nanotubes are 100 times stronger than steel but only one sixth of
its weight. Therefore, they are ideal in lightweight construction, for instance in the automo tive and aviation
industries. Carbon nanotubes are already used in some consumer products, such as tennis rackets to add
strength (without compromising weight).

The mechanical properties of carbon nanotubes are summarised in Table 1. Young's modulus is
a measure of how stiff, or elastic, a material is. The higher the value, the less a material deforms
when a force is applied. Tensile strength describes the maximum force that can be applied per unit
area before the material snaps or breaks. A third interesting measure of a material is its density,
which gives an idea of how light it is. From Table 1, it can be seen that wood is very light but weak,
whereas nanotubes are many times stronger than steel and yet much lighter.

Material Young's Modulus Tensile Strength Density

(GPa) (GPa) (g/cm3)
Single-wall nanotube 800 > 30 1.8
Multi-wall nanotube 800 > 30 2.6
Diamond 1 140 > 20 3.52

Graphite 8 0.2 2.25

Steel 208 0.4 7.8
Wood 16 0.008 0.6

Table 1: Properties of carbon alloptropes and other materials

Because of their mechanical properties, carbon nanotubes are very interesting as fillers in
polymeric and intangible composites.

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Electrical and thermal properties

The electrical properties of a material are based on the movement of electrons and the spaces or
'holes' they leave behind. These properties are based on the chemical and physical structure of the
material. In nanoscale materials, some interesting electrical properties appear. Carbon nanotubes are
the best example of this effect at the nanoscale. If one considers 'building' a nanotube by rolling up a
graphene sheet, the resulting nanotube can be conductive (and, indeed, very conductive!) or semicon
ductive with relatively large band gaps. The electrical properties of the nanotube depend on the way it
was 'rolled up' (technically known as chirality). If it is rolled up so that its hexagons line up straight
along the tube's axis, the nanotube acts as a metal (conductive). If it is rolled up on the diagonal, so
the hexagons spiral along the axis, it acts as a semiconductor.

Why is this so? Graphene (that is, one layer of graphite) is not an insulator, but also neither a metal
nor a semiconductor; it has electrical properties somewhere in between and is called a semi-metal.
When rolled up, it leads to a structure that is either metallic or semiconducting. On the other hand,
diamond has a tetrahedral structure (derived from the fact that carbons are hybridised sp3 rather than
sp2 as in graphene) and is an insulator.

One interesting property found in single-walled carbon nanotubes (SWCNT) is that electric conductance
within them is ballistic (which means that all electrons that go into one end of the conductor come out
the other end without scattering, regardless of how far they need to travel).

Researchers are also investigating whether nanotubes can be superconductors near room stamp
perature, meaning ballistic conductors that also exhibit a resistance of zero. A superconductor can
transport an enormous amount of current flow at tiny voltages. At present, known superconductors
work at very low temperatures. This field of research is very important since if a material were super
conductive at room temperature, it would carry current with no resistance, with no energy lost as heat.
This could lead to faster, lower-power electronics and the ability to carry electricity long distances with
100% efficiency.

Nanotubes as superconductors and their applications are further discussed

in Module 2, Chapter 3: Energy.

In terms of thermal properties, carbon nanotubes dissolved heat better than any other known
material and are excellent thermal conductors.

Chemical reactivity

Carbon nanotubes are very stable: they can withstand the attack of numerous chemicals and resist
exposure to a large temperature range. However, their chemical structure can be changed by the
addition of specific ligands with functional groups that allow interaction with different chemicals. This
allows them to be used in sensors.

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Applications

Carbon nanotubes are very promising materials for numerous applications (these will be described in
more detail in Module 2). Applications include: nanomedicine (drug delivery), environment (chemical
sensors), energy (supercapacitors, hydrogen storage materials, solar cells), ICT (integrated circuits,
electronic paper), advanced materials for construction, transport, sports equipment and more.

ELSA and SAFETY TOPIC Carbon nanotubes are an extraordinary material which could improve
numerous current materials, particularly some plastic composites, and be used in electronics and
sensing. The range of application is fairly broad so the question of their safety is important.
Carbon nanotubes are formed as nanometer-thin, long fibres, so the memory quickly goes back
to asbestos, their exceptional claimed properties, but also their late-found toxicity (they cause
cancer). Some recent research does suggest that carbon nanotubes, inhaled in large amounts,
can be significant toxic. As with other nanomaterials, though, the question of safety is more
complex: carbon nanotubes are used as composites, embedded with polymers or other mater
ials, so consumers would not be directly exposed to them (with the exception of workers in the
industry). But what happens when the product is disposed of and the material degrades? Is
waste containing carbon nanotubes safe? Should this waste be treated differently and undergo
special treatment? There is intense research to find answers to these questions, but time is needed.
Opponents advocate that until these answers are not found, products containing carbon nano
tubes should not be placed on the market, and workers should treat these as hazard materials
and wear the stringiest protection measures.

NANOYOU GAME Carbon nanotubes composites are used in one of the NANOYOU jigsaw
puzzle games (http://nanoyou.eu/en/play-nano.html) — students must match the nanomaterial
to its application, connecting it to a specific need.

Scientists have now developed methods to control the synthesis of carbon nanotubes to obtain regular
structures with specific properties. To date, though, the synthesis methods lead to moderate amount of
CNTs and mostly very limited length (of the order of millimetres). Often, these processes lead to CNTs
which are not totally pure (traces of the catalyst used in the synthesis are present in the product) and
this has been associated with toxicity issues of CNTs.

The cost associated with the production of carbon nanotubes is extremely high. In the future, this cost
must be considerably reduced to allow large-scale production and use of CNTs.

The structure of fullerenes resembles that of a football and youngsters can

familiarise themselves with this structure in a fun way using the Make your
own buckyball activity — Activity 4 in the timefornano NanoKIT (http://
www.timefornano.eu/nanokit#ac04) .

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Composites
The idea behind nanocomposites is to use building blocks with dimensions in the nanometre range to
design and create new materials with unprecedented flexibility and improvements in their physical
properties. This concept is exemplified in many naturally occurring materials, such as bone, which is a
hierarchical nanocomposite built from ceramic tablets and organic binders (see Module 1, Chap ter
2: Nanoscience in nature). When the nanocomposite, scientists can choose constitu ents with
different structures and composition and design, therefore, properties, so that materials built from them
can be multifunctional.

As a general definition, a nanocomposite is a conventional material reinforced by nanoscale particles

or nanostructures which are dispersed throughout the bulk material. The base material itself gener ally
consists of non-nanoscale matrices. Nanocomposites typically consist of an intangible (host) solid
containing an organic component or vice versa or two (or more) intangible/organic phases in some
com binatorial form. At least one component must be nano-sized. In general, nanocomposite materials
can demonstrate different mechanical, electrical, optical, electrochemical, catalytic and
structural properties which are different from those of the individual components. Apart from the
properties of the individual components, interfaces in a nanocomposite play an important role in
determining the overall properties of the material. Due to the high surface area of nanocomposites ,
nanocomposites present many interfaces between the intermixed phases and, often, the special
properties of the nanocomposite are a consequence of the interaction of its phases at interfaces. In
comparison, the interfaces in conventional composites constitute a much smaller volume fraction of
the bulk material.

In this chapter, nanocomposites are subdivided in two main groups: intangible nanocomposites, which
are characterised by an intangible matrix (eg ceramic) reinforced by nanoscale particles or
nanostructures of intangible (eg metal) or organic (eg carbon-based) nature; and polymer
nanocomposites, which are characterised by an organic matrix (eg polymer) reinforced by nanoscale
particles or nanostructures by intangible (eg clay) or organic nature.

Inorganic nanocomposites
High-performance ceramics are sought in many applications, such as highly efficient gas turbines,
aerospace materials, cars, etc. The field of ceramics that focuses on improving their mechanical
properties is referred to as structural ceramics.

Nanocomposite technology is also applicable to functional ceramics such as ferroelectric, piezo

electric, varistor and ion-conducting materials. In this case, the properties of these nanocomposites
relate to the dynamic behavior of ionic and electronic species in electro-ceramic materials. Among
these materials, in this document, the review is limited to nanocomposite with enhanced magnetic
properties.

Structural nanocomposites

now, even the best processed ceramics pose many unsolved problems such as poor resistance to
creep, fatigue and thermal shock; degradation of mechanical properties at high temperatures; and low
fracture toughness and strength. To solve these problems, one approach has been to incorporate

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a second phase such as particulates, platelets, whiskers or fibers in the micron-size range at the matrix
grain boundaries. However, the results obtained with these methods have been generally disappointing.
Recently, the concept of nanocomposites has been considered, where nanometre-size second-phase
dispersions are inserted into ceramic matrices. Large in both the fracture toughness and the strength
of a ceramic can often be improved with nanometre-range particles embedded in a matrix of larger
grains at their grain boundaries. These can involve the incorporation of a nano ceramic in a bulk
ceramic, a nano-metal in a ceramic, or a nano-ceramic in a metal. Another possibility is the
incorporation of a polymer in a ceramic. Without going into too much detail, the following are examples
of intangible nanocomposites that have improved structural properties.

• The incorporation of fine SiC and Si3N4 nanoparticles in an alumina matrix (Al2O3, a
struc tural ceramic material) first demonstrated the concept of structural nanocomposites.
The dispersion of these particles has been shown to improve the fracture toughness from
3 to 4.8 MPa m1/2 and the strength from 350 to 1 050 MPa at only 5 vol. % additions of SiC.
• One possibility for the fabrication of advanced ceramics is the dispersion of metallic second-
phase particles into ceramics which possesses their magnetic structural properties, such as
fracture toughness, and influences other properties including and optical properties.
Nanocomposites of this type are Al2O3/W or MgO/Fe. Granular films can also be made with
a ceramic phase embedded with nano-size metal granules (such as Fe/Al2O3, Fe/SiO2 ).
Such films often show unusual or enhanced transport, optical and magnetic properties.
The inclusion of nano-sized metals in a thin ceramic film can transform it from an insulator
to a conductive film.
• Another possibility is to add fine, rigid ceramic reinforcements to a ductile metal or alloy
matrix (metal matrix composites or MMCs). The reinforcement can be either in the form of
particles (eg silicon carbide, aluminum oxide), fibers (eg silicon oxide, carbon) or a mixture of
both (hybrid reinforcement). Materials produced by this method are particularly useful in the
aerospace, automotive and aircraft industries. The advantage of MMCs is that they combine
metallic properties (ductility and toughness) with ceramic characteristics (high strength
and modulus), leading to materials having greater strength to shear and compres sion and
to higher working temperature capabilities. The properties of MMCs are controlled by the size
and volume fraction of the reinforcements as well as by the nature of the matrix/ reinforcement
interface. The attention is now oriented towards the incorporation of nanopar tiles and
nanotubes for structural applications, since these materials exhibit even greater improvements
in the physical, mechanical and tribological properties compared to MMCs with micron-size
reinforcements.
• Nanoscale ceramic powders with carbon nanotubes provide another method for creating dense
ceramic-matrix composites with enhanced mechanical properties. For instance, hot pressed
alumina with mixed carbon nanotubes results in lightweight composites with enhanced
strength and fracture toughness compared to polycrystalline alumina.
The processing conditions greatly influence the properties of this material, though. In metal
matrix composites (MMCs), the incorporation of carbon nanotubes is considered very
promising since these materials have higher strength, stiffness and electrical conductivity
compared to conventional metals.

Nanocomposites with enhanced magnetic properties

Materials with outstanding magnetic properties are in high demand as these are employed in nearly all
important technical fields including electrical power, mechanical power, high-power electromotors,
miniature motors, computer elements, magnetic high-density recording, telecommunications, navigation,

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aviation and space operations, medicine, sensor techniques, magnetic refrigeration, materials testing
and household applications. Recent developments in the field of magnetic materials have involved
materials with a nanocrystalline structure or, in the case of thin films, layers of nanometre thickness.

Nanostructuring of bulk magnetic materials leads to soft or hard magnets with improved
properties. One example is the Finemet® nanocrystalline soft magnetic alloys, which consists
of melt-spun Fe-Si-B alloys containing small amounts of niobium and copper. When annealing at
tem peratures above the crystallisation temperature, the Fe-Si-B-Nb-Cu amorphous phase
transforms to a crystalline solid with grain size of about 10 nm. These alloys have excellent
magnetic induction and large permeability, and a very small coercive field.

Nano-sized magnetic powders can have extreme properties and have no hysteresis at any tem
perature. These materials are called superparamagnetic and one example is nano-sized powders of
a Ni-Fe-Co alloy.

Nanostructuring has also been studied in the context of hard magnets (permanent magnets). The
strongest known magnets are made of neodymium (Nd), iron and boron (eg Nd2Fe14B). In these
mater ials, it has been found that the coercive field said significantly below approximately 40 nm and
the remnant magnetisation increase. Another approach to improving the magnetisation curve of
permanent magnets has been to fabricate nanocomposites made of hard magnetic phases, such as
Nd2Fe14B and Sm2Fe17N3, within soft magnetic matrices (eg soft phase of iron). The effect of the
inclusion of a soft iron mixed in with a hard material is to increase the remnant field.

The grain size of the material also influences the magnetisation saturation point. For instance, the
magnetisation of ferrite increases significantly below a grain size of 20 nm. Thus, reducing the size
of the grains in the magnet increases the energy product (which is the product of magnetisation
and coercivity). The coercivity also increases with decreasing the grain sizes. In the case of
nanocomposite magnetic films, this is true if the grains are isolated (no interaction), but when the
grains are in contact and exchange interaction kicks in, the coercivity falls rapidly with grain size. The
coercivity is thus highest at percolation, when the grains just start touching each other. This effect is
important in the context of designing thin-film nanocomposites (magnetic multilayer nanocomposites),
for instance for high magnetic density recording.

Magnetic multilayer nanocomposites are becoming an essential component

of the new-generation data storage devices like magnetoresistive
random access memory (MRAM). This and other nanostructured devices
made of nanomagnets with applications in the ICT sector are discussed
in Module 2, Chapter 4: Information and Communication Technologies.

Polymer nanocomposites
Polymer composites are materials where a polymer is filled with an inorganic synthetic and/or natural
compound in order to increase several properties, such as heat resistance or mechanical strength, or
to decrease other properties, such as electrical conductivity or permeability for gases like oxygen or
water vapour. Materials with synergistic properties are used to prepare composites with tailored
characteristics; for instance, high-modulus but brittle carbon fibers are added to low-modulus polymers to create a stiff,

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polymer composite with some degree of lightweight toughness. Current polymer composites are really
filled polymers, since these materials lack an intense interaction at the interface between the two mixed
partners. Progress in this field has involved moving from macroscale fillers to micron-scale fillers, to
even smaller fillers.

In recent years, scientists have started to explore a new approach to the production of polymer com
posites with the use of nanoscale fillers, in which the filler is below 100 nm in at least one dimen
sion. Nanoscale fillers include: nanoparticles; nanotubes; and layered (also called 'plate-like')
intangible materials such as clays (Figure 22).

Figure 22: Schematic representation

of nanoscale fillers

Image: L. Filipponi, iNANO, Aarhus

University, Creative Commons Attribution
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Although some nano-filled composites have been used for more than a century, such as carbon-
black and fumed-silica-filled polymers, researchers have only recently started to systematically
produce and study these materials. The motivation has been the realisation of the exceptional
combined properties that have been observed in some polymer nanocomposites. This, together with
significant morphology development in the chemical processing of nanoparticles and in the in situ
processing of nanocomposites, has led to unprecedented control over the of these materials.

One of the most common reasons for adding fillers to polymers is to improve their mechanical
performance. In traditional composites, this often compromises the ductility of the polymer and, in
some cases, negatively affects its strength because of stress concentration caused by the fillers.
Well-dispersed nano-fillers, such as nanoparticles or nanotubes, can improve the modulus and the
strength and maintain (or even improve) ductility because their small size does not create large stress
concentration. For all nano-fillers, a key requirement is the homogeneous dispersion of the filler within
the polymer matrix. As discussed in the following sections, this is a challenge in many cases, and a topic
of intense research.

Although the scientific community has made remarkable progress in this field in the last years, poly
mer nanocomposites have just started to be explored, and many research questions still need to
be addressed. What is clear so far is that the use of nanoscale fillers opens the way for the
development ment of materials with exceptional properties. For instance, nanoparticles do not
scatter light signifi cantly, thus it is possible to make polymer composites with altered electrical or
mechanical properties that remain optically clear. Nanoparticles are also of interest not just for their
small size, but for their inherent unique properties. Carbon nanotubes, for instance, display the
highest values so far seen of elastic modulus, as high as 1 TPa, and strengths that can be as high as
500 GPa. This could allow, for example, the fabrication of polymeric composites with exceptional strength and flexibi

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Another outstanding property that the use of nanoscale fillers confers on nanocomposites is an
excep rationally large interfacial area. The increase of surface area below 100 nm is dramatic. The
interface controls the degree of interaction between the filler and the polymer, and is thus responsible
for the composite properties. Thus, the largest challenge in nanocomposite science is learning to
control the interface.

Nanoscale fillers can potentially allow the creation of a vast range of different polymeric materials
with advanced properties. In general, macroscopic reinforcement elements have the limitation of
always containing imperfections, but as the reinforcements become smaller and smaller, structural
perfec tion could be reached. The ideal reinforcements would have atomic or molecular dimensions and be
intimately connected with the polymer. The use of nanoscale fillers, however, also introduces a series
of fabrication challenges. Because of their small size and high surface area, nanoscale fillers such
as nanoparticles have a strong tendency to agglomerate rather to disperse homogeneously in a matrix.
This leads to particle-matrix mixtures with high viscosities, which can make the processing of those
materials quite challenging. The result is that even the most exciting polymer nanocomposites have
very low fractions of particle content, and relatively weak mechanical properties when compared
tothose predicted in theory. Therefore, polymer nanocomposites are an exciting type of advanced
materials that hold great promise in many application, but which are still mainly in a development stage.
The research efforts in this area suggest, however, that these materials will become more readily
accessible in the near future.

Nanoparticle-polymer nanocomposites

Nanoparticles are a type of nano-filler that offers the opportunity of developing polymers with new or
advanced properties. As already discussed, the size of a nanoparticle affects its properties: for instance,
gold nanoparticles have different optical absorption spectra depending on the particle size. One of the
advantages of using nanoparticles in polymer composites is that the particle size and distribution can
be tuned. Materials that cannot be grown easily as single crystals can be used at the nanoscale and
dispersed in a polymer to take advantage of the single-crystal properties.

In general, nanoparticle-filled polymers display better mechanical properties, at least at low volume
fractions and if well dispersed in the polymer. The reason is that nanoparticles are much smaller than
the critical crack size for polymers and thus do not initiate failure. Thus, nanoparticles provide a way
for simultaneously toughening and strengthening polymers. Proper dispersion is critical, however,
in achieving this.

The size scale of nanoparticle-polymer composites ranges from hybrid nanocomposites, in which the
polymer matrix and the filler are so intimately mixed that they are no longer truly distinct, to discrete
particles in a continuous matrix. Hybrid nanocomposites often arise from the use of block copolymers,
and this is discussed in the section on polymers in this chapter).

In terms of properties, the use of nanoparticles in filling polymers can influence not only the polymers'
mechanical properties, but also the polymers' mobility and relaxation behaviour, which, in turn, are
connected to the glass transition temperature of the polymer (Tg) (ie the temperature at which a
polymer becomes brittle on cooling or soft on heating). In general, adding well-dispersed, exfoliated
nano-filler increases the Tg of the polymer. Nanoparticle-filled polymers also show an increase in the
abrasion resistance of the composite.

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One of the most exciting prospects of using nanoparticles in polymer composites is to create com
posites with combined functionalities, such as electrically conducting composites with good wear
properties that are optically clear: this is possible because nanoparticles do not scatter light.

Carbon nanotubes printed polymer composites

Carbon nanotubes have very distinct properties compared to graphite, as summarised in Table 1 in the
section on mechanical properties. In the context of nanocomposites, SWNTs are the most promising
nanotube fillers. Some properties are particularly interesting: in particular their flexibility under
mechanical stress, behavior under high temperature conditions and electrical properties. As with other
applications that make use of carbon nanotubes, it has been observed that, in composites, the
processing conditions ultimately affect the properties of the nanotubes and, as a consequence, the
purity of the composite, as well as the purity of the nanotubes . Carbon nanotubes can also be doped,
for example with nitrogen and boron, which changes their surface reactivity. For instance, nitrogen
atoms inserted into the lattice of nanotubes makes them more dispersed in solution (carbon nanotubes
are insoluble in water). Modified nanotubes present different electrical and optical properties and
therefore their use could lead to composites with novel properties.

It should be noted that the inclusion of carbon nanotubes in a polymer does not definitely
improve its mechanical properties. Although, in theory, the modulus of nanotubes is much higher
than any graphite fibre, and therefore the composite should have outstanding mechanical properties, it
has been demonstrated that a number of variables influence this outcome. For SWNT composites, the
SWNTs are in a bundle; until SWNTs are isolated from the bundles or the bundles are cross-linked, the
modulus of composites made of these materials will be limited. For this reason, researchers are con
centrating on developing processing methods that make it possible to obtain significant volume frac
tions of exfoliated nanotubes. As will be discussed later regarding clay-polymer nanocomposites, the
structural arrangement of the nano-filler within the polymer is also important: if the nanotubes are not
straight when placed in the composite, the modulus of the significant composite.

Apart from the mechanical enhancement of polymers, nanotubes are also of interest for their
electrical properties. Carbon nanotubes are inherently more conductive than graphite.
It has been found, for instance, that nanotube-PPV composites show a large increase in electrical
conductivity, compared to simple PPV (poly(p-phenylene vinylene), of nearly eight orders of magnitude.
Recently, an improvement of 4.5 orders of magnitude in the electrical conductivity of nanotube-PVA
nanocomposites has been reported.

Finally, nanotube-polymer composites are promising in the context of light-emitting devices. These
devices were developed after the discovery of electroluminescence from conjugated polymer materials
(such as PPV). The practical advantages of polymer-based LEDs are their low cost, low operating volt
age, ease of fabrication and flexibility. Small loadings of nanotubes in these polymer systems are used
to tune the color of light emitted from organic LEDs.

Polymer-clay nanocomposites

In the late 1980s, it was discovered that adding 5 % by weight of nano-sized clays to Nylon 6, a syn
thetic polymer, greatly increased its mechanical and thermal properties. Since then, polymer-clay
nano composites have been widely studied and many commercial products are available. These
hybrid mater ials are made of organic polymer matrices and clay fillers. Clays are a type of layered
silicates that are characterised by a fine 2D crystal structure; among these, mica has been the most studied.

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Mica is made up of large sheets of silicate held together by relatively strong bonds. Smectic clays, such as montmorillonite,
have relatively weak bonds between layers. Each layer consists of two sheets of K+ and Ca2+. The presence of the cations is
silica held together by cations such as , Na+, necessary to
Li+ compensate for the overall negative charge of the single layers. The layers are 20–200 nm in
diameter laterally and come into aggregates called tactoids, which can be 1 nm or more thick. Naturally
occurring clays include montmorillonite (MMT) and hecrite, and their synthetic equivalents are saponite
and laponite respectively.

For these layered silicates to be useful as fillers in nanocomposites, the layers must be separated,
and the clay mixed thoroughly in the polymer matrix. This is not trivial as silicate clays are inher
ently hydrophilic, whereas polymers tend to be hydrophobic. The solution is to exchange the cations
that keep the layers in the silicate together with larger intangible ions that can thus open the galleries
between the layers (intercalation). When the silicate layers are completely separated, the material is
said to be exfoliated. In the case of intercalation, extended polymer chains are present between clay
layers, resulting in a multilayer structure with alternating polymer/clay phases at repeated distances of
a few nanometres: in the exfoliated state, the silicate layers are totally separated and dispersed in a
continuous polymer matrix.

As already mentioned, the fabrication of a polymer-clay nanocomposite requires mixing two

components that are intrinsically non-compatible. Surfactants are ionic, and thus interact well
with the clay, but not with the polymer. An ideal solution is the use of 'macro-surfactants' such as
block copolymers combining hydrophilic and hydrophobic blocks that can interact with the clay and
the polymer respectively. For instance, poly(ethylene oxide) (PEO) is an excellent intercalation material.

Although dispersion homogeneous of the filler in the polymer is an important parameter, another
important aspect is the packing (or alignment) of the filler in the polymer. To understand this
concept, it is useful to consider a natural nanocomposite, bone. The unique properties of bone are a
list of apparent contradictions: rigid, but flexible; lightweight, but solid enough to support tissue;
mechanic ally strong, but porous. In order to meet these different demands, bone has a hierarchical
structure that extends from the nanoscale to the macroscopic length scale. The hierarchical structure
of bone is responsible for its load transfer ability (see Module 1, Chapter 2: Nanoscience in nature
for details on the structure of bone). Nanoparticle-filled polymer composites have mechanical
properties that are actually disappointing compared to theoretical predictions, and this is due to the
difficulty in obtaining well-dispersed large volume fractions of the reinforcing nano and a lack
of structural control. Taking this into consideration, some scientists have recently reported the fab
rication of ultra-strong and stiff layered polymer nanocomposites. In this work, bottom-up assem bly
of polymer-claynanocomposite allowed the preparation of a homogeneous, transparent material,
where the clay nanosheets have planar orientation. It was found that the stiffness and tensile strength
of these multilayer nanocomposites are one order of magnitude greater than those of analogous
nanocomposites.

Nanoclays are also used as fillers in polymers to increase the thermal stability of polymers.
This property was first demonstrated in the late 1960s for montmorillonite-PMMA composites. The
dispersion of the clays is critical to increasing the thermal stability (that is, raising the degradation
temperature) of the polymer.

In addition to thermal stability, the flammability properties of many polymer-clay nanocomposites

are also improved. Combining traditional flame retardants with intercalated or, better, exfoliated clays
can result in further improvements in flame retardancy.

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Finally, polysaccharide-clay nanocomposites are a class of materials that are important especially to
the food industry. These composites make use of naturally occurring polymers, such as starch,
mixed with clay to make a biopolymer film with enhanced properties, in particular permeability to water
vapour.

Nanocoatings
Nanocoatings are a type of nanocomposite. The layer thickness of a nanocoating is usually 1–100 nm.
Nanocomposite films include multilayer thinfilms, in which the phases are separated along the thick ness
of the film, or granular films, in which the different phases are distributed within each plane of the film
(Figure 23).

Figure 23: Schematic of possible structures for nanostructured coatings: left: multilayered micro
structure (eg TiN/TiC) for nanocomposite coatings; right: homogeneous nanostructured coating
(eg NiCoCrAlY alloy)

Image: L. Filipponi, iNANO, Aarhus University, Creative Commons Attribution ShareAlike 3.0

Nanocoatings make it possible to change the properties of some materials, for example to change
the transmission of visible and IR radiation in glass, or to introduce new properties such as 'self-
cleaning' effects. Here, this first type of nanocoating will be discussed under the umbrella term
'responsive nanocoatings'.

Another important area of application of nanocoatings is tribological coatings. Tribology is the sci
ence and technology of interacting surfaces in relative motion. Tribological properties include friction,
lubrication and wear. Tribological coatings are those coatings that are applied to the surface of a
com ponent in order to control its friction and wear. In this area, the term 'thin films' is often used as
an alternative to nanocoatings — due to the fact that this is an area of innovation that has existed for
many years and has now reached the nanoscale.

Tribological nanocoatings
Tribological coatings play a key role in the performance of the internal mechanical components of a
vehicle, such as the engine and powertrain. They are also key elements in cutting tools and
machinery in general. By reducing wear and friction, these coatings increase the lifetime of the

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working material while also reducing the dissipation of energy as heat, thus increasing the efficiency
of the moving part. When applied to machinery and tools, tribological coatings can reduce (or
eliminate) the need for lubricants, increase cutting speed, increase the rate of material removal,
reduce maintenance costs or reduce processing cycle times.

Traditional materials used in coatings for tribological applications are carbides, cemented carbides,
metal ceramic oxides, nitrides and carbon-based coatings. Since the microstructure controls many
of the physical properties of the coating, having a nanoscaled microstructure may lead to significant
improvements in the mechanical properties of the coating (eg hardness), the chemical properties
(eg corrosion resistance) and the electrical properties. Thus, nanocomposite coatings are now
being Invested tigated as alternatives to the traditional approach of using specific alloying elements
in single-phase coating materials to improve, for instance, properties such as hardness. One type of
nanocomposite coatings is multilayered thin films made of different layers in the order of
nanometres. These films are mostly used for their enhanced hardness and elastic moduli, which is
higher in multilayered films than in homogeneous thin films of either component, and for their wear
properties. Commercial multilayer coatings made with multilayer periods in the nanoscale range
already exist, such as WC/C coatings used in the cutting tool industry. Other examples are films of
alternating layers of TiN and NbN, or TiAlN/CrN multilayers, which are more efficient than TiAlN films.

Responsive nanocoatings
Responsive nanocoatings are those where the properties of the material in the coating react to envir
onmental conditions, such as light or heat, either in a passive or an active way. These coatings allow
the properties of some materials to change, such as glass, by conferring new or improved properties.

The use of glass is very common in modern buildings, since it allows the construction of transparent
and lightweight structures. However, the relative high transmittance of visible and infrared (IR) light is
a major disadvantage, since this leads to a large heat transfer which is particularly undesir able in
summer. The problem is reversed in winter, when heat is dispersed through the glass. In order to
address these problems, various types of nanocoatings that modulate light transmission in glass
are under investigation and being commercialised. The aim is to reduce indoor heating in summer, so
less air conditioning is required to keep the atmosphere cool, with consequent energy saving. One
type of coating, referred to as 'low-e' (meaning 'low emissivity'), is based on a thin silver film, about 10
nm thick, surrounded by dielectric layers. Metallic layers have been widely used to increase the
reflectivity of light (and reduce transmittance) for years, but they have the disadvantage of giving a
mirror-like appearance. Silver its metallic appearance when scaled to a nano-film, thus eliminating this
problem. Such a coating is commercialised by Von Ardenne.

'Low-e' coatings are a type of passive nanocoatings, since the properties of the layers are undis
turbed during its operation. Another class of coatings used in glasses are those often described as
dynamic or 'smart coatings'. In this case, the environmental conditions, such as radiation intensity or
temperature, induce a change in the properties of the coating (eg darkening of windows). When the
effect is a change in the color (including a change to transparency), they are called chromo genic
smart materials. The change can be induced actively by pressing a button. This is the case of
electrochromic coatings where applying a small voltage induces a change in transmittance and in
the case of gaschromic coatings which change their transmittance in the presence of specific gases.
Gaschromic glazing makes use of the properties of tungsten oxide thin films (WO3) which go from
colourless to blue in the presence of hydrogen with a suitable catalyst. Gaschromic windows follow
a double pane model: on one pane a film of WO3 is enabling with a thin layer of catalysts on top.

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Hydrogen gas is fed into the gap producing colouration (windows color with 1.1–10% hydrogen, which
is below the flammability concentration). To switch the color of the window back, another gas is purged
(oxygen). Smart coatings can also be passive in the sense of changing their optical properties due to
a change of external temperature (thermochromic) or light incidence (photochromic). Another
example of nanotechnology applied to smart coatings is the use of a family of wavelength-selective
films for manufacturing 'heat mirrors'. One of these materials is indium tin oxide (ITO), an infrared absorber.
A 300 nm ITO coating on glass provides more than 80% transmission for the wavelengths predominant
in sunlight. The transmission properties of the window can be varied by changing the thickness and
material composition of the coating, so that a combination of materials could be used to produce smart
windows that reflect solar energy in summer but transmit solar energy in winter.

Superhydrophilic coatings
Another example of functional nanocoatings is photocatalytic coatings (commercialised as 'self
cleaning' glass) which use the catalytic properties of titanium dioxide (TiO2 ). When irradiated with UV
light, the coating becomes superhydrophilic: therefore, rain water adheres to the glass providing
'self cleaning'. Pilkington Activ™ Self-cleaning Glass is a commercial example of a glass with a
photocata lytic coating that renders the material easier to clean. Details of this product are given in
Module 2, Chapter 2: Environment.

Superhydrophilic coatings are also useful for rendering a surface fog-resistant. These coatings are
produced using a solution or a colloid that reduces the surface tension of the material (eg glass).
Substances that can be used as anti-fog agents include surfactants (eg soap), hydrogels, hydrophilic
nanoparticles and colloids. The anti-fog agent creates a thin film that does not allow the formation of
water droplets but rather 'forces' the water molecules to spread on the surface. This film reduces the
surface tension of the liquid (the surface tension is the result of the cohesive forces between the
molecules that are responsible for the formation of spherical droplets). In the case of water, its surface
tension is very high (and, for this reason, liquid water reduces to form droplet). The anti-fog agent
creates a superhydrophilic surface (very low contact angle) so that water sprayed on the surface
creates a thin layer instead of forming round droplets. The layer is so thin that it does not scatter light
— meaning that it appears transparent to our eyes. This is explained by the fact that the water
molecules are subjected to two different forces: inherent surface tension that adds to round off the
droplet, and bonding to the antifog nanoparticles that flattens them. Bonding to the surface occurs
through hydrogenbonds, weak forces that can become dominant when numerous. The result is a very
thin layer of water on the surface: the layer is so thin that it does not scatter light, so that it appears
transparent to our eyes and so we can see through it well. This type of technology helps prevent
goggles used for skiing or swimming steaming up.

Superhydrophobic coatings
The opposite to superhydrophilc coatings are superhydrophobic coatings, which totally repel water.
Droplets of water on these surfaces have very high contact angles and 'bead-up' forming nearly spher
ical droplets. Superhydrophobic coatings have surfaces that mimic the surface found in the lotus
leaf and are being developed for many applications that require resistance to dirt and ease of cleaning.
The details of the Lotus effect® are given in Module 1, Chapter 2: Nanoscience in nature while
examples of applications of these coatings are given in Module 2, Chapter 2: Environment.

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EXPERIMENT D in the NANOYOU Experiment Module investigates the

Lotus effect® in real plants and in innovative materials such as Nano-Tex®
fabric and nanoporous silicon.

A simple hands-on activity to show the superhydrophobic effect involves

Magic Sand — a product that creates a superhydrophobic assembly in
water. Details of the Magic Sand activity can be found in the timefornano
NanoKIT — Activity 6 (http://www.timefornano.eu/nanokit#ac07).

Superhydrophilic and superhydrophobic coatings are the opposite of the each other; however, they
share a common feature: they influence water adhesion and, therefore, influence surface
cleaning . Superhydrophilic coatings that use photocatalytic materials are often called 'easier to
clean' in the sense that rain spreads on the surface and reduces the effort needed for cleaning.
Superhydro phobic coatings are often defined as 'self-cleaning' since dirt cannot adhere easily to
the surface and the motion of the water droplet on the surface 'mechanically' cleans it (ie by rolling
on the surface and dragging the dirt away in doing so) ). It should be noted that, in both cases,
water is needed to achieve the cleaning (ie in situations where rain is scarce, these surfaces will not be so effective).

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CHAPTER 6:

CHARACTERISATION METHODS

'Seeing is believing' … therefore, imaging of nanomaterials is an essential part of nanoscience and

nanotechnologies. Imaging in nanoscience does not just mean 'to create an image', but to understand
its meaning. Scientists nowadays have access to a variety of truly amazing instruments that allow them
to see objects at the nanoscale. This was a dream for scientists until just a couple of decades ago, a
dream that came true in the mid 1980s when a revolutionary instrument was invented, the scanning
tunnelling microscope, and shortly after, the atomic force microscope. As a matter of fact, it was the
invention of these instruments that truly opened the doors to the nano-world. Once scientists were able
to see nanoscale objects, they started to be able to analyze them, understand their behaviour, and
imagine ways of manipulating them.

This chapter summarises some of the methods used for imaging and characterisation of nanomater
ials, meaning materials with at least one dimension atthe nanoscale level (1–100 nm). These include
nanostructured surfaces, nanoparticles, nanoporous materials, etc. The aim of this chapter is to answer
the question: How are nanomaterials imaged and characterised?

There are many methods available to image nanostructured materials (eg a nanostructured surface)
and to characterise their physical and chemical properties. Here, only a short review and description of
these methods is provided, but the interested teacher can find more resources at the end of the chapter.

In general, two fundamental types of characterization methods exist: imaging by microscopy and
analysis by spectroscopy. The methods employed have been specially developed to meet the
characterization needs of nanomaterials.

Microscopy
An optical microscope uses visible light (ie electromagnetic radiation) and a system of lenses to mag
nify images of small samples. For this reason, it is also called a light microscope. Opticals are the oldest
and simplest of the microscopes. The resolution limit of an optical microscope is gov erned by the
5
wavelength of visible light ( ). Visible light is the part of the electromagnetic spectrum
with wavelengths between 400 and 700 nm and the resolving power of an optical microscope is around
0.2 µm or 200 nm: thus, for two objects to be distinguishable, they need to be separated by at least 200
nm. Single objects smaller than this limit are not distinguishable: they are seen as 'fuzzy objects'.
This is known as the 'diffraction limit' of visible light.

In order to overcome the limitations set by the diffraction limit of visible light, other microscopes have
been designed which use other beams: rather than light, they use electron beams to illuminate

(5 ) As a general rule of thumb, the resolution is about half the wavelength used in the measurement.

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the sample. Electron microscopes have much greater resolving power than light microscopes that
use electromagnetic radiation and can obtain much higher magnifications of up to two million times,
while the best light microscopes are limited to magnifications of 2 000 times. Both electron and light
microscopes have resolution limitations, imposed by the wavelength of the radiation used. The greater
resolution and magnification of the electron microscope is because the wavelength of an electron (its
de Broglie wavelength) is much smaller than that of a photon of visible light.

There are various types of electron microscopes, such as the scanning electron microscope (SEM)
and or the transmission electron microscope (TEM). Conceptually, these microscopes are similar
to an optical microscope in the sense that they use radiation to visualize a sample: photons in the
case of an optical microscope, and electrons (ie particles) in the case of electron microscopes.

In 1981, a totally new concept of imaging was introduced by Binning and his co-workers from IBM.
They used a small metal tip placed at a minute distance from a conducting surface: when the two are
placed very close together, but not actually touching, a bias between the two can allow electrons to
tunnel through the vacuum between them. This creates a tunnelling current 6 ), which can be measured
( and which is a function of the electron density on the surface. Electron density is the probability of
finding an electron in a particular place: there is high electron density around the atoms and bonds in
molecules.

This type of microscope is called the Scanning Tunnelling Microscope (STM). Variations in current
as the probe passes over the surface are translated into an image. The STM can create detailed 3D
images of a sample with atomic resolution. This means that the resolution is actually so high that it is
possible to see and distinguish the individual atoms (0.2 nm = 2 * 10-10 m) on the surface. The
inven tion of the STM earned Binning and his co-worker Heinrich Rohrer (at IBM Zürich) the Nobel
Prize in Physics in 1986.

Scanning tunneling microscope

The STM is a fundamental tool in nanoscience and nanotechnologies. It is used in both industrial and
fundamental research to obtain atomic-scale images of metal and semiconducting surfaces (Figure 1).
It provides a three-dimensional profile of the surface roughness, It allows the observation of surface
defects and the determination of the size and conformation of molecules and aggregates.

Another astonishing property of the STM is that it can be used to manipulate (move!) individual atoms,
trigger chemical reactions, as well as performing electronic spectroscopy.

Operational principle of the STM

STM is a Scanning Probe Microscopy (SPM) technique. SPM provides images of surfaces by
scanning the surface line by line with a probe. Scanning works very similar to the way the blind read
Braille, line by line, by moving a finger over buds on the paper. In an STM, the probe is a very thin
needle called the 'tip' that is so small that its point is just a few atoms across. The tip is made of a
conducting material (eg metal, typically tungsten). The precise movement of the tip is controlled by a piezomotor.

( 6) For a definition and description of the tunnelling effect, see Chapter 4.

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Figure 1: Nanocatalyst used for cleaning sulfur from crude oil: this
STM image shows two molybdenum-disulfide nanoclusters consisting
of each of 15 Mo atoms and 42 S atoms.

Image: © iNANO

The tip of an STM is about 3 mm (3 * 10-3 m) long and should be located very close to the surface to
be scanned. In practice, the distance between the end of the tip and the surface must be less than
0.1 nm (10-10 m), without the tip actually hitting the surface. To visualize how small and precise this
is actually, it corresponds to placing the 300 m tall Eiffel Tower (3 * 102 m) top down with a distance
of 0.01 mm (1 * 10-5 m) over a neighborhood and scanning across it without actually touching it! (Figure 2).
One of the fundamental elements of the STM is the tip of the probe that scans the surface, which must
be sharpened to a very fine tip (Figure 3). The fabrication of sharper probes allows for better resolution
of surface features. commit, a probe tip sharpened to one atom would provide the best resolution.

Figure 2: Left: 3 mm tip positioned 0.1 nm above the

surface; right: macroscopic analogy: a 300 m high Eiffel
Tower located 0.01 mm above the city

Figure 3: SEM image of a tungsten tip for STM imaging

Image: reprinted from http://www.mse.engin.umich.edu/research/highlights/

electrochemical-etching-of-ultrasharp-tungsten-stm-tips

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When a conducting tip is brought very near to a metallic or semiconducting surface, at a distance of
about 0.1 nm, it can induce the formation of a tunnel current between the tip and the surface: a bias
between the two atoms (tip and surface) can allow electrons to tunnel through the vacuum between
them and induce the formation of a current. Variations in current as the probe passes over the surface
are translated into an image (Figure 4).

Figure 4: Schematic representation of STM scanning over a surface: (left) overview of an STM;
(right) close-up of the tunnelling effect between the tip of the probe and the surface atoms. The
intensity of the tunnel current depends on the distance d.

Image: Michael Schmid, TU Vienna, Creative Commons Attribution ShareAlike 2.0

As the conducting tip of an STM scans over a conducting or semiconducting surface, a 'tunnel current'
is formed, which arises from electrons jumping from the surface to the tip of the STM probe. The
probability of this happening depends significantly on the distance d between the surface and tip, thus
the size of the current depends on this distance. Small changes in the distance between the probe tip
and the substrate surface translate into large changes in tunnel current: atomic scale resolution by
STM is possible in the x, y and z directions due to this phenomenon.

How are images created?

One way of using the STM to image the surface of the substrate is to keep the tunnel current constant,
typically nanoamps (nA) (10-9 A) — by applying a constant tunnel current, the tip of the probe is kept
at a specific distance above the surface. When the tip scans a surface, it will rise when it scans over
an atom and drop when scanning between two atoms in the surface, as shown in Figure 5, where the
STM tip moves from left to right.

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Figure 5: Schematic representation of the

signal trace as a tip of an STM probe scans
a surface

Image: L. Filipponi, iNANO, Aarhus University,

Creative Commons ShareAlike 3.0

The movement of the tip can be transformed into a colored height map of the surface. This map
corresponds to an atlasmap, where each color indicates a specific height, as in Figure 6.

Using the STM, surfaces can be scanned by moving the tip in steps of 0.1 nm (10-10 m), thus providing
a very accurate representation of the surface. For the technique to work, it is necessary that, as the tip
scans the surface, a tunnel flow is induced. Thus, the surface must be conductive to some extent
(the substrate must be a conductor or semiconductor).

Figure 6: (A) model of two layers of graphite; (B) STM image of a graphite sheet (height scale on
the right, note how the image fits the model); (C) relief map of Denmark (height scale on the right)

Image: E. Lykkegaard Poulsen, Aarhus University, Creative Commons ShareAlike 3.0

If it is necessary to scan a surface which in itself is not electrically conductive, it can be coated with
a very thin layer of a conductive material such as gold. This does, however, imply that the STM is less
suitable for some studies (eg to study biological molecules such as DNA (which is not conduct ive)).
For these types of samples, other SPM techniques are more suitable, such as the Atomic Force
Microscope (AFM). An AFM does not measure the tunnel current, but the forces between the tip and

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the surface and, therefore, does not require the surface to be conductive. The AFM was developed in
1985, also by Binning and co-workers at IBM Zürich. It was developed specifically to image materials
that are insulating.

Atomic force microscope

The Atomic Force Microscope (AFM) was specially developed to overcome the intrinsic limitations of the
STM, which is not suitable for imaging surfaces coated with biological entities such as DNA or proteins. The
AFM operates in air and not under a vacuum. Some versions of the instrument also allow operation in liquid,
which is very advantageous when imaging biological samples that often need buffers to remain biologically
active.

Figure 7: Operation principle of an

AFM source

Image: http://www3.physik.uni-greifswald.de/
method/afm/eafm.htm

The AFM measures the interaction force (attractive or repulsive) between the probe and the surface.
The solid probe is located at the end of a very flexible cantilever; an optical system detects the deflec tion
of a laser beam that bounces off the reflective back of the cantilever, thus reporting cantilever fluctuations,
which are proportional to the applied force. The probe is continuously moved along the surface and the
cantilever deflection is constantly monitored. A feedback loop continuously changes the height of the probe
on the surface in order to keep the applied force constant. The vertical movement of the probe is recorded
to create a topographic map of the surface under study.

The AFM probe tip is very sharp, with a radius of curvature in the range of tens of nanometres. If the surface
under analysis is soft, the probe can penetrate it, with the risk of damaging it and degrading the spatial
resolution of the resulting micrograph. To overcome this limitation, instruments working in dynamic modes
have been developed. In these systems, the probe is not simply dragged on the surface but oscillated
vertically with respect to the surface while it is scanned. These techniques (tapping mode and non-contact
mode) significantly reduce the damage that can be caused by the probe and allow the imaging of soft,
compressible samples, such as biomolecules and cells.

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Figure 8: AFM image of an array of pyramidal wells (left) and pyramidal posts (right): the tips of the
posts are about 100 nm wide

Image: L. Filipponi, PhD thesis, 'New micropatterning techniques for the spatial immobilisation of proteins',
© L. Filipponi, 2006 Creative Commons Attribution ShareAlike 3.0

Figure 9: AFM image of DNA double strands

on a mica surface

Image: JPK Instruments AG

On the other hand, the tip of an AFM can be used to deliberately 'scratch' and remove some mol
ecules from a surface or to write with an 'ink'. Both are 'writing' methods in the sense that they
allow the creation of nanostructures on a surface with any geometry. This technique is called Dip
Pen Nanolithography® (DPN®) and is discussed in Chapter 7: Fabrication methods since it is a
fabrication method.

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Spectroscopy methods
Spectroscopy is defined as the branch of science that is concerned with the investigation and
measurement of spectra produced when matter interacts with or emits electromagnetic (EM) radiation.
Depending on the wavelength of the electromagnetic used and the type of interaction with matter that
occurs (absorption, scattering, etc.), different spectra are measured from which much information can
be inferred.

Next, the spectroscopy methods that are most relevant in the characterisation of nanomaterials
(particles and surfaces) are briefly reviewed.

X-ray methods
X-ray methods involve exciting a sample either with X-rays (creating more X-rays) or with electrons (creating
X-rays). X-rays can be also generated by bombarding a sample with alpha particles. The energy of emitted X-
rays is equal to the difference between the binding energies of the electrons involved in the transition. There
are various methods that use X-rays: X-ray fluorescence (XRF), X-ray diffraction (XRD), etc. In the context
of nanomaterials, the most important method is small-angle X-ray scatter ing (SAXS) analysis. Like XRD,
this method is based on the principle of scattering of X-rays. Diffraction of X-rays is a result of scattering from
atoms configured in regular arrays. In conventional XRD, only crystalline materials can be visualized, as it is
necessary to have a periodicity in the structure in the long-range, which nanomaterials lack (owing to their
size). XRD is used for bulk crystals. With SAXS, particle sizes of the order of 1–100 nm can be analyzed. The
method can be used to image powders in the dry state or suspended in a medium. The method can also be
used to measure the nanoparticle
size.

UV-visible plasmon absorption and emission

Metal nanoparticles, in particular gold and silver, are characterised by a plasmon resonance absorption
that gives rise to intensely colored solutions.

The fundamentals of the plasmon resonance effect are described in

Module 1, Chapter 4: Fundamental 'nano-effects'.

The absorption band is due to electrons confined at the particle surface that collectively oscillate at a
specific frequency, commonly referred to as the surface plasmon resonance frequency. As examples,
the plasmon band of a 20 nm silver (Ag) particle is centered at 395 nm, resulting in a yellow solution,
while a 20 nm gold (Au) particle absorbed at 520 nm resulted in a red solution. The plasmon
absorption effect occurs for particles up to approximately 50 nm in diameter and scales with particle volume.
Absorption can be in the visible and UV area of the spectrum. Particles can be visualized by absorbance
in solution at nanomolar and picomolar concentrations.

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Plasmon resonance light scattering

In larger metal nanoparticles (> 30 nm) another effect, light scattering, is observed. When illu
minated with white light, metal nanoparticles in the 50–120 nm diameter size range scatter light of a
specific color at the surface plasmon resonance frequency. This effect is called plasmon resonance
light scattering. As in the case of plasmon absorbance, light scattering scales with particle volume,
but the scattered light can be detected at much lower concentrations than absorbed light. For
example, light scattered by a solution of 80 nm diameter gold particles is detectable down to 5 fM
concentration (fM = 10-15 M). For this reason, metal nanoparticles are interesting materials for use
in techniques that rely on labeling (such as microarray technology).

Metal nanoparticles are also described in Module 1, Chapter 5: Overview

of nanomaterials and their application in the medical sector is described in
Module 2, Chapter 1: Medicine and healthcare.

Surface-enhanced Raman scattering

Metal surfaces with nanometre scale roughness have the property of amplifying the Raman
scattering signals of absorbed molecules. In simple terms, Raman scattering is the inelastic
scattering ing of photons. Normally, when light is scattered from an atom or molecule, it has the
same energy (frequency) and wavelength as the incident light (Rayleigh scattering). This is an elastic scattering.
However, a small fraction of the scattered light (approximately 1 in 10 million photons) is scattered
by excitation, with the scattered photons having energy (frequency) different to the frequency of the
incident photons. Metal surfaces with nanoscale roughness increase the Raman scattering of
molecules absorbed on them. This effect is due to chemical and electromagnetic factors, as well as
increased sur face area. The details of this effect will not be considered here: what is important is
that the surface enhanced Raman scattering (SERS) effect can induce a signal enhancement of up to 108 times.
In one specific case, it has been possible to achieve a Raman enhancement effect of 1015 times! This
means that the SERS effect makes it possible to push the detection limit of surface detection tech
niques. The SERS signal depends on the characteristics of the nano-substrate: the size, shape, orien
tation and composition of the surface nano-roughness. Advancements in SERS technology will allow
detection at the atomole (10-18 mol) level, and single molecule detection.

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Non-radiative and non-electron

characterization methods

There are numerous methods used to characterise nanomaterials which do not rely on the use of EM
radiation. They include methods to determine particle size, surface area and porosity; thermo dynamic
methods (such as thermogravimetric analysis, TGA) to evaluate the temperature dependence of the
nanomaterial (melting, etc.); and mass spectroscopy, to determine the chemical composition of the
nanomaterial. An important surface method is the quartz crystal microbalance (QCM), which can
measure mass changes as small as a few nanogrammes per square centimeter. This is sensitive
enough to detect monolayers of using materials. It can be used to measure the amount of metal
absorbed on a surface after sputtering or evaporation, or to measure the amount of protein absorbed
on a surface. Due to this great sensitivity, the QCM is used in the design of biosensors.

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CHAPTER 7:

FABRICATION METHODS
This chapter summarises some of the methods used in the fabrication of nanomaterials, meaning
materials with at least one dimension at the nanoscale level (1–100 nm). These include nanostructured
surfaces, nanoparticles, nanoporous materials, etc. The aim of this chapter is to answer the questions:
How are nanomaterials made? What fabrication tools are used in nanoscience and nanotechnologies?

Methods for fabricating nanomaterials can be generally subdivided into two groups: top-down meth
ods, and bottom-up methods. In the first case, nanomaterials are derived from a bulk substrate and
obtained by the progressive removal of material, until the desired nanomaterial is obtained. A simple
way to illustrate a top-down method is to think of carving a statue out of a large block of marble.
Printing methods also belongs to this category. Bottom-up methods work in the opposite direction: the
nanomaterial, such as a nanocoating, is obtained starting from the atomic or molecular precursors and
fought assembling it until the desired structure is formed. The method resembles building with Lego®
bricks.

In both methods, two requisites are fundamental: control of the fabrication conditions (eg energy of the
electron beam) and control of the environment conditions (presence of dust, contaminants, etc.).
For these reasons, nanotechnologies use highly sophisticated fabrication tools that are mostly operated
in a vacuum in clean-room laboratories.

Top-down
Numerous top-down fabrication methods used in nanotechnologies are derived from the fabrication
methods used in the semiconductor industry to fabricate the various elements of computer chips (inte
grated circuits). These methods are collectively called lithography and use a light or electron beam to
selectively remove micron-scale structures from a precursor material called resist. In recent years,
there has been a tremendous push to reduce the size of electronic devices and integrate more func
tions into them, which has been possible thanks to the advances in lithographic fabrication methods.
Nowadays, it is possible to obtain single features below 100 nm (the transistors in latest generation
processors are about 45 nm). Therefore, in the semiconductor industry, nanostructures are routine
fabricated. Lithographic methods that are capable of producing nanoscale features are reviewed in the
next section.

There are many more methods to fabricate nanostructures top-down; here, the discussion is limited to
the most common methods.

Conventional lithography

Lithography includes a series of fabrication techniques that share the principle of transferrin an
image from a mask to a receiving substrate. A typical lithographic process consists of three
successive steps: (i) coating a substrate (Si wafer or glass) with a sensitive polymer layer (called a resist);

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(ii) exposing the resist to light, electrons or ion beams; (iii) developing the resist image with a suitable
chemical (developer), which reveals a positive or negative image on the substrate depending on the
type of resist used (ie positive tone or negative tone resist). In conventional micro-fabrication used in
the semiconductor industry, the next step after lithography is pattern transfer from the resist to the
underlying substrate. This is achieved through a number of transfer techniques, such as chemical
etching and dry plasma etching.

Lithographic techniques can be broadly divided into two groups.

1. Methods that use a physical mask, where the resist is irradiated through the mask which is in
contact or in proximity with the resist surface. These methods are collectively called mask
lithography, among which photolithography is the most used.
2. Methods that use a software mask, where a scanning beam irradiates the surface of the resist
sequentially, point by point, through a computer-controlled program where the mask pattern is
defined. These methods are collectively called scanning lithography.

The main difference between mask and scanning lithography is speed: whereas mask lithography is a
parallel, fast technique, scanning lithography is a slow, serial technique. Another important difference
is resolution which, in general terms, is higher for scanning methods. The price paid for higher resolution
is the use of more energetic radiation sources, which entails expensive equipment.

Photolithography

Photolithography uses light (UV, deep-UV, extreme-UV or X-ray) to expose a layer of radiation-sensi
tive polymer (photoresist) through a mask. The mask is a nearly optically flat glass (or quartz, depend
ing on the light used) plate which contains the desired pattern: opaque areas (the pattern, made of an
absorber metal) on a UV-transparent background. The image on the mask can be either replicated as
it is, placing the mask in physical contact with the resist (contact mode photolithography) or reduced,
usually by a factor of 5 or 10, and projected to the resist layer through an optical system ( projection
mode photolithography) (Figure 1).

The resolution of contact mode lithography is typically 0.5–0.8 ÿm when UV light (360–460
nm) is used. Higher resolutions cannot be achieved due to the inability to reduce the gap between
the mask and the flat substrate below approximately 1 µm, even when elaborate vacuum systems
are used to hold the two parts together. To produce patterns with higher resolution, projection
photolithog raphy or 'next-generation photolithography' techniques (ie extreme UV and X-ray
photolithography) need to be employed. These technologies use very expensive equipment and,
therefore, their use is limited to selected applications (such as photomask fabrication). The
equipment needed is available only in specialized laboratories.

Scanning lithography

Energetic particles such as electrons and ions can be used to pattern appropriate resist films
leading to features with nanometre resolution. When using electrons, the technology is called electron
beam lithography (e-beam), whereas using ions, the technology is called focused ion beam lithog
raphy. Finally, a recently established technology uses nanometre scanning probes for patterning resist
films and is therefore referred to as Scanning Probe Lithography (SPL). This technology has been
extended to the deposition of a nanoquantity of material (Dip Pen Nanolithography® or DPN®).

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Figure 1: Conventional use of photolithography in the semiconductor industry for the fabrication of
elements used in integrated circuits (eg computer chips). A photoresist is exposed on a silicon
wafer, and the exposed area selectively removed with a developer.
The resulting pattern can be used as a 'mask'for chemical etchingor as a pattern where a metal is
selectively.

Image: L. Filipponi, PhD thesis, 'New micropatterning techniques for the spatial immobilisation of proteins',
© L. Filipponi, 2006, Creative Commons Attribution ShareAlike 3.0

E-beam lithography

In a typical e-beam lithography process, a tightly focused beam of electrons scans across the surface
of an electron-sensitive resist film, such as poly(methyl methacrylate) (PMMA). The main advantage of
e-beam lithography over photolithography is its high resolution: patterns with features as small as 50
nm can be routine generated. The resolution of this technology is mainly determined by the scattering
of the electrons in the resist film and the substrate. When using particles with a mass higher than
electrons, however, this effect is significantly reduced. Focused ion beam lithography works on the
same principle of e-beam lithography, but ions such as H+ , He++, Li+ and Be++ are used. Both
techniques provide a resolution much higher than photolithography but share a main disadvantage:
both are serial techniques, very slow in process, so their use is mostly limited to producing photomasks
in optical lithography.

Soft lithography
Soft lithography is the name for a number of techniques that fabricate and use a soft mold prepared by
casting a liquid polymer precursor against a rigid master. These methods have been developed
specifically for making large-scale micro and nanostructures with equipment that is easier

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to operate compared to those used in 'conventional' lithography, cheaper and also available in
biological laboratories. Figure 2 shows the general principle of soft lithography.

Figure 2: Overview of a soft lithography replica

tion process. A silicon master is replicated with
PDMS. The pre-polymer is poured (it is a very
vis cous liquid) over the master and cured at 65
°C for two hours (temperature and curing time
can be adjusted). The polymer solidifies but
remains very flexible. The PDMS mould is then
peeled off from the master, and a negative copy obtained.
AFM images of the master and the PDMS replica
are shown in Figure 3.

Image: L. Filipponi, PhD thesis, 'New micropatterning

techniques for the spatial immobilisation of proteins',
© L. Filipponi, 2006, Creative Commons Attribution
ShareAlike 3.0

Figure 3: AFM image of an array of pyramidal wells in a silicon master (left) and pyramidal posts in a
PDMS replica (right)

Image: L. Filipponi, PhD thesis, 'New micropatterning techniques for the spatial immobilisation of proteins',
© L. Filipponi, 2006, Creative Commons Attribution ShareAlike 3.0

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The resolution of soft lithography is mainly determined by van der Waals interactions, wetting and
kinetic factors such as filling the capillaries on the surface of the master, but not by optical diffraction.
This is an important advantage over 'conventional' lithographic techniques. The master is normally
fabricated via a conventional lithographic method.

Various polymers (eg polyurethanes, epoxides and polyimides) can be used for molding: most com
monly, the elastomer poly(dimethylsiloxane) (PDMS) is used. PDMS is non-toxic so it can be used
safely with biological materials, including live cells. This is a big advantage in devices that aim to
integrate nanostructures with biological systems.

A PDMS mold is fabricated by pouring its liquid precursor over a lithographically-made master (eg a
photoresist or silicon master), cured to induce cross-linking, and then peeled off. The stamp can then
be used either for printing a desired material (the 'ink') from the stamp to a suitable surface (micro
contact printing, µCP) or, when in contact with a flat or curved surface, to define physical constraints
where a liquid can be confined.

Nanocontact printing

Microcontact printing is useful for patterning features with lateral dimension of 500 nm or larger. One of
the major challenges for µCP has been to achieve the capability to print with high resolution (ie with
lateral dimension lower than 100 nm). This has recently been achieved by improving the stability of
the PDMS, which, being soft and highly compressible, has a tendency to deform and collapse. One way
to improve the stability of the patterns is to fix a stiff backplane to the stamp or to change the chemical
formulation of the stamp itself, in order to obtain a harder polymer. With these modifications, it is now
possible to print features as small as 50 nm. This printing method, which uses harder stamps, is called
nanocontact printing (nCP).

Nano-imprint lithography
The concept of nano-imprint lithography is to use a hard master with a 3D nanostructure to mold
another material, which assumes its reverse 3D structure. Imagine taking a Lego® block and pressing
hard on a piece of Play-Doh. Since the master has a fine nano-structure, to be successful, the process
must be done under pressure, a coating must first be placed on the master to avoid catastrophic
adhesion to the mould, and the mold must be heated (above its Tg temperature ) in order to be soft
enough to completely enter the fine master nanostructure and be effectively replicated. The method is
the equivalent of embossing at the nanoscale and requires specialised equipment.

Nanosphere lithography
In nanosphere lithography, an ensemble of nanospheres ordered on a surface is used as a mask
(Figure 4). The nanospheres are dispersed in a liquid (ie a colloid) and a droplet placed on a surface
and left to dry. Depending on the surface properties (eg charge) and media used in the colloid (eg
presence of electrolytes) the nanosphere will self-assemble in an ordered pattern. In some conditions,
a colloidal crystal is obtained: each nanoparticle is surrounded by six other nanospheres. This regular
arrangement (which is a 2D colloidal crystal) can be used to create ordered structures on surfaces.

TIP FOR TEACHERS: To illustrate this in class, take a number of spherical beads and pour them onto
a shallow plate. The beads will self-organise in the same way.

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Figure 4: Nanosphere lithography: SEM images of a latex nanosphere mask (2 µm SiO2 beads)
(left) and triangular gold nanoprisms (right) obtained by evaporating gold over the colloidal mask
(nanosphere lithography)

Image: R. Ogaki, iNANO, Aarhus University, © 2008

In the regular arrangement of nanospheres, there will be an empty space between them, which is
regularly repeated over the entire surface. In the simplest method, this space is employed to create
relatively flat nanopatterns on the surface. The nanosphere pattern is used as a mask, and a material
(eg gold, silver) sputtered on top of it. Once the nanospheres are removed, a regular pattern of 'dots'
is left, each shaped like a triangle but with concave sides.

The gold pattern (dots) can also act as growth sites, for example for the growth of carbon nanotubes
or ZnO. The result is a regular array of nanotubes or nanowires, as shown in Figure 5.

Nanosphere lithography has now evolved into a method that allows the fabrication of very complex
arrays of nanostructures, including 3D features with small holes in them.

Figure 5: Top and 30° view of aligned ZnO nanorods, where the hexagonal pattern is apparent: (d)
aligned ZnO nanorods at the edge of the growth pattern

Image: Wang et al., Nano Letters, 2004, 4(3):423–6, reprinted with the permission of the American Chemical Society,
© 2004

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Colloidal lithography
Colloidal lithography shares the same principle of nanosphere lithography by using a colloid as a
mask for the fabrication of nanostructures on surfaces (Figure 6). In this method, electrostatic forces
are employed to obtain short-range ordered arrays of nanospheres on the surface.

The array can then be used to create a number of different nanostructures, through various processes
such as etching, lift-off, etc.

Without going into details of the method, what is interesting to note is the different types of nano
structures that can be formed: holes, cones, rings, 'sandwiches' made of different materials, etc.
(Figure 7).

If made of metals, these nanostructures present a localized surface plasmonic resonance effect (LSPR)
which can be used for sensing. These materials are therefore under study for various sensing
applications (eg for medical devices).

Figure 6: (left) effect of increasing the electrolyte concen

tration in the formation of the ordered array; (right) general
principle of colloidal lithography

Images: D. Sutherland, iNANO, Aarhus University

Figure 7: Summary of the various

nanostructures that can be formed as
regular arrays on surfaces

Image: D. Sutherland, iNANO, Aarhus

University

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Scanning probe lithography

Scanning probe microscopy (ie STM, AFM, etc.) uses small (< 50 nm) tips to image surfaces with atomic
resolution (these methods are described in Module 1, Chapter 6: Characterisation methods). This
ability suggests opportunities for their use in generating nanostructures and nanodevices. In this form,
they are referred to as Scanning Probe Lithography (SPL), which uses the tip of an AFM to select
ively remove certain areas on a surface and Dip Pen Nanolithography® (DPN®), which, similarly, uses
the AFM tip to deposit material on a surface with nanometre resolution (Figure 8).

Figure 8: (left) The operation principle of DPN: the A is coated with a liquid containing the tip
molecules to be conveyed and as the tip scans the surface, the molecules are forms through the
water meniscus between the tip and the surface ; (right) part of the famous speech 'There is plenty
of the room at the bottom' by Professor RP Feynman written with SPL

Images: (left) reprinted from 'Small science gets to the heart of matter', Science and Technology Review, 2001; (right)
C. Mirkin, Northwestern University

Both are direct writing techniques and their main advantages are high resolution and the ability to
generate patterns with arbitrary geometries. Like e-beam and ion-beam lithography, SPL and DPN are
serial techniques whose main limitation is speed.

Writing 'atom by atom'

A particular feature of an STM is that it can be used for more than just to visualise atoms. Twenty years
ago, researchers at IBM were able to demonstrate that they could use the STM tip to carefully move
atoms on a surface and write the company logo with atoms, as shown in Figure 9.

If one were to write using atoms, letters would be around 1 nm each. With letters of this size, the
whole of Encyclopaedia Britannica could be reproduced in an area as small as the tip of a human hair
(10-4 m2 ). Indeed, with letters of this size all the world's books would fit on a single A4 sheet, but it
would take incredibly long to write, and in addition they could only be read with the STM.

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Figure 9: Actual sequence of STM images as reported in

the original paper that demonstrated for the first time that
writing with the STM is possible

Image: D. M. Eigler., E. K. Schweizer, 'Positioning single atoms with

a scanning tunnelling microscope', Nature, 5 April 1999, Vol. 344,
reprinted with the permission of Macmillan Publishers Ltd, © Nature
Publishing Group, 1999

however, the ability to move individual atoms using an STM has great potential for the future
generation of data storage devices. Today, data is stored on CD-ROMs using minute 'bits' of semi
conductors around 0.1 µm (10-7 m) in size. If these bits were written with atoms instead, far greater
data capacity would be achieved. One of these 'nano-CDs' with 'atomic bits' could contain as much
information as one million current CD-ROMs.

The STM allows a material to be built atom by atom independently of its chemistry and physics, as
shown in Figure 10. This can lead to new materials that most likely have completely new properties.
The process is still very slow, since the atoms can be moved only manually, and this must be one atom
at a time. Mass production of new nano-materials using this method is thus not yet possible.

Figure 10: This corral is an artificial structure created

from 48 iron atoms (the sharp peaks) on a copper
surface. The wave patterns in this scanning tunneling
microscope image are formed by copper electrons
confined by the iron atoms

Image: D. Eigler, IBM Almaden Research Center, NISE Network

(http://www.nisenet.org), reprinted under NISE Network Terms
and Conditions

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Bottom-up
Bottom-up methods can be divided into gas-phase and liquid-phase methods. In both cases, the
nanomaterial is fabricated through a controlled fabrication route that starts from the single atom or
molecules:

•gas-phase methods: these include plasma arcing and chemical vapour deposition;
•
liquid phase: the most established method is sol-gel synthesis; molecular self-assembly is
emerging as a new method.

Plasma arcing
This is the most common method for fabricating nanotubes. The method uses a plasma which is an
ionised gas. A potential difference is placed between two electrodes and the gas in between ionises.
A typical arcing device is made of two electrodes, and an arc passes from one electrode to the other.
The first electrode (anode) vaporises as electrons are taken from it by the potential difference. For
instance, a carbon electrode is used to produce carbon nanotubes and this is consumed during the
reaction, producing carbon cations. These positively changed ions pass to the other electrode, pick up
electrons and are displayed to form nanotubes.

Plasma arcing can also be used to deposit nanolayers on surfaces rather than making new structures.
The deposit can be as little as a few atoms in depth (and must be at least 1 nm thick to be consid ered
a nanomaterial). In this sense, plasma arcing is complementary to chemical vapour deposition
(described next).

Chemical vapour deposition

In this method, the material to be showing is first heated to its gas and then allowed to deposit as a solid on
a surface. This method is normally performed under vacuum. The deposition can be direct or through a
chemical reaction so that the material shows is different from the one volatilised. This process is routine used
to make nanopowders of oxides and carbides of metals if carbon or oxygen are present with the metal. The
method can also be used to generate nanopowders of pure metals, although not so easy to do.

Chemical vapour deposition is often used to deposit a material on a flat surface. When a surface is
exposed to a chemical vapour, the first layer of atoms or molecules that deposit on the surface can act
as a template on which material can grow. The structures of these materials are often aligned.
During deposition, a site for crystallisation may form in the depositional axis (the axis perpendicular to the
surface to be coated). As a result, aligned structures start to grow vertically. This is therefore an example of
self-assembly.

Molecular beam epitaxy

This is essentially a very sophisticated evaporation method in which molecular beams interact on a
heated crystalline substrate under ultra-high vacuum (UHV) conditions to produce a single crystal film.
Molecular Beam Epitaxis (MEB) makes it possible to fabricate crystals one atomic layer at a time. The
growth process is highly controlled to avoid being introduced during the

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crystal growth. A range of surface analysis techniques is used to monitor the growth process and ensure
purity of the crystal. MBE is presently used in the semiconductor industry, where the perform ance of
the device (eg computer chip) depends on precise control of dopants and on the production of extremely
thin crystal layers with hyper-abrupt interfaces. MBE is used for the fabrication of numerous important
devices such as light-emitting diodes, laser diodes, field effect transistors, read-write heads for computer
drives and more.

Sol-gel synthesis
This method is carried out in the liquid phase. It is a useful self-assembly process for fabricating nano
particles as well as nanostructured surfaces and three-dimensional nanostructured materials such as
aerogels.

A 'sol' is a type of colloid ( 7) in which a dispersed solid phase is mixed into a homogeneous liquid
medium. An example of a naturally occurring sol is blood. As the name suggests, the sol-gel process
involves the evolution of networks through the formation of a colloidal suspension (sol) and gelation of
the sol to form a network in a continuous liquid phase (gel).

The first stage in the sol-gel process is the synthesis of the colloid. The precursors are normally ions of a
metal. Metal alkoxides and alkoxysilanes are the most popular since they react readily with water
(hydrolysis). The most widely used alkoxysilanes are tetramethoxysilane (TMOS) and tetraethoxysilane
(TEOS) which form silica gels. Alkoxides such as aluminates, titanates and borates are also used, often
mixed with TMOS or TEOS. In addition, since alkoxides and water are immiscible, a mutual solvent is
used, such as an alcohol.

The sol-gel process involves four steps. First, the hydrolysis reaction, in which the -OR group is replaced
with an -OH group. The hydrolysis reaction can occur without a catalyst but is more rapid and complete
when catalysts are used. As in any hydrolysis reaction, the catalyst can be a base (NaOH or NH3 ) or an
acid (HF or CH3COOH).

After hydrolysis, the sol starts to condense and polymerise. This leads to a growth of particles which,
depending on various conditions such as pH, reach dimensions of a few nanometres. The condensation/
polymerization reaction is quite complex and involves many intermediate products, including cyclic
structures. The particles then agglomerate: a network starts to form throughout the liquid medium,
resulting in thickening, which forms a gel.

All four steps described are affected by the initial conditions for the hydrolysis reaction and the con
densation/polymerisation. These conditions include pH, temperature and time of reaction, nature of the
catalyst, etc.

The sol-gel process is very commonly used to make silica gels. Other type of gels can also be formed:
aluminosilicate gels are special because they form tubular structures. One such product is imogolite
which has an external diameter of about 2.5 nm and internal tube diameter of 1.5 nm. These types of
nanostructures are known to be good adsorbents of anions such as chloride, chlorate, sulphate

( 7) A colloid is a type of chemical mixture where one substance is dispersed evenly throughout another but the particles of the
dispersed substance are only suspended in the mixture, they are not completely dissolved in it. Generally speaking, a colloid is
composed of particles 10–200 nm. The dispersed phase can be solid, liquid or gas and the medium in which it is dispersed
(called continuous medium) can also be solid, liquid or gas.

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and phosphates. The imogolite structure can be dissolved away with hydrofluoric acid (HF). Therefore,
these nanostructures can be used for template synthesis: the tube can be filled with atoms and then
dissolved away, leaving rows of atoms (2.5 atoms of gold in a row measuring 1 nm).

Sol-gel process for making nanostructured surfaces

Figure 11 summarises the different sol-gel processes. To make the most of the large surface area of
nanoparticles, the gel can be placed on a surface. This way a greater bulk-area ratio is obtained.
Another strategy is to form an airgel. These are three-dimensional continuous networks of particles with
air (or any other gas) trapped at their interstices. Aerogels are characterised by being porous and very
light yet able to withstand 100 times their own weight.

Figure 11: Schematic overview of different materials that can be obtained through a sol-gel process

Image: Lawrence Livermore National Laboratory

A versatile way to create ordered surface nanostructures is to perform the sol-gel synthesis in a liquid
which is itself ordered. Liquid crystals are precisely this: they have a crystalline structure but exist in a
liquid (rather than solid) phase. Nanostructured silica with controlled pore size, shape and ordering can
be made in this way.

The liquid crystalline casting method just described can also be used to produce nanostructured
metals. This development is very useful for making nanostructured catalytic surfaces, such as plat
inum or palladium surfaces. Since these metals are very rare and expensive, it is highly advantageous

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to have surfaces where nearly all metal atoms can take part in the catalytic reaction (being on the
surface), and not just surface atoms as in conventional solids.

Functionalized silica glass surfaces

The sol-gel method also allows the incorporation of organic, inorganic and bio-organic molecules within
the silica glass structure. Most organic and inorganic molecules cannot be incorporated (doped) in
glass because this is prepared using very high temperatures. The sol-gel process occurs at relatively
low temperatures (in some cases at room temperature), so these molecules can be incorporated in the
process. This makes it possible, for example, to incorporate molecules such as enzymes inside the
silica glass. The result is a material that has the advantages of plastics (the product can be made in
any form, it can be attached to other materials, etc.) but also many improvements: the glasses are inert,
more stable to heat and chemical attack, the entrapped molecules do not leach out, and are protected
in their reactivity, and the glasses are transparent ( 8 ).

Molecular self-assembly
Self-assembly is the 'fabrication tool' of nature: all natural materials, organic and intangible, are
produced through a self-assembly route. In natural biological processes, molecules self-assemble to
create complex structures with nanoscale precision. Examples are the formation of the DNA double
helix or the formation of the membrane cell from phospholipids. In self-assembly, sub-units spontaneously
organise and aggregate into stable, well-defined structures through non-covalent interaction. This
process is guided by information that is coded into the characteristics of the sub-units and the final
structure is reached by equilibrating to the form of the lowest free energy.

TIP FOR TEACHERS: Self-assembly is a concept that can easily be integrated into conventional
lessons on genetics or biology. There are various size scales of self-assembly, from the molecular level
(from proteins to DNA) to 'macro' level (evolution of a foetus into a baby). Basically, all natural processes
are examples of self-assembly.

To date, devices have been fabricated starting from the top (a large piece of metal) and carving down to small pieces; now
scientists are considering and studying ways to truly build materials from the bot tom up, mimicking nature's own fabrication
strategy. Instead of carving nanostructures out of larger materials (which is the typical top-down approach used to fabricate
integrated electronic circuits such as micromachining and microlithography), nanostructures could be created bottom-up, from
atomic building blocks that self-assemble into larger structures.

It must be noted that this is now possible for extremely small objects. The idea of using a computer
assisted program to actually build a device, such as an electronic circuit, atom by atom, through a
self-assembly program is still a vision, but it is possible to fabricate some very small components of
an integrated circuit through a self-assembly process (eg a nanowire).

(8 ) If nanoparticles or even smaller molecules are added to the glass, it remains transparent since nanoparticles do not scatter
light — refer to Chapter 4 for more details.

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In the laboratory, scientists can make use of this self-organization of matter as a way of programming
the construction of novel structures with specific functions. Thus, the fabrication process is a molecular
recognition-directed self-organisation. To build bottom-up, specific patterns are inserted into molecules
to form organized supermolecules — nanostructures making use of supermolecular chemistry. This
can be understood as a lock-and-key self-organization of matter: scientists can pre-organise a 'key' in
a molecule to fit a 'lock' inanother, or vice versa. Once in proximity, the two (or more) molecules
assemble together: the lock-and-key mechanism serves to bind the two molecules together in a spe
cific geometry. In supermolecular chemistry, there are no chemical bonds formed during the self
assembly process: the molecules are held together through metal-ion coordination, hydrogen bonding,
donor-acceptor interactions, van der Waals forces and mediation effects (eg solvent). Transition
metal-mediated structures are a type of supermolecular structure. In the structure, metal cations are
the cement that holds the molecules (the 'bricks') together. Interest in supermolecular structures
derives from the fact that they can have properties that are dramatically different from those of their
components (eg change in electric properties). Another method uses the structural motifs and self
recognition properties of DNA to self-assemble pre-designed nanostructures in a bottom-up approach.
This field is called DNA nanotechnology.

Two other important types of supermolecular structures that are created through a self-assembly process
are dendrimes and cyclodextrins (Figures 12 and 13).

Figure 12: Dendrimer with 54 ferrocenes

attached

Image: Wiki Commons, image for public domain

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Figure 13: Three-dimensional model

of the chemical structure of
beta-cyclodextrin

Image: Wiki Commons, image for public

domain

DNA nanotechnology

DNA nanotechnology exploits the structural motifs and self-recognition properties of DNA to self
assemble pre-designed nanostructures in a bottom-up approach. Two and three-dimensional structures
have been fabricated using this self-assembly method. Recently, the revolutionary DNA origami method
was developed to build two-dimensional addressable DNA structures of arbitrary shape that can be used
as a platform to arrange nanomaterials with high precision and specificity. Researchers at the Center for
DNA Nanotechnology (Aarhus University) have developed a software package to facilitate the design of
DNA origami structures and it was initially applied in the design of the dolphins in the former logo of
Aarhus University (Figure 14).

Figure 14: Researchers began by cutting a dolphin out of the

University of Aarhus logo, which was then used as a template to
design a dolphin-like DNA structure. After producing this in the
laboratory, AFM images were taken of the DNA structure thus
formed and an image of the DNA dolphin was reinserted in the
Aarhus University logo.

Image: Danish National Research Foundation, Center for DNA Nanotechnology (cDNA), and the Interdisciplinary
Nanoscience Center (iNANO) at Aarhus University, © 2009

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The design program was further applied in the design of a three-dimensional DNA box with dimensions
42 × 36 × 36 nm3 that can be opened by external 'key' signals (Figure 15). The controlled access to
the interior compartment of the DNA container opens the way for several interesting applications of
the DNA box, for example as a logic sensor for multiple sequence signals and for the controlled
release of nano-cargos with potential applications in the emerging area of nanomedicine.

Figure 15: (left) atomic models of DNA boxes with dimensions of 42 x 36 x 36 nm3 that are large
enough to harbour, for example, a whole ribosome; (right) cryo-electron microscopy (cryo-EM)
reconstruction of the same DNA boxes

Image: Danish National Research Foundation, Center for DNA Nanotechnology (cDNA), and the Interdisciplinary
Nanoscience Center (iNANO) at Aarhus University, © 2009

DNA nanotechnology represents one of the latest developments in nanotechnology. It has applications
for the fabrication of nano-guides (eg waveguides), sensors (for diagnostic and imaging), logic gates,
drug release, nano-motors and electronics (wires, transistors). It could lead to bottom-up electronics
and DNA computing, which could become the computing of the future.

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MODULE 2:
APPLICATIONS
AND IMPLICATIONS
Module addressing
the main technological applications
and societal implications
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CHAPTER 1:

MEDICINE AND HEALTHCARE

The application of nanotechnologies to the medical sector is referred to as nanomedicine. Specif
ically, this area of application uses nanometre scale materials and nano-enabled techniques to
diagnose, monitor, treat and prevent diseases. These include cardiovascular diseases, cancer,
musculoskeletal and inflammatory conditions, neurodegenerative and psychiatric diseases, diabetes
and infectious diseases (bacterial and viral infections, such as HIV), and more. The potential contribu
tion of nanotechnologies in the medical sector is extremely broad and includes new diagnostic tools;
imaging agents and methods; drug delivery systems and pharmaceuticals; therapies; implants and
tissue engineered constructs.

Why nanotechnologies? Nanomaterials are defined as materials at the nanoscale level, which, in
nanomedicine, often goes beyond 100 nm and up to about 500 nm. This is the size range of biomol
ecules (eg proteins, enzymes, DNA) and molecular complexes such as the ion pump. These natural
nanomaterials are the components of larger hierarchical structures that regulate the function of the cell.
Bacteria and viruses are larger (a few micrometres), but their functions (including toxicity to healthy
cells) derive from the interactions between the biomolecules that compose them and the surrounding
media (including surrounding cells). Basically, nanotechnologies make it possible to create engineering
materials (such as drug delivery systems, disease imaging probes, or even engineered tissue
constructs) that have dimensions on the scale of biomolecules which, in turn, is the scale that regulates
the functions of cells. Nanotechnologies have the potential to improve the whole care process that
starts for a patient once a disease is suspect, from diagnosis to therapy and follow-up monitoring. The
aim is the development of new materials and methods to detect and treat diseases in a targeted,
precise, effective and lasting way, with the ultimate goal of making medical practice safer, less intrusive
and more personalised. The timescale from invention of a medical device or drug to release for clinical
use is extremely long. In a few cases (such as drug delivery devices), nanotechnology is already in use
for improving patient care but, in most of the areas to be discussed, the applications are still some
years from being useable products.

Diagnosis
Diagnosis of a suspect disease is one of the most critical steps in healthcare and medicine. Diag
noses are wanted quickly, but must also be reliable, specific and accurate, and with the minimum risk
of 'false positives'. Nanomedicine has the potential to greatly improve the entire diagnostic process.
Instead of collecting a blood sample in a vial and sending this to a specialised laboratory for testing
(which can take days), doctors will be able to use miniaturized in vitro diagnostic devices in their
Surgery. These are small but highly integrated devices capable of carrying out many tests quickly at
the same time using very small quantities of sample to perform the analysis. Some miniaturised in
vitro diagnostic devices already exist such as the breathalysers that the police carry for alcohol
screening or the portable glucosetest devices used by diabetics. These devices can measure ions,
small molecules or proteins, or can test for specific DNA sequences that are diagnostic for a particular
disease or medical condition. In the last years, there has been a trend to make these devices even smaller, able to pe

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hundreds of tests at the same time and be easier to use. Nanotechnologies have an important role in
this development: nanomaterials, such as nanoparticles or nanotubes, can be integrated into the device.
Scientists can engineer nanomaterials to be very specific, so their use will make the device even more
accurate and capable of carrying out even more tests simultaneously. Nanomaterials have the
characteristic of exhibiting some peculiar quantum effects that can be used to amplify the signal
arising from the detection. Thus, the use of nanomaterials in miniaturized in vitro diagnostic devices will
make it possible to improve the specificity of the analysis, its throughput (the number of tests that can
be done simultaneously) and its read-out. In the future, these types of devices will make it possible to
perform 'point-of-care diagnostics': it will be possible to make a diagnostic test anywhere, not just in the
doctor's surgery or hospital. The nature of the sample to be tested will probably change, and become
saliva rather than blood, which is much more convenient and safer to handle. This will allow large
numbers of patients to be tested, for example in the event of an epidemic, or large numbers of diseases,
or the many parameters needed for one specific disease to be considered for the diagnosis of complex
medical conditions.

Miniaturized diagnostic devices include biosensors, microarrays and 'lab-on-a-chip' (LOC) devices, also
called miniaturized total analysis systems (µTAS). The first two are based on a parallel processing
technique, whereas LOC devices are based on a serial processing technique.

Biosensors
Generally speaking, a sensor is a device capable of recognizing a specific chemical species and 'signal
ling' the presence, activity or concentration of that species in solution through some chemical change.
A 'transducer' converts the chemical signal (such as a catalytic activity of a specific biomolecule) into a
quantifiable signal (such as a change in color or intensity) with a defined sensitivity. When the sens ing
is based on biomolecular recognition, it is called a biosensor. There are various types of biosensors,
such as those based on antibodies/antigens, nucleic acids and enzymes. Furthermore, depending on
the technique used in signal transduction, biosensors are classified as optical detection biosensors (as
in the example above), electrochemical biosensors, mass-sensitive biosensors or thermal biosensors.

There are numerous nanoparticles that can be used as biosensor components. These work as probes
recognising an analyte or differentiating between analytes of interest. In such applications, some bio
logical molecular species are attached to the surface of the nanoparticles to recognize the target of
interest through a lock-and-key mechanism. The probes then signal the presence of the target by a
change in colour, mass or other physical change. Nanoparticles used as elements for biosen sors
include quantum dots, metallic nanoparticles, silica nanoparticles, magnetic beads and fullerenes, which
are hollow cages of carbon atoms, shaped like footballs.

Other biosensors use nanostructured particles as nano-sieves through which charged molecules are
transported in an electric field. In this case, particles with engineered nanopores are used.

Carbon nanotubes and nanowires are also employed for sensing. The latter can be fabricated out of
a semiconductor material and their size tuned to have a specific conducting property. This, together
with the ability to bind a specific analyte on their surface, yields a direct, label-free electrical read-out.
These nanowire biosensors allow the detection of a wide range of chemical and biological species,
including low concentrations of protein and viruses, and their application ranges from the medical to
the environmental sector. Figures 1 and 2 illustrate a silicon nanowire biosensor based biorecognition.

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Figure 1: Biorecognition on a silicon nanowire biosensor: the surface of the nanowire is modified
with avidin molecules (purple stars) which can selectively bind a streptavidin-functionalized molecule
or nanoparticle

Image: L. Filipponi, iNANO, Aarhus University, Creative Commons ShareAlike 3.0

Figure 2: Scanning electron micrograph depicting the

functional part of a nano-biosensor containing silicon
nanowires

Image: P. Mohanty, Boston University, NISE Network

(http://www.nisenet.org), licensed under NISE Network Terms
and Conditions

Nanoscale biosensors have the potential to greatly aid in the diagnosis of diseases and monitoring
of therapies. A large number of approaches have been developed in recent years while relatively
few have so far been converted into clinical diagnostic tools — their wide application in patient care
is foreseen in the next 5–10 years.

Cantilever biosensor

A cantilever biosensor is a biosensor made of numerous 'arms' (called cantilevers) which are tens of
micrometres long but very thin (a few micrometres). These devices are fabricated through lithography
and etching. The surface of the cantilever is functionalised with a nanometre-thick layer of coating
which ensures anchorage of the probe material (which can be a DNA strand or a protein, for example).
Each cantilever is different and can probe for a different target, as schematised in Figure 3. In this type
of sensor, the adsorption of the analyte to the specific targets on a cantilever causes a surface stress
and bends the cantilever. The most common read-out is optical where the angular disturbance of a
laser beam is measured following the bending of the cantilever. Although common, this method suffers
from the limitation that measurements are difficult in opaque liquids, such as blood, because of the
absorption of the laser light. An alternative to this method is the piezoresistive read-out, where a
piezoresistor is integrated into the cantilever. Upon detection of the analyte, the stress applied to the
resister changes, which is reflected in a change of its resistance, which in turn is measured as an

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electrical signal. This approach offers the advantage of allowing the detection in opaque media, the
possibility of miniaturising the sensor and incorporating it in portable devices for point-of-use sensing.

Figure 3: Schematic diagram of a cantilever-based

biosensor: the yellow molecules bind specifically to the
red molecules on the right-hand cantilever and are
detected by the bending of the cantilever

Image: M. Lorenzen, iNANO, University of Aarhus, © M. Lorenzen

Plasmonic biosensors

The optical properties of noble metal nanoparticles have received significant research attention in
recent years for their potential as components in many applications, including chemical/biochemical
sensors. The optical properties of noble metal nanoparticles are dominated by an effect called local
ised surface plasmon resonance (LSPR), which was described in Module 1, Chapter 4: Fundamental
'nano-effects'. One of the consequences of the LSPR effect in metal nanoparticles is that they have
very strong visible absorption due to the resonant coherent oscillation of the plasmons. As a result,
colloids of metal nanoparticles such as gold or silver can display colors that are not found in their bulk
form, such as red, purple or orange, depending on the shape, size and surrounding media of the
nanoparticles. The energy of LSPR is sensitive to the dielectric function of the material and the sur
roundings and to the shape and size of the nanoparticle. This means that if a ligand such as a protein
attaches to the surface of the metal nanoparticle, its LSPR energy changes. similarly, the LSPR effect
is sensitive to other variations such as the distance between the nanoparticles, which can be changed
by the presence of surfactants or ions. The fact that the LSPR depends on the dielectric environment
means that the refractive index can be used as the sensing parameter: changes in the local dielectric
environment, induced by the sensing process, are used to detect the binding of molecules in the
particle nano-environment .

In a plasmonic biosensor, the nanoparticles can be dispersed in a medium (in which case the
biosensor is a colloidal plasmonic biosensor) or supported on a surface (surface plasmonic
biosensor). Both types of sensors exploit the fact that the sensing event changes the LSPR of the
metal nanoparticles, but use different read-out report strategies.

In a colloidal plasmonic biosensor (eg made of gold nanoparticles), the sensing event results in a
change of aggregation among the nanoparticles that form the colloid (Figure 4), which can deter
mine a color change of the colloid. Absorption spectroscopy is used to measure the biosensing event.
In the case of gold colloid, which is normally red, the sensing event can result in the colloid becoming
blue. Thus, metal colloids can be used as plasmonic colorimetric biosensors. In nanomedicine, this
effect is used, for example, in genetic screening, where scientists look for a specific gene sequence in
a sample which can be indicative of a specific disease. How is this done? First, the sequence of bases

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in the target DNA is identified. Then, two sets of gold particles are prepared — one has DNA attached
that binds to one end of the target DNA, and the second set carries DNA that binds to the other end.
The nanoparticles are dispersed in water. When the target DNA is added, it binds both types of nano
particle together, linking them to form an aggregate. The formation of this aggregate causes a shift in
the light-scattering spectrum from the solution (ie a color change in the solution which can easily be
detected). An example is illustrated in Figure 5.

Figure 4: Schematic representation of a colloidal plasmonic

biosensor

Figure 5: Plasmonic colloidal nanosensor

Image: Jin et al., Journal of the American Chemical Society, 2003, 125(6):1643–1654, reprinted with the permission of
the American Chemical Society, © 2003

EXPERIMENT C in the Experiment Module deals with synthesising and

testing a gold colloidal plasmonic nano-sensor. In the experiment,
students use electrolytes to see the color change due to the change in
aggregation of the nanoparticles as the salt is added to the colloid.

In a surface plasmonic sensor, metal nanoparticles are immobilised on a surface as illustrated in

Figure 6(a). The metal nanoparticles are attached to the surface by means of chemical linkers or
prepared by nanolithography (b), and are then modified with the sensor moiety (c). The analyte (the
target) attaches from solution specifically on to the recognition function adsorbed on to the particles
(d), causing a change in the refractive index around the particle, resulting in an LSPR shift. The LSPR
shift is measured through a technique called extinction spectroscopy (e).

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Figure 6: Schematic representation of the preparation and response of LSPR biosensors based on
refractive index changes

Image: Borja Sepúlveda et al., 'LSPR-based Nanobiosensors', Nano Today, 2009, 4(3):244–251, reprinted with the
permission of Elsevier

Artificial nose biosensor

An artificial nose biosensor is a device that mimics the ability of some mammals, such as dogs, to
detect explosives and drugs through their olfactory system. Recent research has shown that this fine
capacity in dogs may also be used to detect molecules which, if present, are early indicators of various
diseases such as cancer. Numerous research programs are under way around the world to create an
artificial nose: one such is the European project BOND. The application of such types of biosensor
ranges from medicine (early disease detection) and security (explosives detection) to the food industry
(to measure whether food has gone off). This type of biosensor is an electrochemical sensor that
mimics the natural mammal olfactory system. The nose-biosensor, like our own noses, is composed
of three main parts, a biomolecule receptor, an electrode and a transducer. When the detector finds
the target, a chemical reaction occurs between the detector and the receptor biomolecules for odor.
The chemical reaction between the receptor and the substance we smell emits a chemical signal. The
translate electrodes this chemical signal into electrical signals and transports them to the brain or, in
the case of the nose biosensor, they are transported to a transducer. In mammals, the equivalent of
the electrodes would be neurons. The transducer (the brain in mammals) receives the electrical signal
and translates it into analytical information. In the nose-biosensor, the transducer would give information on a screen.

NANOYOU GAME Students can become'nano-scientists' and fabricate and test a nose biosensor
through the NANOYOU Virtual Game (http://www.nanoyou.eu/virtual-lab.html).

NANOYOU DILEMMA Diagnostic nanosensors (cantilever-based, plasmonic, nanowires-based,

etc.) will allow for the early detection of various diseases, such as cancer, at the very onset of
the symptoms, before the disease is perceived by the patient. Early detection means a higher
chance of successfully treating and overcoming the disease. On the other hand, some worry that
this will give doctors access to a large amount of personal information. The question is: Where is
this information going to be stored, and who will have access to it? Also, what if those devices
are used not as a diagnostic tool but as a mean to assess a person's medical condition by other
entities, such as insurance companies or job agencies? The dilemma is: Should nanosensors be
used to diagnose medical conditions in the early stages when there are still no definite restric
tions in place to protect patients' privacy? This dilemma is part of the NANOYOU role-playing
game (http://www.nanoyou.eu/en/decide).

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Microarrays
These devices are used for diagnostic purposes such as DNA analysis (DNA microarray), protein
detec tion (protein microarrays) as well as whole cell analysis. Microarrays are platforms made of
hundreds of detection sites that have micron-sized dimensions and allow the specific detection of a
(bio)chemical within a mixture or the simultaneous detection of many (bio)chemicals. The detection is
related to the chemical functionality on the micron-sized spots in the array and it leads to a single
chemical 'yes/no' reaction per spot. Microarrays are used as screening tools, not only for diagnostic
purposes but also for screening new drugs. Nanotechnology can impact microarray technology by
creating densely packed, smaller, nano-sized arrays (nanoarrays) that could allow faster screening of
a larger number of (bio) chemicals. There are, however, some problems associated with the handling
of ultra-small quantities of liquid so nanotechnologies offer the most promising advantages in sample
detection on arrays. The conventional method used for detecting the 'yes/no' reaction at each spot is
fluorescence. This tech nique uses fluorescent probes made of organic molecules attached to the
species to be detected (eg a protein or a fragment of DNA): when reaction occurs, this is attached to
the detection spot, which becomes fluorescent in a 'color' corresponding to the emission of the
fluorescent probe. Fluorescent staining suffers from some disadvantages, mainly fast bleaching of the
fluorescent molecules (that is, loss of 'brightness' of the color in time during imaging); limited numbers
of dye molecules that have distinct 'colors' and that can be simultaneously imaged; and limited
sensitivity. Nanoparticles in the form of quantum dots (QD) can be used as an alternative to
conventional organic dyes, being more stable, sensitive and monochromatic. A significant (tenfold)
enhancement in sensitivity compared to common fluorescent markers has been accomplished through
the use of gold and silver particles of uniform dimensions in the range 40 to 120 nm. Signal amplification
is also obtained using metal nanoparticle labels, such as DNA-modified gold nanoparticles. These nano-
sized probes have molecules attached to their surface that ensure the selectivity of the detection, while
the nano-properties of the probe are responsible for enhancing the signal. The overall effect is an
improvement in the sensitivity and selectivity of microarray technology.

Nanobarcodes

The unique properties of nanoparticles, such as the relationship between particle size and colour, can
also be used to create multiplexed detection systems in the form of nanobarcodes, for example using
quantum dots to create different color-based codes. alternatively, fragments of DNA on nanospheres
can be used to create a 'bio-barcode', for example for protein detection. A bio-barcode has been used
to detect small levels of the cancer marker prostate-specific antigen (PSA) in serum. The results
showed an increased sensitivity to the PSA protein compared to conventional protein assays,
demonstrating the potential of such approaches for detecting cancers at an earlier stage.

Lab-on-a-chip
These devices are 'miniaturized integrated laboratories' that allow the separation and analysis of bio
logical samples (eg blood) in a single device. They are made of microfluidic systems, including micro
pumps and micro-valves, integrated with microelectronic components. The devices can also integrate
one or more sensors. As with microarray technology, the impact of nanotechnologies in this area is in
further miniaturisation of these devices, although the handing of ultra-small volumes of samples would
pose a problem. Currently, nanotechnologies are making an impact in improving specific components
and functions of lab-on-a-chip devices. For example, analysis is commonly done by dielectrophoresis,
where non-uniform alternating electrical fields are used to separate and guide small objects through
field gradients: this manipulation requires high electrical field strengths that can be obtained using

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nano-sized electrodes. Another example is nanopore-based separation systems that can be integrated
into the membranes sequencing used in lab-on-a-chip devices — for example, nanopore-membranes
are proposed for DNA.

Imaging
The second step in the diagnosis of a disease involves in vivo imaging, which searches for the symp
toms of the disease within the live tissue suspect of being infected without the need to perform surgery.
Nanotechnologies are having a very important impact in this area, particularly by developing molecular
imaging agents. The latest improvements in the area of imaging deal with the capability of tracking
changes at the cellular and molecular level through the analysis of some specific biological markers (a
technique called 'targeted molecular imaging' or 'nano-imaging'). A biomarker is an indicator of a
biological process or state, such as a disease, or the response to a therapeutic intervention. This can
be an altered gene, or a change in protein production, or even a physical feature of a cell. The aim is
to detect biomarkers of disease and diagnose illnesses before, or at the onset of, the first symptoms,
in this way making in vivo imaging a tool for the early detection of a disease. Effective early detection
is crucial for planning a therapy with less severe and costly demands, especially in diseases such as
cancers, where timing is vital for the success of the treatment. Biomarkers could also be used as early
indicators of the success of a treatment, thus reducing treatment time and cost. Targeted molecular
imaging is important not only for diagnostic purposes, and for monitoring the progress of a therapy, but
also for research in controlled drug release, in assessment the distribution of a drug within the patients'
body, and for the early detection of unexpected and potentially toxic drug accumulations.
The ability to trace the distribution of a drug leads to the possibility of activating it only when and where
needed, thus reducing potential drug toxicity.

Diagnostic imaging
Techniques such as X-ray, computer tomography (CT), ultrasound (US), magnetic resonance imaging
(MRI) and nuclear medicine (NM) are well established imaging techniques, widely used in both
medicine and biochemical research. Originally, imaging techniques could only detect changes in the
appearance of a tissue when the symptoms of the disease were relatively advanced. Later, targeting
and contrast agents were introduced to mark the disease site at the tissue level, increasing imaging
specificity and resolution. It is in this specific area that nanotechnologies are making their greatest
contribution by developing better contrast agents for nearly all imaging techniques. The physiochemical
characteristics of the nanoparticles (particle size, surface charge, surface coating and stability) allow
the redirection and concentration of the marker at the site of interest. An example of nanoparticles
used in research for imaging is perfluorocarbon nanoparticles employed as contrast agents for nuclear
imaging, magnetic resonance imaging and ultrasound, with applications in the imaging of blood
clots, angiogenesis, cancer metastases and other pathogenic changes in blood vessels. Gadolium
complexes have been incorporated into emulsion nanoparticles for the molecular imaging of thrombi,
resulting in a dramatic enhancement of the signal compared to conventional MRI contrast agents.
Fullerenes are also used in magnetic resonance imaging research, filled with smaller molecules that
act as contrast-enhancement agents. Metals and silicon nanoparticles are also used to enhance MRI.
Silicon particles fabricated into different shapes and coated with conductive layers can have enhanced
magnetic resonance interactions with an imaging field.

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In X-ray imaging, to enhance the signal, an agent must deliver a detectable number of heavy atoms
into targeted tissue without toxic effects. Nanoparticles of heavy metals have the highest density of
surface atoms but they must be inert and stable. Nanoparticles of inert metals like silver and gold are
too expensive and would render the technique not cost-effective. A solution has been proposed by
General Electric in the form of nanoparticles made of heavy metal compounds encapsulated in
gold shells. The added advantage is that organic compounds with sulphide (-SH) groups (thiols) can
easily be attached to the gold surface through the thiol end (forming an S-Au bond). The thiol molecule
can be functionalised at the other end with groups that act as receptors for specific binding of anti
gens, antibodies or even target compounds on the surface of the cell. By targeting receptors unique to
a certain type of cancer cell, gold nanoparticles can enhance an X-ray image of a suspect cancer tissue
by many orders of magnitude.

Gold nanoshells are a promising material for the optical imaging of cancer. Optical technologies
could provide high resolution, non-invasive functional imaging of tissue at competitive costs. However,
at present, these technologies are limited by the inherently weak optical signals which come from the
endogenous chromophores and the small spectral differences between normal and diseased tis sue.
Gold nanoshells are made of a dielectric core (silica) covered in a thin metallic (gold) shield. Gold
nanoshells possess physical properties similar to gold colloid (as described previously), in particular,
a strong optical absorption due to the collective electronic response of the metal to light (the LSPR
effect). By changing the relative dimensions of the core and shell, the optical resonance of the nano
particles can be precisely and systematically varied over a broad region ranging from the near-UV to
the mid-infrared (Figure 7).This range includes the near- infrared (NIR) wavelength region where tis
sue transmissivity is higher. Researchers are using these gold nanoshells cells as contrast agents for
Optical Coherence Tomography (OCT) 9 ) of cancer cells. As discussed later, gold nanoshells are also
( capable of treating cancer cells through overheating of the cells.This is discussed in the next section.

Figure 7: (left) SEM image of gold nanoshells each being about 120 nm; (right) optical image of the
same nanoshells after being dispersed in water and dried on a microscope slide. The colors are
due to selective scattering of light by the nanoparticles.

Images: G. Koeing, University of Wisconsin-Madison, NISE Network (http://www.nisenet.org), licensed under NISE
Network Terms and Conditions

(9 ) Optical Coherent Tomography (OCT) is a state-of-the-art imaging technique which produces high resolution (typically 10-15 µm) real-time cross-sectional
images through biological tissues. The method is often described as an optical analogue to ultrasound.

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In situ diagnostic devices

In recent years, in situ diagnostic devices have been developed, such as wireless capsule endoscopy
cameras. These devices are swallowed by the patient and make it possible to closely monitor and
locate the site of bleeding and other intestinal problems. Currently, many of these devices, such as
the CamPill® produced and sold by Given Imaging Ltd, can only image the problem. In the future,
these devices could also incorporate sensors for the detection of specific chemicals, pH, bacteria, viruses, etc.
Micro and nanotechnologies now allow the creation of extremely small sensors and research is being
conducted on integrating them into swallowable capsules. This will widen their applicability and utility.
In the future, they could also be drug-loaded for targeted drug delivery.

Therapy
The same disease, such as cancer, can express itself in many different forms: for example, there are
at least 14 different types of breast cancer. Thus, in an ideal world, a therapy should be specific, in
order to remove only the 'bad' cells, and effective, both in terms of action and time.

A therapy normally involves a pharmaceutical route (drugs) to treat the disease from the inside of the
body, or, when a pharmaceutical therapy is not possible or not effective, other routes to fight the
disease from the 'outside' of the body, such as radiative therapies. In some circumstances, surgery is
required, and an organ-substitute is inserted into the body in the form of an implant or a donated
organ. In all these approaches, which are often used in combination, the aim is always the same: to
eliminate selectively the source of the disease in a long-lasting way. Nanotechnologies are making a
tremendous impact in this field, with new drugs and new types of cures, some of which has already
proven effective and have entered the market.

Drug development and targeted drug delivery

Advances in the field of pharmacology stem from two main concepts: the development of new biologic
ally active drugs (drug discovery) and the development of new drug delivery systems able to reach the
specific site of the disease. Drug delivery systems (DS) are not a new concept: research in this field
started in the mid 1960s and resulted in the type of drugs used today (ie medicines where the active
ingredient is encapsulated and released inside the body by gradual dissolution, osmotic effects , or
other mechanisms). Drug delivery systems are in the same form as the 'pills' that are frequently taken
and that release their active component fought in time (slow release drugs) or that dissolve based on
some physiological conditions (eg acidity of the environment). Drug delivery systems also exist in the
form of implants, inserts or other drug-releasing systems.

Drug design and screening

The structure of biological macromolecules defines a three-dimensional nano-environment that medi

ates specific functions in the cell. The design of new drugs requires a very detailed understanding of
this nano-environment. Therefore, gain insight into the structure of macromolecules on the nanoscale
through electron microscopy, nuclear magnetic resonance spectroscopy (NMR) and X-ray crystallography
is of fundamental importance tounderstanding processes and for the development of new medicines.

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One of the bottlenecks in drug discovery is the necessity to screen thousands of candidate drugs for their
effectiveness in fighting targeted macromolecules in a disease state. Micro and, now, nanotechnologies
have enabled the development of microarray platforms and new detection methods (including label-free)
to investigate the effects of candidate drugs against disease macromolecules with unprecedented speed.

Targeted drug delivery

Pharmaceutical drugs developed using conventional synthesis routes are limited by problems such as
low efficiency, low solubility in water and lack of selectivity. In addition, physiological barriers often
pre vent the drug from reaching and acting at the target site — a phenomenon called drug resistance.
The low solubility and limited bioavailability of conventional drugs is responsible for their limited
effective ness: the body often clears away the drug before its action is complete. The effectiveness of
drugs is also dependent on the dose used, but dose-dependent side effects often limit their acceptable
usage. The lack of selectivity is especially detrimental, for example, in cancer therapies, since anti-
cancer drugs, usually distributed in large volumes, are toxic to both normal and cancer cells.

A recognized need exists to improve drug composition, delivery, release and action, and thus to develop
new drugs that can act at the specific site of the disease, maximising the drug's therapeutic action while
minimising side effects. For drugs to be able to do this, the delivery systems need to be miniaturized to
much smaller than the target, and specific in composition to elicit a certain response. With the use of
nanotechnologies, targeted drugs (in terms of composition and delivery system) are becoming a reality.
In the future, this could lead to targeted therapies and personalized medicine. The aim is to design and
deliver drugs in such a way that they can recognize the 'bad' cells at a molecular level, penetrate the
cell membrane, and act inside the infected cell. This is often crucial for the effectiveness of a drug, since
most viral replication and other disease conditions take place across the cell membrane and inside the cell.
This way, the treatment will be delivered where it is needed and will be specific, eliminating the problem
of the drug killing healthy cells. An example of this approach is siRNA drug delivery.

Targeted drugs and targeted DDS could allow the creation of drug formulations with optimal loading,
which deliver to the body only the necessary amount of the drugs and reduce side effects for the patients.
Together with the possibility of having nano-DDS that are biodegradable inside the body, this will help to
reduce drug toxicity. Drug safety can be further enhanced by the possibility of introducing inside the drug
formulation a label that changes color when the drug reaches its expiry date or is no longer functioning.
This will allow for the improvement of drug shelflife and better monitoring of drug safety.

siRNA drug delivery

RNA interference is a natural, fundamental mechanism in gene regulation that occurs in both plants
and animals, humans included. Genes carry the genetic material of an individual, the DNA, and are
contained in the nucleus of a cell. When genes are express (ie activated), the genetic information is
copied from DNA to messenger molecules, called messenger RNA (mRNA), which then orchestrate
the formation of proteins outside the nucleus of the cell. In 1998, Andrew Fire and Craig Mello
discovered that double stranded RNA (dsRNA) can interfere with and break down the mRNA for a
specific gene, thus stopping the production of a specific protein. The gene is, therefore, 'silenced' and
the production of the protein is turned off. Fire and Mello found that this RNA interference mechanism
is specific and can be obtained with a few molecules of dsRNA, and that the effect of dsRNA could
spread from cell to cell and from tissue to tissue, and even passed on to offspring. The discovery won
the scientists the Nobel Prize in Medicine in 2006. Now researchers know that RNA interference
plays an important role in switching off genes during an organism's development and controlling cellular functions. But

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interference not only enables scientists to better understand the fundamentals of gene regulation: it also
opens new possibilities for genetic engineering in biological and medical research. In the laboratory,
scientists can now tailor RNA molecules — silencing RNAs — that activate the breakdown of endogenous
mRNAs (ie RNA that belongs to that specific cell). When silencing RNA (siRNA) molecules enter the
cell, they activate RNA interference and endogenous mRNA molecules that bind to the added siRNA
are destroyed. Researchers are now hoping to use RNA interference to treat diseases such as viral
infections, cardiovascular diseases, cancer and metabolic disorders. So far, many experiments with
RNA interference have yielded promising results, but in order to maximise the therapeutic efficacy of the
technique, some fundamental difficulties must be overcome. These include the low stability of siRNA in
biological fluids and low specificity of action due to gene off-target effects caused by the similarity in
behavior of synthetic siRNA to natural microRNA produced by the cell. Therefore, there is the need to
develop delivery methods capable of overcoming the extracellular and intracellular barriers and getting
the siRNA molecules into the right type of cell (targeted delivery) while maintaining the stability of siRNA.

Researchers at iNANO (Aarhus University) and other institutions worldwide are developing nanocarriers
for the targeted delivery of siRNA. For example, they are studying a novel chitosan-based siRNA
nanoparticle delivery system for RNA interference in vitro and in vivo. Chitosan is a naturally occurring
cationic polysaccharide that has been widely used in drug delivery systems. It contains positively
charged amine groups that can interact with the negatively charged backbone of siRNA and form
polyplexes in the form of nanoparticles about 200 nm in size. The protonated amine groups allow
transport across cellular membranes and subsequent endocytosis into cells. It has been shown that a
chitosan/siRNA nanoparticle delivery system silences genes both in vivo and in vitro (Figure 8).
Furthermore, this delivery system has been shown to be biocompatible, non-toxic and biodegradable.
Another requirement in targeted siRNA delivery is the capability of the carrier to reach a specific cellular
compartment and release the cargo (the siRNA) inside that cell. Synthetic vectors based on polycations
such as poly-L-lysine have been widely used but have several drawbacks such as high cellular toxicity,
sequestration in subcellular compartments and lack of intracellular targeting. In contrast, bioresponsive
copolypeptides containing reducible disulfide bridges that respond to intracellular acidity conditions have
proven advantageous in delivering nucleic acids into cells. These systems exploit the redox potential
gradient existing between the extracellular and the intracellular environment so that the disulfide bridges
are broken (and the cargo released) only in one compartment of the cell (in this case, the nucleus). For
these reasons, research is being conducted in developing nano-carriers rich in histidine groups.

Figure 8: Live cellular uptake of

chitosan/siRNA nanoparticles into
NIH 3T3 cells: fluorescence
microscopy was used to visualise
cellular uptake and translocation of
Cy5-labelled siRNA within Chitosan nanoparticles after four hours of reaction. Images show
fluorescent overlay of siRNA (red Cy5-labelled) and nuclei (blue Hoechst-labelled) adjacent to
phase contrast image (scale bar, 10 µm).

Image: K. A. Howard et al., Molecular Therapy, 2006, 14(4):476–484, reprinted with the permission of Macmillan
Publishers Ltd, © 2006

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Stimuli-activated drug delivery

In this area of research, the idea is to incorporate some specific properties into the delivery system so
that the drug can be activated only on reaching the target, and the active component released at a
controlled rate. This is called stimuli-activated drug delivery. Controlled activation could be linked to
some environmental property, such as pH, or 'lock-and-key' molecular recognition mechanisms. One
example is stimuli-activated gene delivery.

In gene therapy, one of the biggest challenges is the targeted delivery of the nuclei acid load to the
target (eg plasmid-DNA or siRNA) either to silence (RNA silencing) or to activate the expression of a
protein as a way to treat a number of diseases. In the previous section, how nanocarrier delivery
systems formed by electrostatic interactions between cation polymers and DNA or RNA have been
developed to overcome extracellular and intracellular barriers to maximise the delivery of the nucleic
acids in the cell was discussed. One way to control the spatial and temporal activity of nucleic acids is
to use polymers that change properties in response to stimuli such as temperature and redox potential
gradients. This approach to targeted delivery is being evaluated at iNANO and is schematically
illustrated in Figure 9. The idea is to utilise a nanocarrier that passively accumulates in the diseased
tissues (eg tumours), followed by stimuli-induced activation at the required site (inside or outside the
cell). In the case of thermoresponsive systems, the application of heat in precise locations of the
tissue can induce the deposition of the nanocarrier in the extracellular target region.

Researchers are studying, for example, the use of a thermoresponsive polymer to form a polyplex with
plasmid DNA and using AFM to visualize the resulting nanoparticles. They found that the size of the
polyplex nanoparticles from around 50 to more than 200 nm could be changed by heating the particles.
The AFM images revealed that smaller particles merged to form larger particles during the temperature
treatment. Since the ability of polyplexes to cross vasculature endothelial barriers and enter/exit
tissues depends on particle size, a thermostimulus could be used to control migration inside tissues.
The idea is to apply a thermostimulus in the diseased tissue so as to induce a size increase in the
nanoparticles and prevent these from re-entering the blood (Figure 9). This general approach could
be used for nanocarriers containing drugs or imaging agents for therapeutic and diagnostic applications.

Figure 9: Schematic rep

resentation of a nanocar
rier thermo-activated for
gene therapy

Image: Howard et al., Small,

2007, 3(1):54–57, reprinted
with the permission of
Wiley-VCH GmbH &
Co. KGaA, © 2007

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Current and future nano-drug carriers

Nano-sized drug carriers currently under development include either materials that self-assemble, or
conjugated multicomponent systems, for instance a drug linked to a protein and a polymer (called a
polymer-drug conjugate, Figure 10). Numerous nanosystems are now being evaluated and include
micelles, nanoemulsions, nanotubes, nanofibres, liposomes, dendrimers, polymer therapeutics,
nanoparticles, nanocapsules, nanospheres and hydrogels. Some of these nano-sized drug carriers
are established in the field of drug delivery, such as liposomes: others have made their way to the
market in recent years, such as polymer-protein conjugates (polymer pharmaceutics).

Many are now used for treating some forms of cancer, hepatitis, and leukaemia. An example is an anti
cancer drug called DOXIL (Sequus Pharmaceuticals, Inc.).

Figure 10: (Left) schematic representation of a polymer-drug conjugate, and of a targeted polymer
drug conjugate (right)

Image: Duncan R., Nature Reviews Cancer, 2006, 6(9):688–701, reprinted with the permission of Macmillan Publishers Ltd,
© 2006

The future of nano-DDS enabled by nanotechnologies could be miniaturized implantable chips loaded
with different drugs that can be released by external stimuli. This could free patients, such as diabetics,
from having to administer drugs repeatedly during the day. Research in this area is very active but still
requires years for commercial realisation.

Externally activated therapies that use nanoparticles

One of the distinguishing properties of nano-sized drug carriers is their ability to accumulate passively
in cancerous solid tumor tissue due to an effect called enhanced permeability and retention (EPR).
This passive mechanism has been attributed to the 'leaky' nature of tumour vessels. The blood vessels
that supply tumours with nutrients have tiny gaps in them that allow nano-DDS (60–400 nm in size) to
enter the tumour region and accumulate there. This further targeted the approach to treating infected
cells. Furthermore, this allows the accumulation of therapeutic agents inside the tumour region with
activation by an external source. Based on this concept, some new anti-cancer therapies have been
developed and have entered advanced clinical trial stages. Print these therapies, nanoparticles

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are delivered to the tumour site, where they accumulate. An external source is then used specifically
to activate the nanoparticles and overheat the tumour region (the therapy is called hyperthermia). Due
to the EPR effect, the nanoparticles accumulate only in the tumour region, so the treatment is extremely
localized and healthy tissue is not affected. Overheating the tumour site can be achieved, for example,
by activating magnetic nanoparticles with an alternating magnetic field so that they start vibrating and
thus generate heat. This is the principle on which a new anti-cancer therapy, MagForce®, has been
devel oped: this therapy entered Phase II clinical trials in 2007 for the treatment of prostate cancer.
Another approach uses gold nanoshells (as described previously) designed to absorb light in the near
infrared (NIR) region. This is the region where light penetration through tissue is optimal (800–1 300
nm). The nanoshells absorb NIR light, delivered with a laser, converting light into heat. In animal
model stud ies, the nanoshell treatment has been shown to induce complete resorption of a tumour in
10 days, with all the animals remaining healthy and tumour-free for more than three months after
treatment. These examples show the innovative approach to tumour treatment enabled by nanoparticles.

Theranostics

One of the most exciting opportunities that nanotechnologies have brought to the therapeutic field is
the possibility of integrating the diagnosis, therapy and follow-up of a disease. This is referred to as
theranostics, and could be enabled by nanoparticles incorporated inside a drug that can change some
property — such as color — once the drug has reached the target (eg quantum dots). Drugs could
therefore have a feedback action. Together with a slow targeted release system, the nanoparticles
could combat color during the drug action, thus informing doctors of the progress of a therapy. This
approach is called 'find, fight and follow' and could become a reality as a result of the parallel progress
in the field of molecular imaging. One vision is that, one day, the entire process of diagnosis, pre-
imaging, therapy and post-imaging of a specific disease will be integrated. An example of theranostics
is the use of gold nanoshells for imaging and treating cancer cells at the same time.

Regenerative medicine

At times, the only way to treat a disease is the removal of the infected organ or tissue. Such loss can
also derive from an injury or a congenital condition (eg vision or hearing impairment). To compensate
for the lost or impaired body function, an artificial construct is implanted in the body. Depending on the
type, site and extent of the loss, this construct can be in the form of an engineered tissue or an implant.

Tissue and biomaterial engineering

Tissue engineering deals with the fabrication of artificial scaffolds to support the growth of
donor cells, which differentiate and grow into a tissue that mimics the lost natural one. This
tissue engineered construct is then implanted in the patient and, in time, resorbed by the body
and fully integrated by the host tissue. Current applications of tissue-engineered constructs include
engineering of skin, cartilage and bone for autologous implantation (ie the implantation of a tissue
regenerated by seeding cells of the patient).

The 'scaffold' that supports cell growth is the core of this technique. In the body, cells are supported in
their growth and function by a natural scaffold, called the extracellular matrix (ECM). This is a very
complex and intricate 'web' of nanofibres that provides the mechanical architecture for cellular growth.

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Furthermore, the ECM is filled with small molecules (eg growth factors) and proteins that direct many
cell processes, such as adhesion, migration, growth, differentiation, secretion and gene expression.
The three-dimensional spatial organization of these 'cues' is critical in controlling the entire life cycle of
the cell. this three-dimensional nano-architecture guides cells to form tissues as complex as those
found in bone, liver, kidney and heart. The biggest challenge in regenerative medicine is the artificial
replication of this 'perfect nano-scaffold'. The ability to engineer materials having a similar level of
complexity is now becoming a reality through nanotechnology.

Micro-fabrication techniques derived from the semiconductor industry (such as photolithography or ion beam
lithography) have long been used for the fabrication of microstructures to support and control cellular growth:
one of the pioneering works in this field was published in the late 1970s. In recent years, new nanotechnology
techniques have enabled studies at higher and higher resolution, reveal ing the nanoscale detail of the
ECM. Analytical tools, such as the AFM, and nanofabrication tools have allowed scientists to fabricate
scaffolds with nanoscale features. A great deal of research is now dedi cated to engineering scaffolds with
tailored material composition and properties, including nanotopog raphy and controlled alignment, to study
how these can support and direct cellular growth. The aim is the fabrication of scaffolds that most closely
resemble natural ECM. Researchers now have access to techniques which produce macroscale structures
with nanometre details. Conventional polymer chem istry combined with new nanofabrication methods is
now used to manufacture a wide range of struct tures, such as nanofibres of different and well-defined
diameters and surface properties; nanofibrous and porous scaffolds; nanowires, nanotubes, nanospheres
and nanocomposites.

Close to the field of tissue engineering, and in many cases an integral part of it, is biomaterial
engineering engineering. Materials used in regenerative medicine are called biomaterials in the
sense of being able to trigger and support a biological response. One of the distinguishing features
of nanotechnologies is their ability to create new functional materials. This can be exploited in the
fabrication of new biomater ials that have better mechanical properties: to increase the implant
stability and reduce fatigue failure in orthopedic implants for example and materials that have
enhanced electrical properties, needed in neural prostheses, for example. Nanotechnologies can
also be used to fabricate implants made of materials that are more resorbable, to increase
functionality and durability. For example, nanocoatings are being studied which will better integrate
synthetic implants with the biological tissue, in order to prevent tissue and the onset of rejection.

Nanotechnologies are also employed in the fabrication of biomaterials that are responsive to the
environment (eg responsive to pH or the presence of specific biomolecules) and, for this reason, are
called 'smart biomaterials'. Furthermore, research is being conducted to include nanoscale patterns in
the biomaterial, which will simulate the natural cues and mimic molecular signaling mechanisms, in
order to trigger desired biological events, such as cell adhesion, differentiation and spreading. This
could facilitate the fabrication of dynamic implants that are not limited to simply replacing a lost organ
but truly restore the loss.

Finally, nano-sized sensors could be inserted inside a biomaterial (eg nanowire biosensors) function
alised with receptors that can monitor the presence of small organic molecules, proteins, cells (eg
cancer cells) and viruses. This could be used to collect information on the implant status and activity.
This feedback information could be used to maximize the implant effectiveness and safety.

Tissue and biomaterial engineering have applications in basically all aspects of regenerative medicine (ie
neuroprosthetics and neuron regeneration (eg spinal cord repair), bone restoration, hearing and vision
restoration, motor restoration, etc.).

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Nanoengineering bone regeneration

Bones and teeth are material that have to bear complex loads of moving bodies, provide a protective
cage for vital organs, anchor tendons and muscles, and act as joints and levers. This functional com
plexity is reflected in a structural complexity. Bones have a complex hierarchical structure at the nano,
micro and macro-levels, which determines their amazing properties.

The 'classic' way to promote the regrowth of bone after injury is to provide a scaffold into which
bone forming cells can migrate and grow attached (fused) to the scaffold (Figure 11). In the past,
numer ous scaffolds have been used, mainly coated with hydroxylapatite which is a natural bone component.
More recently, research has focused on trying to mimic the nanostructure of the scaffold. This involves
working on the topography of the scaffold (surface nano-roughness) but also at anchoring specific
biomolecules to the nano-surface of the scaffold. The idea is to mimic the natural fine organization of
natural bone, which is a combination of nano-topography and (bio)chemistry.

Figure 11: SEM mage showing a hydrogel scaffold grown to

study brain tissue engineering and nerve regeneration. The
image is 100 µm wide.

Image: D. Nisbet, Monash University, NISE Network

(http://www.nisenet.org), licensed under NISE Network Terms
and Conditions

A novel approach is the development of 'artificial bone', which means using macromolecules that
self-assemble into large structures that mimic the natural structure of bone. This is a bottom-up
approach to bone engineering which leads to materials with nanoscale-level control. For example,
some researchers have developed a bone scaffold by biomimetic synthesis of nano-hydrohylapatite
and collagen. Collagen is the most abundant protein in the human body. It is found in most human
tis sues including bone, cartilage, the heart, eye and skin and gives these tissues their structural strength.
These biomaterials assemble into 3D mineralized fibrils that mimic key features of human bone. This
material shows some similarities with natural bone in terms of hierarchical micro and nanostructure,
and three-dimensional porosity. Cells seeded in vitro over this scaffold grew and proliferated well. The
advantage of this approach is that the 'building blocks' are biomimetic macromolecules: once assem
bled, the final 'macro' material can integrate with natural tissues, opening the way to new clinical
approaches to bone regeneration.

When these synthetic nanofibres form, they make a gel that could be used as a sort of glue in bone
fractures or to create a scaffold for other tissues to regenerate on to. As a result of its chemical
structure , the nanofibre gel would encourage attachment of natural bone cells which would help to
patch up the fracture. The gel could also be used to improve implants or hip and other joint replacements.

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NANOYOU DILEMMA The example of artificial bone is one of the NANOYOU dilemmas, part
of the NANOYOU role-playing game (http://www.nanoyou.eu/en/decide). The dilemma almost
arises from the fact that if such technology is developed to heal bones, the natural progression
might be that it is then used to strengthen otherwise healthy bones to make them unbreakable.
This solution might not be available for some people (due to cost or accessibility restriction), so it
could become a human-enhancement tool only for a few. The dilemma is: Is it acceptable to use
processes developed for medical treatment to enhance the human body?

Nanoengineering neuron regeneration

The loss of neuron functions is one of the most dramatic medical conditions in terms of consequences
for the patient: it interferes with basic functions (eg movement) and cognitive capabilities. There are
numerous neurodegenerative diseases (Parkinson's disease, Alzheimer's disease, etc.) that are
connected with neurological damage (neurodegenerative diseases). Neuron function loss can
also derive from a severe accident (spinal cord injury) or a minor one (peripheral neuron damage).
The loss or impairment of a person's neurological function has detrimental effects on their life. The
research in this field is therefore massive, and covers a very wide range of disciplines and sub-discip
lines. There are basically two main approaches to neuron regeneration: tissue engineering and
neuron prosthetics. Until recently, these two approaches were fairly separate, mainly due to the type
of materials employed in the two approaches: 'soft' biomaterials in the first case (biopolymers,
proteins, peptides, etc.), and microchip-type materials in the second case (semiconductors, metals,
etc.). With the advent of nanotechnologies, these two types of materials are starting to integrate not
just in terms of physical attachment (eg protein coatings) but in terms of function: for example, in
nanotechnologies, biomolecules are used as nanoscale motors, or as energy- harvesting materials.
Therefore, in the future the approach to neuron regeneration will be in the form of hybrid nanoscale
devices. A short review of neuron tissue engineering now follows and neuroprosthetics are discussed in the next sect

Neuron tissue engineering

The use of scaffolds to encourage neuron regrowth after injury is an established method. At first,
simple biocompatible polymers were used but, nowadays, the need to engineer the scaffold at the
nanoscale level in two ways is recognised: physically, by inserting nanoscale 'paths' to encourage
directional growth, and biochemically, by adding 'cues' in the form of neuron growth factors and other
essential biomolecules to encourage regrowth (Figure 12). These two elements must be engineered
so that their coordinated action results in neuron regrowth. In the last few years, the research in this
area has been impressive and nanotechnologies have been the enabling tool. For example,
researchers at the Stupp Laboratory (Northwestern University, USA) have fabricated a nanogel of
elongated micelles arranged in a nanofibre matrix and demonstrated that this can support the
directional growth of neurons. The aim of this and other work is to engineer nano-scaffolds that can
support the regrowth of neurons to heal patients affected by neurodegenerative disease or severe
neuronal losses, as in the case of spinal cord injury.

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Figure 12: An engineered nanomaterial that supports specific cellular growth and can promote
desired neurobiological effects: the material is formed of small bioactive molecules that resemble
parts of natural proteins which spontaneously assemble in nanofibres (A) making a macro-gel (B).
The gel supports and steers the growth of stem cells (C).

Images: G. A. Silva, Nature Reviews, 2006, 7(1), 65–74, reprinted with the permission of Macmillan Publishers Ltd, © 2006

Neuroprosthetics
A 'neuron prosthesis' is a device implanted to restore a lost or damaged neuron function. There are two
main kinds of neuron prosthesis: motor and sensory. Much progress in the last decade has been
facilitated by miniaturisation. Nanotechnologies offer opportunities to continue this miniaturisation trend
but also to introduce new features, such as electrodes that actively interface with the nerves, smaller
and more powerful sensors, actuators, and control systems throughout the prosthesis to render it more
natural and effective.

A motor neuroprosthetic device takes signals from the brain or motor pathway and converts that
information to control an actuator device which executes the patient's intentions. Examples include
artificial limbs or hands. The task is extremely complicated, since the motor neuroprosthesis must
also be integrated with the owner's nervous system. Therefore, prostheses have a sophisticated
distributed network of control, actuation and feedback. Limb and hand prostheses also need to be
mechanically similar to natural limbs, otherwise the task of learning to use them will be difficult.
Therefore, to be effective, the device must be designed with nanoactuators and nanosensors fully
integrated into the control system from design to implementation, including the very special ergonomic
interface between patient and device.

What can nanotechnologies do? Progress in current motor neuroprosthetic devices has already been
made possible by nanotechnologies, which are enabling more natural prosthesis by providing:

•smaller and more affordable sensors, processor elements, and the wiring and interconnectors
needed to network them in a distributed control system;
• smaller, more powerful, efficient and responsive actuators that move smoothly, resembling
natural movement — possible because these actuators are based on molecular forces;
• engineering materials that match the strength/weight ratios, elasticity/rigidity, and mechanical
energy storage characteristics of key components of natural limbs.

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A key contribution of nanoscience is in the form of novel materials (eg carbon nanotubes) that can
become elements of new sensors, computing elements and even artificial muscles. Nanoscale mag
netometers, accelerometers, pressure sensors and gyroscopic devices will be able to detect even min
ute movements and angle changes more precisely. These nanomaterials will support the design of
internal movement devices to render the prosthetic movement more natural, and to ensure the accu
rate transmission of control and feedback information between device and patient. The impact of
nanotechnologies will not be in the form of miniaturized robots but rather assemblies of connected
networks that compute, communicate, sensing, actuate, etc., to make up a prosthesis that resembles
as much as possible the natural lost limb.

Motor neuroprosthetics commonly integrate sensory neuroprosthetics as well, since the

reconstruction of motor functions needs to be associated with the reconstruction of haptics — the
sense of touch (or more specifically, the sense of pressure and force feedback from the body to the
brain). Haptics, along with vision, hearing, and balance, is an essential component of the stream of
feedback informa tion that the nervous system sends to the brain. So-called smart materials (or
dynamic materials, meaning materials that change their shape or function in response to an external
stimulation) and nanosensors are expected to provide many options to implement sensory neuroprosthetics.

Research in the area of motor and sensory prosthetics is very active and is not only directed to the
fab rication of human motor prosthesis but also to robotics for computer-assisted surgery, deep-marine
investigation, astronomy, etc.

In addition to neuroprosthetics that restore motion functions, vision and auditory neuroprosthet ics
are also extremely important. Both technologies have made enormous progress in the last decade and
much has been enabled by micro and nanotechnologies. One such example is cochlear implants,
which are a type of electronic neuroprosthesis implanted in the middle ear, where they stimulate the
ossicles electromechanically, rather than acoustically, through either electromagnetic or piezoelectric
transducers. Nanotechnologies have enhanced microelectronics, batteries and micromechanical trans
ducers in cochlear implant devices. Problems in those devices still exist, in particular refinement of the
signal processing (eg to recognise voice pitch in music), improvement in their long-term biocompatiability
(build-up of biofilms and plaques) and prevention of bacterial fungal infections. Nanomaterials are
expected to have an important impact in all these areas.

Neuronal stimulation, monitoring and pain management

The cardiac pacemaker is one of the bestknown and most widely used neuroprosthetics. Other types
of electronic stimulators are cardiac defibrillators, cochlear implants, bone-growth stimulators, neural
stimulators for the deep brain to control tremors in Parkinson's disease, neuronal stimulators for spinal
cord, sacral and other nerve stimulators. Nanotechnologies are impacting these electronic stimulators
through improved battery technologies, biocompatible materials and surface treatments for enclosures
and leads, electrode miniaturisation and efficiency improvements, and smaller-sized integrated circuits
for control and power with increased speed and processing capabilities.

Electrical stimulation of neural tissue by surgically implanted neuroelectronic devices is already an

established modern therapy. Integrated micro and nanoscale devices allow many more electrodes to
be applied to the target site with fine resolution and in a coordinated, dynamic way. Recording of
neural activity is also implemented using nanoscale electrodes, since a much larger number of
recording sites is possible. These implanted probes must be resistant to challenging environments,
compared to the nanoscale surface engineering of these probes is essential. In addition to protecting the probes,

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nanotechnologies are contributing in developing improved active interfaces between neurons and
electrostimulation devices.

An example of an electronic stimulator is a deep brain stimulator. This device will make it possible to
treat patients with severe Parkinson's disease — a disorder of the central nervous system that often
impairs the sufferer's motor skills, speech and other functions. It has been found that the
uncontrollable tremor of patients can be prevented if a fine nano-size electrode delivering a continuous
electrical stimulus is inserted into the brain. This electrical stimulus has the effect of eliminating the
precise tremors.

Reduction insize and power requirements with the integration of microelectronic devices makes it
feasible in many cases to power an implanted device by RF electromagnetic transmission of power,
thus eliminating wires and batteries. This is already the case for implanted pacemakers. Improvements
in energy storage through nanoengineered energy materials, such as supercapacitors and conductive
polymers, coupled with the low power requirements of nanoengineered electronics, will allow huge
improvements in terms of size and the capabilities of such devices. These devices make it possible to
perform electrical stimulation at selected points of nervous, sensory and neuromuscular systems. Such
improvements might eventually make it possible to use implanted electrical stimulation for bone and
tissue grafts, and to stimulate functions in the endocrine system and other organs.

NANOYOU DILEMMA The example of deep brain stimulation is part of the NANOYOU role
playing game (http://www.nanoyou.eu/en/decide). The dilemma from considering a deep brain
stimulator to treat Parkinson's disease. Now, this device could also be used to treat other
medical and health conditions such as intractable epilepsy, as well as mood and eating
disorders. Could this nanotechnology be used to increase the capability of the brain in areas
for which it was not originally developed? An example of this might be students enhancing their
concentration during exams. The dilemma is: Is it ethically acceptable to use technologies
developed for specific medical treatments for other purposes such as improving human capabilities?

Non-invasive brain-machine interfaces

The control of physical objects by the power of thought alone has always captured the imagination of
man. Until recently, this possibility was only envisioned in science fiction. Now, with the aid of new
tech nologies, and as a result of decades of studies on neuron activity in the brain, the control of
machines and computers by the brain is becoming a reality. Systems are being developed where the
patterns of neuronal firing in the brain are translated into electronic controls to support the
communication, mobility and independence of paralysed people. This is possible because the firing
of neurons and the travel of ion currents along axon membranes generate an electrical current, which,
in turn, generate a magnetic field. A steady electrical current generates a static magnetic field, but if
the electrical current changes (due to neuronal activity), so does the magnetic field. a change in
external magnetic field can induce a change in electrical (neuronal) activity. Therefore, magnetism
can become a non-invasive communication tool with nerves without implanted electrodes and painful transcutaneous

The technique is called magnetic monitoring and it requires extremely sensitive magnetometers
because the magnetic fields produced by brain activity are very small. Today, magnetoencephalography

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(MEG) can map brain activity on a 1 mm grid or less. The first generation of MEG equipment was very
bulky, requiring shielded rooms, high power consumption, cryogenic cooling of detectors and significant
processing time. The technique has so far been limited to research labs or extremely specialised
medical investigations. Nanofabrication is enabling a reduction in size of most of the components of
MEG equipment (sensors, magnets, etc.) and new concepts are being developed: in prototypes, this
progress has already led to thousandfold improvements in sensitivity and reductions in size and power
requirements by factors of 10 to 100.

Magnetism can also be used to induce electrical currents in the neuron cell membrane such as
those induced by implanted electrodes, but without physical contact. Magnetic stimulation is a new
medical technique which requires strong magnetic fields that must vary or pulse in order to generate
an electric field. The impact of nanotechnologies in this case is the nanofabrication of compounds and
alloys that produce better high-temperature conducting materials. This will make it possible to reduce
the size of the device and the cryogenic environment needed for the performance of superconducting
magnets. Nanoparticle thin films are also being developed as shielding materials.

Numerous new nanoscale magnetometer designs are being developed, one of which is the optical
atomic magnetometer. This instrument is based on the interaction of laser light with atoms oriented
in a magnetic field in a gas phase. The instrument measures the change in alignment when atoms with
a magnetic spin moment interact with a beam of a laser. In the absence of a magnetic field, the atoms
will align with the electrical and magnetic field of the laser beam crossing the atoms. Any disturbance
by a magnetic field will disorient the alignment with the beam, reducing the amount of light transmit
ted through the gas. A prototype of such a system has been developed by NIST (USA) containing
about 100 billion atoms of rubidium gas in a vial the size of a grain of rice. The change of spin was
easily detectable and scalable to much smaller sizes. The NIST prototype was able to detect the
heartbeat of a rat. Researchers predict that with their small size and high performance such sensors
could lead to magnetocardiograms that provide similar information to an electrocardiogram (ECG)
without requir ing electrodes on the patient's body, even outside clothing. This technique could become
a realistic alternative to MRI and PET imaging, without the injection of contrast-enhancement agents or tracers.
What is really exciting is that, even with the laser and heating components, this new device uses rela
tively low power and can be extremely small compared to any current magnetic stimulation device. It
might one day be possible to use sensors to make portable MEG helmets for brain-machine interfaces.

Although much progress has been made and much research is underway, there are some major obs
tacles to overcome before brain-machine interfaces become a reality. Wireless signal transmission
from brain implants is still futuristic, along with wearable magnetic brain-machine interfaces. Another
challenge is the optimisation of the microelectrodes that record neuronal activity, which tends to
degrade in time due to biofilm formation. Risk of infection is also a major problem. Better engineering
of interfaces using nanoengineered materials is needed to improve biocompatibility and durability
and to allow lower stimulation potentials.

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ELSA TOPIC Neuroprosthetics raises a number of ELSA issues. Normally, these types of devices
are only considered when other pharmacological and neurosurgical options have been exhausted.
Bioengineers and medical engineers say that their role should be to compensate for a body's
deficit (as result of an accident or a disease), not to replace any existing function. It should not
lead to the enhancement of human capabilities. however, nanotechnologies are making these
developments more feasible and affordable, obliging researchers in the field, as well as
regulators, ethicists and sociologists to reflect on the social, medical and ethical consequences
of these devices. The same applies to the concept of cognitive prostheses: a system developed
to support and augment the cognitive abilities of its user. Of course, such devices could be
extremely useful to people with impaired communication. However, the concept raises the pos
sibility of enhancement of cognitive capabilities for other uses, which brings up many social,
ethical and regulatory questions. One such is access to these types of devices. Will these be
affordable for everybody, covered by social health systems, or available only to wealthy people?
Is it ethical to have a technology that can enhance a person's mental ability, but only if they can
afford it? How will this technology be regulated in situations where the mental/cognitive ability of
numerous individuals is assessed (job interviews, competitions, etc.)?

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CHAPTER 2:

ENVIRONMENT

In industrialized nations, the air is filled with numerous pollutants caused by human activity or indus
trial processes, such as carbon monoxide (CO), chlorofluorocarbons (CFCs), heavy metals (arsenic,
chromic , lead, cadmium, mercury, zinc), hydrocarbons, nitrogen oxides, organic chemicals (volatile
organic compounds, known as VOCs, and dioxins), sulfur dioxide and particulates. The presence of
nitrogen and sulfur oxide in the air generates acid rain that infiltrates and contaminates the soil. The
high levels of nitrogen and sulfur oxide in the atmosphere are mainly due to human activities, especially
the burning of oil, coal and gas. Only a small portion comes from natural processes such as volcanic
action and the decay of soil bacteria. Water pollution is caused by numerous factors, including sewage,
oil spills, leaking of fertilizers and pesticides from land, by-products from manufacturing and extracted
or burned fuels.

Contaminants are most often measured in parts per million (ppm) or parts per billion (ppb) and their
toxicity defined by a 'toxic level'. The toxic level for arsenic, for instance, is 10 ppm in soil whereas for
mercury it is 0.002 ppm in water. Therefore, very low concentrations of a specific contaminant can be
toxic. In addition, contaminants are mostly found as mixtures. Consequently, there is a need for
technologies that are capable of monitoring, recognising and beginning, treating such small amounts
of contaminants in air, water and soil. In this context, nanotechnologies offers numerous opportunities
to prevent, reduce, sense and treat environment contamination. Nanotechnologies can enhance and
enable pre-existing technologies and develop new ones.

What can nanotechnologies do? Nanotechnologies offers the ability to control matter at the
nanoscale level to create materials with specific properties that can serve specific functions. This is
particularly important in environmental issues where pollution often arises from the presence of a
spe cific contaminant within a mixture of materials, in solid, liquid or gas form. The small size of
nanoma terials, together with their high surface-to-volume ratio, can lead to very sensitive detection.
These properties allow the development of highly miniaturized, accurate and sensitive pollution-
monitoring devices (nano-sensors). Nanomaterials can also be engineered to actively interact with a
pollutant and decompose it into less toxic species. Thus, in the future, nanotechnology could be used
not only to detect contaminated sites but also to treat them. Finally, this technology can be used to
reduce the production of harmful wastes in manufacturing processes by reducing the amount of
material used, and by employing less toxic compounds.

Another application area is the engineering of coatings that are nanostructured in such a way that they
resist the attack of pollutants or have self-cleaning properties so that are easily cleaned by rain water
and, therefore, require less detergent to be washed.

The starting point for any discussion on the applications of nanotechnologies to the environment is the
ability of nanoscience to create new nanostructured materials with specific properties to serve specific
functions. These aspects were previously discussed in Module 1, Chapters 4 and 5.

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Remediation and mitigation

Soil and groundwater contamination arising from manufacturing processes are a matter of great com
plexity and concern. Affected sites include contaminated industrial sites (including lakes and rivers in
their vicinity), underground storage tank leakages, landfills and abandoned mines. Pollutants in these
areas include heavy metals (eg mercury, lead, cadmium) and organic compounds (eg benzene, chlor
inated solvents, creosote). Nanotechnology can develop techniques that will allow for more specific
and cost-effective remediation tools. Currently, many of the methods employed to remove toxic con
taminants involve laborious, time-consuming and expensive techniques. A pretreatment process and
removal of the contaminated area is often required, with consequent disturbance of the ecosystem.
Nanotechnology facilitates developing technologies that can perform in situ remediation and reach
inaccessible areas such as crevices and aquifers, thus eliminating the necessity for costly 'pump-and
treat' operations. In addition, as a result of its ability to manipulate matter at a molecular level, nano
science can be used to develop remediation tools that are specific to a certain pollutant (eg metal),
therefore increasing affinity and selectivity, as well as improving the sensitivity of the technique.

Drinking water quality and its contamination from pollutants is another matter of concern. Mercury and
arsenic are, in particular, two extremely toxic metals that pose very high health risks. Remediation
methods that allow the fast, economic and effective treatment of water tarnished with such contam
inants is urgently needed. Nanotechnology can introduce new methods for the treatment and purifiation
of water from pollutants, as well as new techniques for wastewater management and water desalination.

Nanomaterials is currently evaluated for remediation use include iron and bimetallic nanopar tiles,
semiconductor nanoparticles, magnetic nanoparticles and dendrimers. Some detailed examples follow.

Remediation using metal nanoparticles

The use of zero-valent (Fe0 ) iron nanoparticles for the remediation of contaminated soil and soil is a
good example of how environmental remediation can be improved with nanotechnology. When exposed
to air, iron oxidises easily to rust; however, when it oxidises around contaminants such as trichlorethylene
(TCE), carbon tetrachloride, dioxins, or PCBs, these organic molecules are broken down into simple,
far less toxic carbon compounds. Since iron is non-toxic and is abundant in the natural environment
(rocks, soil, water, etc.), some industries have started using an 'iron powder' to clean up their new
industrial wastes. However, the 'iron powder' (ie granular zero-valent iron with dimensions in the micron
range) is not effective for decontaminating old wastes that have already soaked into the soil and water.
Furthermore, bioremediation using granular iron powder is often incomplete: some chlorinated
compounds, such as PCE or TCE, are only partially treated and toxic by-products (such as DCE) are
still found after treatment. This effect is due to the low reactivity of iron powders.

Another matter of concern is the decrease in reactivity of iron powders over time, possibly due to the
formation of passivation layers over their surface.

Nanotechnology has offered a solution to this remediation technology in the form of iron nanoparticles.
These nanoparticles are 10 to 1,000 times more reactive than commonly used iron powders. They have
a larger surface area available for reacting with the organic contaminant and their small size

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(1–100 nm) allows them to be much more mobile, so they can be transported effectively by the flow of
groundwater. A nanoparticle water slurry can be injected into the contaminated plume where treatment
is needed (Figure 1). The nanoparticles are not changed by soil acidity, temperature or nutrient levels,
so they can remain in suspension maintain their properties for extended periods of time to establish an
in situ treatment zone. Experimental results collected both in the laboratory and in the field have shown
that nanoscale iron particles are very effective for the complete transformation and detoxifica tion of a
wide variety of common environmental contaminants, such as chlorinated organic solvents,
organochlorine pesticides and PCBs.

Figure 1: Nanoscale iron

particles for in situ remediation

When nano-sized iron powders are used, no toxic by-products are formed, a result of the increased
reactivity and stability of the nanoparticles compared to the granular iron powder. Contaminant levels
around the injection level are considerably in a day or two and eliminated within a few days. As a
result of their stability, nano-iron particles remain active in a site for six to eight weeks before they
become dispersed completely in the groundwater and become less concentrated than naturally
occurring iron. Researchers are sources assessing whether the technique could also be used for the
remediation of dense non-aqueous phase liquid (DNAPL) within aquifers, as well as for the
immobilisation of heavy metals and radionucleotides.

Bimetallic iron nanoparticles, such as iron/palladium, have been shown to be even more active and
stable than zero-valent iron nanoparticles, thus further improving this remediation technology. Finally,
iron or bimetallic nanoparticles could be anchored on solid supports such as activated carbon or silica
for the ex situ treatment of contaminated water and industrial wastes.

Remediation using semiconducting nanoparticles

Semiconducting nanoparticles made of TiO2 and ZnO are used in photocatalytic remediation. Being
semiconductors, these materials produce an electron-hole pair when irradiated with a light having
energy in the order of the material band gap. TiO2 has a band gap of 3.2 eV so when the material is
irradiated with UV light an electron-hole pair is formed. Both TiO2 and ZnO are capable of transferring
the charge to organic pollutants (such as halogenated hydrocarbons) and induce their oxidation to less

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harmful by-products, such as CO2, H2O and other species. Since TiO2 and ZnO are readily available and
inexpensive, their use for remediation has been studied for many years. Recently, nano-sized TiO2 and ZnO
have been considered, as these have more active surface given the same volume of material. The vision is
to create solar photocatalysis remediation systems where TiO2 or ZnO are used to convert toxic
contaminants, such as chlorinated detergents, into benign products using the radiation. There is evidence
that these semiconductors can photodegrade numerous toxic compounds, but the technology requires
improvements in term of efficiency, since TiO2 or ZnO only absorb UV light which represents only 5 % of
the solar spectrum. In this context, nanotechnology could bring an improvement in two
ways.

1. When noble metals like gold and platinum are chemisorbed to the TiO2 and ZnO nanoparticles, the
photocatalytic activity is accelerated. The reason is that the presence of the metal helps to keep
the electrons and holes from recombining in the semiconductor and thereby increases the efficiency
of the photocatalysis.
2. To increase the photoresponse window of TiO2 and ZnO from UV to visible light, the nano
particles can be modified with organic or inorganic dyes. This is an area of intensive research.

Nanomaterials have also been found able to remove metal contaminants from air. For example, silica
titania nanocomposites are being evaluated for use in the removal of elementary mercury (Hg) from vapours
such as those from combustion sources. In these nanocomposites, silica acts as a support material and
titania transforms mercury to a less volatile form (mercury oxide).

Remediation using dendrimers

Dendrimers are highly branched polymers with controlled composition and nanoscale dimensions.
Chelating agents in the form of dendrimers are also studied for the removal of metal contaminants.
These can be designed so as to be able to act as 'cages' and trap metal ions and zero-valent metals, making
them soluble in appropriate media or able to bind to certain surfaces. The vision is to use dendrimers as
nanoscale chelating agents for polymers supported ultrafiltration systems.

Remediation using magnetic nanoparticles

Another class of nanoparticles that have environmental applications is magnetic nanoparticles. For example,
researchers from Rice University's Center for Biological and Environmental Nanotechnology (CBEN) have
recently shown that nanoparticles of rust can be used to remove arsenic from water using a magnet. The
concept is simple: arsenic sticks to rust, being essentially iron oxide, which to be magnetic so it can be
removed from water using a magnet. Nano-sized rust, about 10 nm in diameter, with its high surface area,
has been found to improve removal efficiency while reducing the amount of material used. Compared to
other techniques currently used to remove arsenic from contaminated water, such as centrifuges and
filtration systems, this method has the advantage of being simple, and most importantly, not requiring
electricity. This is very important, given that arsenic-contaminated sites are often found in remote areas with
limited access to power. Magnetic nanoparticles modified with specific functional groups are also used for
the detection of bacteria in water samples.

Arsenic and arsenate may also be precipitated using nanoscale zero-valent iron (Fe0) as indicated by
recent studies. The removal mechanism in this case involves the spontaneous adsorption and co of
arsenic with the oxidised forms of Fe0. As already noted, zero-valent iron is extremely reactive when
it is nano-sized, so it is currently considered a suitable candidate for both in situ and ex situ
underground treatment.

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ELSA and SAFETY TOPIC Although research seems to show that remediation using iron
oxide nanoparticles is effective, there are currently some concerns regarding the use of
nanoparticles for soil and water remediation. They are related to the fate of the nanoparticles
once they are injected into the contaminated site, and the possibility they might be so mobile
as to disperse outside the targeted area. It is not clear if such a situation would pose an
environmental problem such as interference with plant or animal life cycles. For these reasons,
the method is not yet approved and used in the EU. Research is underway to clarify these
issues and discussions are taking place on possible strict regulation for this remediation technology.

Remediation using airgels and solid absorbents

The problem of oil spills in seawater is of great concern and has detrimental environmental conse
quences. Currently, there are numerous bioremediation strategies that use microbial cultures, enzyme
additives or nutrients additives to clean up oil spills. The purpose of these additives is to boost the nat
ural nanotechnology of the microbial community to decompose the oil material. Another method gain
ing acceptance is the use of aerogels (a nanomaterial) modified with hydrophobic molecules to
enhance the interaction with the oil. These airgels have very large surface areas so they can absorb
16 times their weight of oil. They act as a sponge: once the oil has been absorbed, the 'oil-soaked
sponge' can be removed easily. The problem is that these materials are expensive, so alternatives are
under study. The company Interface Scientific Corporation has developed a new nanomaterial
modified with self-assembled monolayers (SAMs) which appears to be very effective in remediating oil
spills. The company does not provide details of the material but claims that the nanomaterial can
absorb 40 times its weight in oil — a method that exceeds any other currently available — and that the oil can be recov

As outlined, the use of nanoparticles is very promising in the field of environmental remediation and
treatment, precisely because of their small size and reactivity. however, some concern exists
regarding their use in soil and water treatment: dispersed once in a contaminated site, would the
nano particles be mobile to a point that they could be taken up by plants or animals at the site and
affect them? Biodegradable nanoparticles are likely to be less problematic; nevertheless, there is a
need to investigate these safety aspects, and this is the subject of numerous international research
pro grammes. These concerns belong to the more general field of environmental impact assessment
of the use of nanoparticles, which includes both risk assessments and life-cycle analysis to
understand the short-term and long-term effects of nanoparticles in the environment.

Nanomembranes and nanofilters

Nanotechnology can also be employed for the fabrication of nanofilters, nano-adsorbents and
nanomembranes with specific properties to be used for decontaminating water and air. As with other
applications, it is the ability to manipulate matter at a molecular level that makes nanotechnology so
promising in this field, together with the small size and high surface-to-volume ratio of nanomaterials
that are employed in the fabrication of these products.

In principle, 'nanotraps' designed for a certain contaminant can be produced, for example with a spe
cific pore size and surface reactivity. An example is given by the work carried out at Rice's CBEN,
where researchers are developing reactive iron oxide ceramic membranes (ferroxane membranes)
that are capable of remediating organic waste in water (Figure 2).

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Figure 2: Ceramic nanomembrane

Image: Professor M. Wiesner, Wiesner Laboratory,

Duke University

Filters and membranes can also be engineered to be 'active' in the sense of being able not only to trap
a certain contaminant, but also to chemically react with it and convert it to a non-toxic product. For
example, at the University of Tennessee are investigating a new type of nanofibre for the removal of
micro-organisms via filtration that can also kill them on contact.

An interesting application of nanomembranes has been developed by researchers at the University of

California Los Angeles (UCLA) in the form of a new reverse osmosis (RO) membrane for seawater
desalination and wastewater remediation. The membrane is made of a unique cross-linked matrix of
polymers and engineered nanoparticles designed to draw in water ions but repellant. This is possible
due to the nano-size of the holes forming the membrane, which are 'tunnels' accessible only to the water
molecules. Another distinctive feature of this nanomembrane is its ability to repel organics and bacteria,
as a result of the chemical composition of the nanoparticles embedded in the membrane.
Compared with RO membrane, these membrances are thus less prone to clogging, which increases the
membrane lifetime with an obvious economic benefit.

Superhydrophilic filters

In many circumstances, access to clean and safe water is a problem. Nanofilters allow such contaminants
as arsenic and other heavy metals to be filtered from water. One commercial reality is the LifeSaver®
bot that has a superhydrophilic filter inside blocks material up to 15 nm in size, which includes viruses
and bacteria. The filter is inserted in a plastic bottle and enables contaminated water to be cleaned on-site.

Pollution prevention
Nanotechnologies offer many innovative strategies to reduce pollution in numerous processes includ
ing the reduction of waste in manufacturing processes, a reduction of the use of harmful chemicals,
reduced emission of greenhouse-effect gases in fuel combustions and the use of biodegradable plas
tics. These are only a few of the many approaches that can be taken to reduce pollution of the environ
ment. Nanotechnologies are already actively involved in this sector, either as a technology producing
advanced materials that pollute less, or as a method to increase the efficiency of certain industrial
processes (eg catalytic processes).

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Materials
Materials that are manufactured in a more environment-friendly way using nanotechnologies include bio
degradable plastics made of polymers that have a molecular structure optimal for degradation; non-toxic
nanocrystalline composite materials to replace lithium-graphite electrodes in rechargeable batteries; and
self-cleaning glasses, such as Activ™ Glass, a commercial product available worldwide from Pilkington.
The glass has a special coating made of nanocrystals of TiO2 which, when exposed to daylight, reacts in
two ways. First, it breaks down any organic dirt deposits on the glass and, secondly, when exposed to
water, it allows rain to 'sheet' down the glass easily and wash the loosened dirt away. In this product,
TiO2 is found in the form of a thin film 2–20 nm thin gas phase by a high-temperature gas phase. The
thickness of the film is essential for enabling maximum photocatalytic activity and transparency (Figure 3).

Figure 3: Explanation on how Pilkington Activ™ Self-cleaning Glass works as described by the
manufacturer (http://www.pilkington.com)

The coating is hydrophilic (water contact angle (CA) is 20° compared to conventional soda glass for
which the CA is 40°). When dirt is reducing, the contact angle of the surface increases, but is then
reduced again upon irradiation. The photochemical reaction, which requires oxygen, is quite complex
and involves a number of radical sub-products. Titanium oxide is not consumed in the reaction but acts
as a catalyst. As a result, organic material is decomposed to CO2. Concurrently, the contact angle of
the surface is further reduced upon irradiation (from 20° to about 15°). After irradiation, dirt can be more
easily removed from the glass by rain. The result is that water spreads very effectively (form ing a
'layer' over the glass), washing the surface easily. The coating is partially durable to abrasion.
Although the name of the product suggests otherwise, this is not a truly 'self-cleaning' layer since it
requires water to allow the surface to be cleaned.

Lotus effect® surfaces and textiles

Sometimes, the term 'self-cleaning' is also associated with surfaces that have been engineered to
imitate the natural 'self-cleaning' effect found in some leaves, such as the leaf (the effect is described
in detail in Module 1 , Chapter 2: Nanoscience in nature). In this case, the coating is not a uniform
layer with a specific chemical functionality (as in the case of photocatalytic coating), but

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a surface with an engineered topography at the nanoscale level. This leads to a surface which is
super hydrophobic (extremely water repellent). Water droplets rolloff the surface and in doing so
collect and remove dirt on the surface.

The Lotus effect® has been an inspiration for several innovative materials, such as coatings and tex
tiles. The realisation that certain surface properties can induce water repellence is important in numer
ous applications. Materials scientists are now engineering numerous types of materials to render them
superhydrophobic.

There are many instances where avoid the wetting of a surface is an advantage, for instance in
textiles, which are routine stained by liquids (juices, coffee, etc.) and solids (mustard, ketchup, etc.).
Some companies such as Nano-Tex, Inc., are now commercialising textiles that are engineered to
confer superhydrophobic properties on their textiles (Figures 4 and 5). This effect is obtained by the
presence of 'nano-sized whiskers' on the surface of the fibres that make up the fabric.

Figure 4: Liquid staining on a Nano-Tex®fabric

Image: Nano-Tex, Inc., © Nano-Tex, Inc.

NANO--TEX LOTUS

Figure 5: (left) High resolution images of the Nano-Tex® fabric; (right) contact angle images of
water droplet on Nano-Tex® fabric and lotus leaf

Images: (left) Nano-Tex, Inc., © Nano-Tex. Inc.; (right) iNANO; Aarhus University, Creative Commons Attribution
ShareAlike 3.0)

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Experiment D in the Experiment Module studies the Lotus effect® and

how materials can be engineered to mimic this effect.

The inclusion of TiO2 nanoparticles in textiles is also being evaluated, as this material catalyses the
degradation of organic dirt.

Surfaces and materials engineered to mimic the Lotus effect® are useful in construction as they
allow a reduction in the need for cleaning. Currently, there are various products commercialized
or under research that make use of this principle, for example Lotusan®, an exterior paint from the
firm Sto launched in 1999. The application of this exterior paint reduces the attack of dirt on the
façade to which it is applied, and induces self-cleaning properties when rain droplets roll off and drag
dirt away with them.

The above mentioned applications are examples of cases where the superhydrophobic properties of an
engineered material, such as a textile or a coating, can reduce cleaning needs, with a consequent
reduction in water usage and obvious environmental benefit.

It should be noted that, in contrast to photocatalytic coatings, those based on the Lotus effect® are non-
transparent: light is scattered due to the rough nature of the coating. Researchers are thus also
investigating transparent superhydrophobic surfaces.

Antimicrobial coatings, textiles and other products

Antimicrobial coatings are needed in many applications, for example to protect medical surfaces and
tools, or to reduce microbial attack on the hulls of boats. Sprays and coatings for this use already exist
but improvement in this area is needed as many microbes are becoming resistant to the antibiotic
treatments that have been used so far. To prevent bacteria attachment, surfaces with nanocoating with
specific functionalities and topography are under investigation. Antifouling surfaces are being evaluated
for use in the coating of medical utensils and instruments and household appliances, as well as for
coating boats. A nanomaterial that is becoming widely used is silver nanoparticles.

Silver is a metal with a long history used for its antibacterial properties — even the Romans used it to
dress wounds. This property explains why silver has been used to produce the highest-quality cutlery
(silverware) or to store water in vessels in antiquity (even by the Phoenicians). In medicine, 1% silver
nitrate was used in the past as an eye solution to prevent infections in newborn children, and until
antibiotics were discovered, silver nitrate was added to germicides and antiseptics as a disinfectant.

The antibacterial properties of silver are due to the silver ions (Ag+) released by the bulk metal
once this is oxidised. In fact, silver tableware or dishware has antimicrobial activity only if oxidised
spe cies are present on their surface. Silver ions induce the oxidative stress of the bacteria cell wall,
where many cellular functions are performed, affect the bacteria's ability to respire and to maintain an
intra-cellular environment suitable for life. Silver ions inhibit bacteria growth, suppress respiration and
metabolism and generally induce cell death. Silver toxicity has been shown towards many strains of
bacteria, both gram-negative and gram-positive, and to fungi (less towards viruses).

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Silver is not considered toxic to the cardiovascular, nervous or reproductive systems in humans. In
some people, exposure to silver leads to argyria (or argyrosis) which is due to a process of sequestration
of silver ions in an innocuous form which is not reversible and leads to pigmentation or discolouration of
the skin. The few cases of death due to silver intoxication have been related to very high concentrations
of silver.

In recent years, silver nanoparticles (often called 'nanosilver') have been added to numerous con
sumer products to give them antimicrobial properties. Because of their antibacterial effectiveness
and low toxicity towards mammalian cells, silver nanoparticles have become one of the most com
mon nanomaterials used in consumer products. The range of products is quite wide and includes
kitchen utensils (pots, pans, etc.), personal wear (socks, shoe liners, underwear), outerwear and
sports wear, bedlinen (sheets and mattress covers), appliances (refrigerators, washing machines ,
air filtration devices, computer keyboards), disinfectant sprays (deodorants) and cosmetics.
Nanosilver is incorp orated into these different materials through various impregnation techniques
(sprayed, painted over the product, incorporated into plastics, etc.).

ELSA TOPIC Silver has been used for centuries so exposure to silver, its ions and associated
forms is not new to humans, animals and plants. There is growing concern, however, that the
steady increase in consumer products using nanosilver might lead to detrimental environmental
consequences. The concern is twofold and involves the possible release of silver nanoparticles
from the product and silver ions (and colloids formed with other salts) either through use of the
material (eg washing of fabrics containing nanosilver), or after their disposal. Currently, it is not
clear what is more dangerous for the environment: the actual silver nanoparticles or the ions
they release. Since it is known that nanomaterials are normally more reactive than their bulk
counterparts, and that they can display new properties, there is concern that silver nanoparticles
could behave unexpectedly towards cells (human, bacteria, viruses, plant cells, etc.). Questions
have also been raised concerning silver nanoparticle uptake by plants and other systems that
might come in contact with nanosilver well before humans through waste water or other water
systems. In model experiments, it has been shown that silver nanoparticles are very toxic to the
benign bacteria used to remove ammonia in waste water. The concern is that if large quantities
of consumable products (eg socks, toothbrushes, jackets, etc.) are used, high levels of silver
ions, silver nanoparticles or their aggregate forms could be released into rivers and lakes and
damage the ecosystem. Many agencies are calling for stricter safety testing of nano-based
products and for research on the safety of these products.

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NANOYOU DILEMMA The example of silver nanoparticles in a consumer product (socks) is

one of the NANOYOU dilemmas included in the NANOYOU role-playing game 'Antibacterial
Socks' (http://www.nanoyou.eu/en/decide). In this dilemma, students consider the case of
socks with silver nanoparticles in their fabric to eliminate the bacteria which cause smelly
feet and fun gal infections. Based on the fact that exists regarding the ecotoxicity of nanosilver,
students are encouraging to reflect on this product through a benefit versus risk analysis. The
dilemma is: Is it right to sell antibacterial socks containing silver nanoparticles when it is not
yet known if they are entirely safe for the environment?

The use of silver nanoparticles in personal hygiene products, such as toothbrushes, is

debated the NANOYOU NT virtual dilemma 'Nano toothbrush' (http://www.nanoyou.eu/en/
decide). Here, the question asked is if the prolonged use of the toothbrush can cause the
degradation of its material and the accidental release of nanoparticles in the saliva, and if this
could have some negative health effects.

Anti-fouling coatings for boats are the NANOYOU NT virtual dilemma 'Boat coating'.
These coatings reduce the attachment of micro-organisms to the surface of the boat, which
otherwise reduce its speed. In time, the coating can degrade, so we ask students to consider if
this could have an unwanted environmental effect.

Other coatings
A number of products are appearing on the market that can confer some specific property to the sur
face and which contains nanoparticles (eg silica) or other nanomaterials. Examples are anti-graffiti
coatings, anti-fog coatings, anti-fingerprint coatings, etc.

NANOYOU GAME Anti-graffiti coatings are used in one of the NANOYOU jigsaw puzzle games
(http://nanoyou.eu/en/play-nano.html) — students must match the nanomaterial to its application,
connecting it to a specific need.

Fertilisers and wood treatment products

Another area where nanotechnologies are making a contribution is in the development of fertilityers
and wood treatment products that are more stable and leach less into the environment. For example,
researchers at Michigan State University have incorporated biocides for wood treatment inside poly
meric nanoparticles. The small size of the nanoparticles allows them to travel efficiently inside the very
fine, sieve-like structure of wood and, at the same time, the biocide, being safely trapped inside a
'nanoshell', is protected from leaching and random degradative processes.

Biomimetic water harvesting

In Module 1, it was shown how natural nanomaterials are inspirational for the fabrication of advanced
materials (Module 1, Chapters 2 and 5). One example is biomimetic water-harvesting materials.
Some plants and insects have the ability to capture water from fog. For example, the Namibian desert
dwelling beetle Stenocara has bumps on its wing scales with superhydrophobic nanostructured

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surfaces. The peaks of the bumps are extremely hydrophilic, whereas the slopes of the bumps and the
area between them are covered with hydrophobic wax. As a result of this fine nanostructure, as drop
lets accumulate in size, they roll from the peaks to the waxy channels to a place in the beetle's back that
supplies its mouth. A UK company, QinetiQ Ltd, has developed sheets that capture water vapour from
cooling towers and industrial condensers based on the nanostructure of the beetle's wing. These
materials can capture 10times more water than conventional technology.

Nanocatalysis
A catalyst is a substance that increases the rate of a chemical reaction without being consumed or
chemically altered. Conventional catalysts are rare earth metals such as palladium (Pd) and platinum
(Pt), which are very expensive. One of the most important properties of a catalyst is its 'active surface'
where the reaction takes place. The active surface increases when the size of the catalysts is decreased
(Figure 6). The greater the catalyst's active surface, the greater the reaction efficiency.
Research has shown that the spatial organization of the active sites in a catalyst is also important.
Both properties (nanoparticle size and molecular structure/distribution) can be controlled using
nanotechnology. Hence, one area of intense nanoscience research is the development of new
nanostructured catalytic surfaces.

Figure 6: (left) Overview of the hydrodesulphurisation (HDS) catalytic reaction; (right) schematic
representation showing how nanoparticles could be included in the catalyst material of a desul
phurising fuel reactor. The image on the far right is a real STM image of a MoS2 nanocrystal on
Au(111) showing peculiar atomic distribution at the edges of the crystal.

Images: F. Besenbacher, iNANO, Aarhus University

In the environmental field, nanocatalysis is being evaluated, for example, in the desulfurization of
fuels, with the aim of developing 'clean' fuels containing very low sulfur products (produced in the fuel
during its refining process and responsible for generating sulphuric acid during fuel) combustion).
Recent nanotechnology research at iNANO has also aided the Danish company Haldor Topsøe A/S in
implementing a new generation of hydrodesulphurisation catalysts (BRIM™ Technologies) to be used
for sulfur clean-up of fossil fuels worldwide. The hydrodesulphurisation (HDS) catalytic reaction is

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a reductive hydrogen treatment of fuels to clean up sulfur-containing oil compounds, preventing the
emission of many tons of harmful sulfur into the environment on a daily basis.

Another example is Oxonica's Envirox fuel, which uses nano-sized cerium oxide as a catalyst to enhance
the efficiency of the fuel combustion. This enhanced-fuel was tested in 2003 and 2004 in 1 000 buses in
the United Kingdom (another 500 buses were tracked as control). It was found that the test buses used 5
% less fuel than the controls and that the fuel savings more than paid for the additive.

Nanoscale catalysts are also showing promise in improving air quality and for treating particularly
challenging contaminants in water that must be reduced to a very low level.

Catalytic gold

As a bulk material, gold is notably inert: it does not react with many chemicals (including strong acids and
bases). However, when in a nano-size form, gold becomes extremely reactive and this has opened the
way for its use in catalytic processes. Conventional materials used in catalysis are rare earth mater ials
such as platinum and palladium, which are extremely expensive. There is great need for catalysts and
alternatives are in huge demand. Nano-gold has been shown to be an extremely efficient catalyst in
numerous pollution control studies. For example, it has been shown that it is able to remove carbon
monoxide from room air under ambient conditions and from fuel cell hydrogen feed gas. Another study
has shown that an Au-Pt co-catalyst was able to break down trichlorethylene (TCE) 100 times faster than
a catalyst made of a traditional material. Recently, the company Nanostellar Inc. has announced an
engineered nano-gold oxidation catalyst which can reduce diesel hydrocarbon emission by 40 % more
commercially available materials. Considering that there are over 14 million light-duty diesel vehicles
worldwide, and two million heavy-duty vehicles, the impact of this nanotechnology could be
enormous.

Recovery of catalytic material

One of the problems associated with catalysis is that it often makes use of rare earth materials such as
palladium (Pd). Natural Pd resources are limited so there is a need to recycle industrial waste from
processes that have used Pd as a catalyst. Recycling Pd requires reduction of Pd(II) to Pd(0). For an
environmentally friendly alternative to chemical recycling processes, iNANO is investigating the use of
bacteria to mediate Pd reduction. The enzyme hydrogenase found in the membrane of many bacteria has
the potential to transfer electrons from an organic substrate to Pd(II). In the presence of some bacteria,
the Pd is produced as nanoparticles located on the cell surface and in the periplasmic space of Gram-
negative bacteria (known as 'bio-Pd'). Figure 7 shows an example. The catalytic properties of the bio-Pd
are similar to commercially available Pd nanoparticles. The hope is to use bacteria to recover catalytically
active Pd from industrial waste, and to use recover Pd for other catalytic processes.

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Figure 7: SEMANTIC image of Desulfovibrio desulfur

icans, a Gram-negative bacterium after palladium
recycling. Palladium is produced as nanoparticles
(black particles in the image) located on the cell
surface and in the periplasmic space of the bacterium.

Image: Rikke Lousie Myer, iNANO, © iNANO

Green manufacturing
Manufacturing processes are always accompanied by the production of diverse waste products, many
of which pose a threat to the environment and thus need to be removed and treated. Ideally,
manufacturing processes should be to minimise material usage and waste production, while designed
the use of the least amount of energy possible. 'Green manufacturing' is a generic name to broadly
cover methods and technologies that are directed towards achieving this goal. It includes the
development of new chemical and industrial processes (eg water-based rather the solvent-based
processes); reduction in the use of unsafe compounds (such as metals); development of 'green'
chemicals that are more environment-compatible; and the efficient use of energy. In terms of its
application to the reduction of manufacturing waste, nanotechnology can contribute in two ways: by
helping the manufacturing to be more controlled and efficient, and by using nanomaterials (such as
catalysts) that can raise the manufacturing efficiency while reducing or eliminating the use of toxic
materials. Overall, nanotechnology has the potential to make industrial processes more efficient in
terms of energy usage and material usage, while minimising the production of toxic wastes. Sometimes
the application of nanotechnology to 'greener' manufacturing processes is referred to as 'green
nanotechnology' and this includes, for example, bottom-up atomic-level synthesis for developing
improved catalysts; inserting information into molecules to build new materials (such as DNA) through
highly specific synthesis routes; scaling down material usage during chemical reactions by using
nanoscale reactors; and improving manufacturing to require less energy and less toxic materials.

An example of 'green nanotechnology' is the development of aqueous-based microemulsions as an

alternative to volatile organic compounds (VOCs) in the cleaning industry. These toxic and potentially
carcinogenic compounds, such as chloroform, hexane and percholoroethylene, are conventionally used
in the cleaning, textile and oil extraction industries. Microemulsions contain nano-sized aggregates that
can be used as 'receptors' for extracting specific molecules at a nanoscale level. Researchers from the
University of Oklahoma have synthesised microemulsions with water-attractive and water-repellent
'linkers' inserted between the head and tail parts of a surfactant molecule. The result is a surfactant that
has a very low interfacial tension with a wide range of oils. When tested for cleaning textiles from motor
oil residues and for extracting edible oil from oilseeds, the microemulsions were found to be very
competitive with conventionally used VOCs, both in terms of extraction yield and simplicity of the process.

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Environment sensing
Protection of human health and the environment requires the rapid, sensitive detection of pollutants
and pathogens with molecular precision. Accurate sensors are needed for in situ detection, both as
miniaturized portable devices and as remote sensors, for real-time monitoring of large areas in the
field. Generally speaking, a sensor is a device built to detect a specific biological or chemical
compound, usually produces a digital electronic signal on detection. Sensors are now being used for
the identification of toxic chemical compounds at ultra-low levels (ppm and ppb) in industrial products,
chemical substances, water, air and soil samples, or in biological systems. Nanotechnologies can
improve current sensing technology in various ways. By using nanomaterials with specific chemical
and biological properties, the sensor selectivity can be improved, thus making it possible to isolate a
specific chemical or biological compound with little interference. Hence, the accuracy of the sensors is
improved. As with other nano-engineered products discussed in this document, the high surface-to-
volume ratio of nanomaterials increases the surface area available for detection, which, in turn, has a
positive effect on the limit of detection of the sensor, thereby improving the sensitivity of the device.
Nanosensors are generally faster, as they can detect the targeted analyte (eg bacteria) at a lower
concentration than a conventional sensor, so the positive response arrives quicker. Scaling down using
nanomaterials allows detection sites to be packed into the same device, thus allowing the detection of multiple analysi
This scaling-down capability, together with the high specificity of the detection sites obtainable using
nanotechnology, will allow the fabrication of super-small 'multiplex' sensors, thus lowering the cost of
the analysis and reducing the number of devices needed to perform the analysis with an economic
benefit. Advances in the field of nanoelectronics will also allow the fabrication of nanosensors capable
of continuous, real-time monitoring.

Research in the field of nanosensors various areas such as: synthesising new nanoma terials with
specific detection sites able to recognize a certain pollutant; developing new detection methods to
increase the limit of detection of the sensors while electrical testing a 'readable' signal; and miniaturising
the size of the sensor elements while integrating them with larger parts of the device.

An example of how nanoscience can be applied to sensing technology is shown in Figure 8, which
schematises the operational principle of a heavy-metal nanosensor developed for monitoring heavy
metals in drinking water. The sensor is made of an array of electrode pairs fabricated on a silicon
chip and separated by a few nanometres. When the electrodes are exposed to a solution of water
contain ing metal ions, these deposit inside the nano-gap between the electrodes. Once the metal
bridges the gap, a 'jump' in conductance between the electrodes is registered. The size of the gap,
being only a few nanometres, allows the detection of a very low concentration of metal ions. This type
of sensor is called a 'nanocontact sensor'.

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Figure 8: Schematic representation of a nanocontact sensor: (A) a drop of sample solution con
taining metal ions is placed onto a pair of nanoelectrodes separated with an atomic scale gap on a
silicon chip; (B) holding the nanoelectrodes at a negative potential, electrochemical deposition of a
single or a few metal atoms into the gap can form a nanocontact between the two nanoelectrodes
and result in a quantum jump in the conductance

Image: adapted from Proceedings — Nanotechnology and Environment: Applications and Implications — Progress Review
Workshop III, 26–28 October 2005, p. sixty seven

Nanowire and nanotube-based sensors

Some nanomaterials in the form of nanowires or nanotubes offer outstanding opportunities as sensor
elements in chemical and biological sensors. Individual single-walled carbon nanotubes (SWNTs) have
been demonstrated to exhibit a faster response and a significantly higher sensitivity, for example
towards gaseous molecules (such as NO2 and NH3) than that of existing solid-state sensors. In this
case, the mechanism involved in sensing is the direct binding of the gaseous molecule to the surface of
the SWNT, upon which the electrical resistance of the SWNT significantly increases or increases.
Furthermore, this sensitivity has been registered at room temperature, whereas conventional solid-state
sensors operate at very high temperatures (200–600 °C) to achieve enhanced chemical reactivity
between molecules and the sensor material.

Although SWNTs are promising candidates as nanosensors, they also have some limitations that could
curb their development. First, existing synthesis methods produce a mixture of metallic and semicon
ducting nanotubes with only the latter being useful as sensors. Second, in order to be able to sense a
variety of chemical and biological species, the surface of nanotubes needs to be modified to have
specific functions to bind those species. Flexible methods to modify the surface of nanotubes to bind a
large variety of analytes are not yet well established. nanowires of semiconductors such as silicon do
not have these limitations: they are always semiconductors and there is established knowledge for the
chemical modification of their surface. Boron-doped silicon nanowires (SiNWs) have been used for the
sensitive real-time electrical detection of proteins and antibodies. The small size and the capability of
these semiconductor nanowires to detect a wide range of analytes in real time could be used to develop
sensors to detect pathogens, chemical and biological agents in water, air and food.

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Cantilever sensors
A cantilever sensor is a device made of an array of silicon cantilevers, each coated with a nano-layer
which is sensitive to a specific pollutant. The cantilevers are typically 10–500 µm long, but have a
thickness of a few micrometres or less. The pollutant-specific layer on top of the cantilever 'arm' is at
the nanoscale level. The interaction of the pollutant with the 'arm' of the cantilever causes this to bend
as a consequence of a change in surface stress. A laser beam detects this minute bending, which can
also lead to quantitative mass measurement of the pollutant detected. Cantilever sensors have been
developed to detect VOCs, heavy metals, pesticides and harmful bacteria like salmonella.

Figure 9: Schematic diagram of a cantilever-based bio

sensor: the yellow molecules bind specifically to the red
molecules on the right-hand cantilever and are detected
by the bending of the cantilever

Image: M. Lorenzen, iNANO, University of Aarhus, © Lorenzen

Food packaging and monitoring

Nanotechnology may have a tremendous impact on the way food is produced, packaged, stored and
transported. Applications include improved processing and packaging, enhanced flavor and nutrition,
tracking of products and ingredients from farm to shelf, and monitoring of taste, ripening, and micro
biological contamination. These areas are of major public and industrial interest and technical solutions
require that profound insights from materials science are combined with a thorough understanding of
chemical, molecular, and physical composition of foods and their nutritional effects. Hopes are high that
nanotechnology can provide solutions to many of these diverse challenges. Meeting these challenges
is, for example, the mission of the NanoFOOD consortium at iNANO (Aarhus University). One project in
particular focused on the characterisation and exploitation of proteins immobilised on surfaces.
Immobilisation strategies need to be developed to ensure the surface attachment of functional pro teins
in order to modify surface properties to include enzymatic activity. Such enzymatic surfaces have huge
potential in many applications including food production, healthcare and environmental control.
An example of the latter is the development of substitutes for the ecotoxic tributyltin antifouling
paint used on ships. This paint must not be used after 2008, and the race is on to find effective and
environmentally friendly alternatives. Scientists are working to develop surfaces and paint formulations
with antifouling properties. Apart from marine vessels, such surfaces and paint may find applications
in food production and hospitals. The approach is to engineer surfaces with antifouling effects against
a wide range of organisms by immobilising enzymes that either degrade key components of biofilms
or have toxic effects on the fouling organisms. The hope is that such properties will inhibit bacterial
adhesion and growth. Long-term functionality and sustained release of active compounds are key goals.

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Another area where nanotechnology will have an important impact is food packaging and tracking.
The vision is to be able to create packaging systems that are 'smart' in the sense of being able to detect
the freshness of the food they contain, report any spoilage, and allow tracking of the package through
the entire supply chain. Some technologies already exist that combine the plastic of the package with a
dye which changes color in the absence or presence of a specific chemical, such as oxygen or ethanol
(two gases that are indicative of spoilage), therefore seemingly alerting the consumer that the package
is compromised, even before there are visible signs of spoilage. Latest advancements in this field
consider the use of nanomaterials, such as nanoparticles, or nanofibres, embedded in the inner side of
the plastic used in the packages and in combination with dyes. Nanosensors such as the one described
in the previous section could be used, capable of detecting ultra-small quantities of material.
Nanomaterials have the advantage of having high surface areas, so they are very reactive, and can be
functionalised to be very sensitive to detect a specific chemical species, such as oxygen, and provide a
fast response. In a similar way, nanoparticles could be used to detect other chemicals that indicate food
spoilage, such as ethanol, or even the presence of bacteria. This nanosensor could even be engineered
to continuously wireless communicate the status of the product it contains to the manufacture.

NANOYOU DILEMMA The use of nanosensors to monitor food quality and freshness during its
storage and retail forms one of the NANOYOU dilemmas included in the NANOYOU role
playing game 'Nanotechnology in food packaging' (http://www.nanoyou.eu/en/decide ). Cur
rently, there is little knowledge on the degradation process of materials containing nanoparticles.
Numerous studies exist to provide life-cycle analysis of nanomaterials, but this type of research
requires time. In the meantime, should these materials be disposed of as normal plastic, or is a
different waste system needed? The dilemma is: Should nanoparticles be used in our food or
pharmaceutical packages to detect freshness, when we still do not know the full ramifications of
the using them?

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