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Atul Thakur · Preeti Thakur ·
S.M. Paul Khurana Editors

Synthesis and
Applications
of Nanoparticles
Synthesis and Applications of Nanoparticles
Atul Thakur • Preeti Thakur •
S. M. Paul Khurana
Editors

Synthesis and Applications

of Nanoparticles
Editors
Atul Thakur Preeti Thakur
Centre of Nanotechnology Department of Physics, Amity School of
Amity University Haryana Applied Sciences
Gurugram, Haryana, India Amity University Haryana
Gurugram, Haryana, India

S. M. Paul Khurana
Science Instrumentation Centre
Amity University Haryana
Gurugram, Haryana, India

ISBN 978-981-16-6818-0 ISBN 978-981-16-6819-7 (eBook)

https://doi.org/10.1007/978-981-16-6819-7

# The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Singapore
Pte Ltd. 2022
This work is subject to copyright. All rights are solely and exclusively licensed by the Publisher, whether
the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of
illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and
transmission or information storage and retrieval, electronic adaptation, computer software, or by
similar or dissimilar methodology now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication
does not imply, even in the absence of a specific statement, that such names are exempt from the relevant
protective laws and regulations and therefore free for general use.
The publisher, the authors, and the editors are safe to assume that the advice and information in this
book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or
the editors give a warranty, expressed or implied, with respect to the material contained herein or for any
errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional
claims in published maps and institutional affiliations.

This Springer imprint is published by the registered company Springer Nature Singapore Pte Ltd.
The registered company address is: 152 Beach Road, #21-01/04 Gateway East, Singapore 189721,
Singapore
Preface

In this fast-pacing world of science and technology, nanotechnology is making its

presence felt in everyday life. This multidisciplinary science is filling the gap and
bridging all the major branches of science and providing a common platform for
scientists and technologists. As a result, new innovative nanoproducts are being
developed making our lives all the more easier.
Synthesis and Applications of Nanomaterials provides a comprehensive introduc-
tion to nanomaterials, their properties, processing techniques, and applications. This
book covers the basics of nanotechnology and provides a solid understanding of the
subject. Starting from the basics of nanomaterials to their types, structure and
synthesis techniques, the book gradually gives an insight to the properties of
nanomaterials. It includes chapters on the various applications of nanoscience and
nanotechnology. It is written in a simple form, making it useful for students of
physical and material sciences.
The editors wish to thank all the authors for their efforts in writing their chapters
and, also Springer Nature Publishing who have rendered every possible help for the
successful completion of this book.

Gurugram, India Atul Thakur

Preeti Thakur
S. M. Paul Khurana

v
Contents

1 Introduction to Nanotechnology . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Preeti Thakur and Atul Thakur
2 Nanomaterials, their Types and Properties . . . . . . . . . . . . . . . . . . . 19
Preeti Thakur and Atul Thakur
3 Synthesis of Nanoparticles by Physical Route . . . . . . . . . . . . . . . . . 45
Lucky Krishnia, Preeti Thakur, and Atul Thakur
4 Synthesis of Nanomaterials by Chemical Route . . . . . . . . . . . . . . . . 61
Shilpa Taneja, Pinki Punia, Preeti Thakur, and Atul Thakur
5 Synthesis of Nanomaterials by Biological Route . . . . . . . . . . . . . . . 77
Atul Thakur, Deepika Chahar, and Preeti Thakur
6 Structural and Morphological Characterization of
Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
Munirah A. Almessiere, Yassine Slimani, Alex V. Thurkanov,
and Abdulhadi Baykal
7 Optical Characterization of Nanomaterials-I . . . . . . . . . . . . . . . . . . 139
Vladimir Pavelyev
8 Optical Characterization of Nanomaterials-II . . . . . . . . . . . . . . . . . 151
Vladimir Pavelyev and Nishant Tripathi
9 Magnetic Characterization of Nanomaterials . . . . . . . . . . . . . . . . . 177
Yassine Slimani, Sadik Guner, Munirah A. Almessiere,
Essia Hannachi, Ayyar Manikandan, and Abdulhadi Baykal
10 Electrical Characterization of Nanomaterials . . . . . . . . . . . . . . . . . 239
Artem Kozlovskiy, Inesh Kenzhina, Maxim V. Zdorovets,
Kayrat K. Kadyrzhanov, and Alex V. Trukhanov
11 Electromagnetic Characterizations of Nanomaterials . . . . . . . . . . . 255
Atul Thakur, Preeti Thakur, Dinesh Kumar, and P. B. Sharma

vii
viii Contents

12 Electromagnetic Characterization of Nanomaterials: Preliminary

Study of 60 GHz Millimetre Wave Li-NGD Circuit in Microstrip
Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
Fayu Wan, Xiaoyu Huang, Samuel Ngoho,
Kishore Ajay Kumar Ayyala, Preeti Thakur, M. S. Prasad,
Atul Thakur, Sébastien Lalléchère, Wenceslas Rahajandraibe,
Nour Mohammad Murad, and Blaise Ravelo
13 Nanomaterials for Antenna Applications . . . . . . . . . . . . . . . . . . . . . 297
Anwer S. Abd El-Hameed, Asmaa I. Afifi, Moustafa A. Darwish,
and Trukhanov Alex
14 Advancement in Crops and Agriculture by Nanomaterials . . . . . . . 319
Sandeep Kaur, Kajal Sharma, Rajat Singh, and Naveen Kumar
15 Micronutrient Nanoparticles: Synthesis, Properties and
Application in Agriculture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
Kartik Pal, S. M. Paul Khurana, Nitai Debnath, and Sumistha Das
16 Phytosynthesis of Silver Nanoparticles and Their Role as
Antimicrobials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
Alka Yadav and Mahendra Rai
17 Microbicidal Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 371
Nishant Srivastava and Shailendra K. Saxena
18 Advancement in Water Purification by Nanomaterials . . . . . . . . . . 387
Andrei Ivanets, Vladimir Prozorovich, and Tatyana Kouznetsova
19 Nanotechnology in Healthcare . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
Deepak Kala, Shagun Gupta, and Ankur Kaushal
20 Graphene Quantum Dots and Their Hybrid Hydrogels:
A Multifaceted Platform for Theranostic Applications . . . . . . . . . . 417
Sujata Sangam, Piyush Garg, Trinanjana Sanyal, Siddhartha Pahari,
S. M. Paul Khurana, and Monalisa Mukherjee
21 Functionalized Nanoparticles in Drug Delivery: Strategies to
Enhance Direct Nose-to-Brain Drug Delivery via Integrated
Nerve Pathways . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 455
Fakhara Sabir, Qurat-ul-Ain, Abbas Rahdar, Zhugen Yang,
Mahmood Barani, Mauhammad Bilal, and Nikhil Bhalla
22 Environmental Nanomedicine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 487
Nishant Srivastava, Gourav Mishra, and Shailendra K. Saxena
23 Development of Nanostructured Material by Severe Plastic
Deformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 503
Sanjeev Sharma and P. B. Sharma
Contents ix

24 Nanotechnology for Functional/High-Performance/Smart

Textiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
Sapna Gautam, Anupama Mishra, and Pooja Koundal
25 Toxicity of Nanomaterials: An Overview . . . . . . . . . . . . . . . . . . . . . 535
Preeti Thakur, Yeshvandra Verma, and Atul Thakur
Editors and Contributors

About the Editors

Atul Thakur is professor and director of the Amity

Institute of Nanotechnology & Amity School of Applied
Sciences, Amity University, Haryana. His research
interests are spinel ferrites for antenna miniaturization
and sensor applications, magnetic nanoferrites for water
purification and agriculture applications, synthesis and
characterization of nanoferrites for high-frequency
applications, and radar-absorbing materials. He has
published more than 150 research articles in journals
of high repute and filed 18 patents till date. He has
worked on several funded research projects from
MNRE, Jal Shakti, MeitY, DST, DAE, DRDO and is
recipient of Royal Academy of Engineering UK award.

Preeti Thakur is a professor and head of the Depart-

ment of Physics, Amity School of Applied Sciences,
Amity University, Haryana. She is Gold Medalist in
electronics. Her areas of interest are spinel ferrites
synthesis and characterization of RADAR-absorbing
materials, sensor, high-frequency materials, and appli-
cation of magnetic nanoferrite materials for wastewater
treatment and agriculture purposes. Till now, she has
published more than 100 research articles in journals of
high repute and filed 15 patents till date. She has worked
on several funded research projects from DST, DAE,
DRDO and is recipient of Royal Academy of Engineer-
ing UK award.

xi
xii Editors and Contributors

S. M. Paul Khurana PhD is a retired professor of

biotechnology and head of the University Science
Instrument Centre, Amity University, Haryana,
Gurgaon. Earlier, he served as the vice chancellor of
Rani Durgavati University, Jabalpur, from 2004 to
2009, project coordinator AICRP (Potato) from 1994
to 2004, and director of the Central Potato Research
Institute, Shimla, from 2002 to 2004. He is the founder
director of Amity Institute of Biotechnology, Gurgaon
Haryana; Dean, Science, Engineering, and Technology;
consultant at CIP/FAO, 1992, 1996, and 1997. He has
more than 54 years of experience in pathology, virology,
and nanotechnology. He has published more than
230 research papers, 135 reviews/chapters, and authored
and/or edited 25 books.

Contributors

Anwer S. Abd El-Hameed Center for Northeast Asian Studies, Tohoku Univer-
sity, Sendai, Miyagi, Japan
Electronics Research Institute, Giza, Egypt
Asmaa I. Afifi Electronics Research Institute, Giza, Egypt
Trukhanov Alex National University of Science and Technology, MISiS,
Moscow, Russia
SSPA “Scientific and Practical Materials Research Centre of NAS of Belarus”,
Minsk, Belarus
South Ural State University, Chelyabinsk, Russia
Munirah A. Almessiere Department of Biophysics, Institute for Research and
Medical Consultations (IRMC), Imam Abdulrahman Bin Faisal University,
Dammam, Saudi Arabia
Department of Physics, College of Science, Imam Abdulrahman Bin Faisal Univer-
sity, Dammam, Saudi Arabia
Kishore Ajay Kumar Ayyala Centre of Nanotechnology, Amity University
Haryana, Gurugram, India
Mahmood Barani Department of Chemistry, Shahid Bahonar University of
Kerman, Kerman, Iran
Abdulhadi Baykal Department of Nanomedicine Research, Institute for Research
and Medical Consultations (IRMC), Imam Abdulrahman Bin Faisal University,
Dammam, Saudi Arabia
Editors and Contributors xiii

Nikhil Bhalla Nanotechnology and Integrated Bioengineering Centre (NIBEC),

School of Engineering, Ulster University, Newtownabbey, Northern Ireland, UK
Healthcare Technology Hub, Ulster University, Newtownabbey, Northern Ireland,
UK
Mauhammad Bilal School of Life Science and Food Engineering, Huaiyin Insti-
tute of Technology, Huaian, China
Deepika Chahar Department of Physics, Amity School of Applied Sciences,
Amity University Haryana, Gurugram, India
Moustafa A. Darwish Physics Department, Faculty of Science, Tanta University,
Tanta, Egypt
National University of Science and Technology MISiS, Moscow, Russia
Sumistha Das Amity Institute of Biotechnology, Amity University Haryana,
Gurugram, India
Nitai Debnath Amity Institute of Biotechnology, Amity University Haryana,
Gurugram, India
Piyush Garg Amity Institute of Biotechnology, Amity University, Noida, Uttar
Pradesh, India
Amity Institute of Click Chemistry Research and Studies, Amity University, Noida,
Uttar Pradesh, India
Sapna Gautam Department of Textiles & Apparel Designing, College of Home
Science, CSK HP Agricultural University, Palampur, India
Sadik Guner Institute of Inorganic Chemistry, RWTH Aachen University,
Aachen, Germany
Shagun Gupta Department of Biotechnology, Maharishi Markandeshwar Univer-
sity, Mullana, Ambala, Haryana, India
Essia Hannachi Department of Nuclear Medicine Research, Institute for Research
and Medical Consultations (IRMC), Imam Abdulrahman Bin Faisal University,
Dammam, Saudi Arabia
Xiaoyu Huang School of Electronics and Information Engineering, NUIST,
Nanjing, China
Andrei Ivanets Institute of General and Inorganic Chemistry, National Academy
of Sciences of Belarus, Minsk, Belarus
Kayrat K. Kadyrzhanov L.N. Gumilyov Eurasian National University, Nur-Sul-
tan, Kazakhstan
Deepak Kala Department of Biotech Engineering and Food Technology,
Chandigarh University, Mohali, Punjab, India
Sandeep Kaur Department of Life Sciences, RIMT University, Mandi
Gobindgarh, Punjab, India
xiv Editors and Contributors

Ankur Kaushal Department of Biotechnology, Maharishi Markandeshwar Uni-

versity, Mullana, Ambala, Haryana, India
Inesh Kenzhina L.N. Gumilyov Eurasian National University, Nur-Sultan,
Kazakhstan
The Institute of Nuclear Physics, Almaty, Kazakhstan
S. M. Paul Khurana Science Instrumentation Centre, Amity University Haryana,
Gurugram, Haryana, India
Pooja Koundal Department of Fashion and Textile Design, NBSCFF, Subharti
University, Meerut, Uttar Pradesh, India
Tatyana Kouznetsova Institute of General and Inorganic Chemistry, National
Academy of Sciences of Belarus, Minsk, Belarus
Artem Kozlovskiy L.N. Gumilyov Eurasian National University, Nur-Sultan,
Kazakhstan
The Institute of Nuclear Physics, Almaty, Kazakhstan
Research School of Chemistry and Applied Biomedical Sciences National Research
Tomsk Polytechnic University, Tomsk, Russia
Lucky Krishnia Centre of Nanotechnology, Amity University Haryana,
Gurugram, India
Dinesh Kumar Centre of Nanotechnology, Amity University Haryana, Gurugram,
India
Naveen Kumar Amity Institute of Biotechnology, Amity University Rajasthan,
Jaipur, India
Sébastien Lalléchère Université Clermont Auvergne (UCA), CNRS, SIGMA
Clermont, Institut Pascal, Aubière, France
Ayyar Manikandan Department of Chemistry & Center for Catalysis and Renew-
able Energy, Bharath Institute of Higher Education and Research (BIHER), Bharath
University, Chennai, Tamil Nadu, India
Anupama Mishra Central Agricultural University, Tura, Meghalaya, India
Gourav Mishra Department of Biotechnology, Meerut Institute of Engineering
and Technology, Meerut, India
Monalisa Mukherjee Amity Institute of Biotechnology, Amity University, Noida,
Uttar Pradesh, India
Amity Institute of Click Chemistry Research and Studies, Amity University, Noida,
Uttar Pradesh, India
Nour Mohammad Murad PIMENT Lab, Network and Telecom Lab, Institut
Universitaire de Technologie, University of La Reunion, Saint Pierre, France
Editors and Contributors xv

Samuel Ngoho Association Française de Science des Systèmes (AFSCET), Paris,

France
Siddhartha Pahari Amity Institute of Click Chemistry Research and Studies,
Amity University, Noida, Uttar Pradesh, India
Kartik Pal Amity Institute of Biotechnology, Amity University Haryana,
Gurugram, India
Vladimir Pavelyev Samara National Research University, Samara, Russia
M. S. Prasad Amity Institute of Space Science and Technology, Amity University
Noida, Noida, India
Vladimir Prozorovich Institute of General and Inorganic Chemistry, National
Academy of Sciences of Belarus, Minsk, Belarus
Pinki Punia Department of Physics, Guru Jambheshwar University, Hisar, India
Qurat-ul-Ain Institute Teknologi Bandung, Bandung, Indonesia
Wenceslas Rahajandraibe Aix-Marseille University, CNRS, University of
Toulon, IM2NP UMR7334, Marseille, France
Abbas Rahdar Department of Physics, Faculty of Science, University of Zabol,
Zabol, Iran
Mahendra Rai Department of Biotechnology, Sant Gadge Baba Amravati Univer-
sity, Amravati, India
Department of Microbiology, Nicolaus Copernicus University, Torun, Poland
Blaise Ravelo School of Electronics and Information Engineering, NUIST,
Nanjing, China
Fakhara Sabir University of Szeged, Faculty of Pharmacy, Institute of Pharma-
ceutical Technology and Regulatory Affairs, Szeged, Hungary
Sujata Sangam Amity Institute of Biotechnology, Amity University, Noida, Uttar
Pradesh, India
Amity Institute of Click Chemistry Research and Studies, Amity University, Noida,
Uttar Pradesh, India
Trinanjana Sanyal Amity Institute of Biotechnology, Amity University, Noida,
Uttar Pradesh, India
Shailendra K. Saxena Centre for Advanced Research (CFAR), Faculty of Medi-
cine, King George’s Medical University (KGMU), Lucknow, India
Kajal Sharma Chitkara School of Health Sciences, Chitkara University, Rajpura,
Punjab, India
P. B. Sharma Centre of Nanotechnology, Amity University Haryana, Gurugram,
India
Department of Mechanical Engineering, Amity University, Manesar, Haryana, India
xvi Editors and Contributors

Sanjeev Sharma Department of Mechanical Engineering, Amity University,

Manesar, Haryana, India
Rajat Singh Department of Food Technology, Eternal University, Sirmour,
Himachal Pradesh, India
Yassine Slimani Department of Biophysics, Institute for Research and Medical
Consultations (IRMC), Imam Abdulrahman Bin Faisal University, Dammam, Saudi
Arabia
Nishant Srivastava Department of Biotechnology, Meerut Institute of Engineering
and Technology, Meerut, India
Shilpa Taneja Department of Physics, Amity School of Applied Sciences, Amity
University Haryana, Gurugram, India
Atul Thakur Centre of Nanotechnology, Amity University Haryana, Gurugram,
India
Preeti Thakur Department of Physics, Amity School of Applied Sciences, Amity
University Haryana, Gurugram, India
Alex V. Thurkanov Department of Physics, College of Science, Imam
Abdulrahman Bin Faisal University, Dammam, Saudi Arabia
South Ural State University, Chelyabinsk, Russia
SSPA “Scientific and Practical Materials Research Centre of NAS of Belarus”,
Minsk, Belarus
L.N. Gumilyov Eurasian National University, Nur-Sultan, Kazakhstan
Nishant Tripathi Samara National Research University, Samara, Russia
Alex V. Trukhanov National University of Science and Technology MISiS,
Moscow, Russia
SSPA “Scientific and Practical Materials Research Centre of NAS of Belarus”,
Minsk, Belarus
South Ural State University, Chelyabinsk, Russia
Yeshvandra Verma Department of Toxicology, C.C.S. University Campus,
Meerut, India
Fayu Wan School of Electronics and Information Engineering, NUIST, Nanjing,
China
Alka Yadav Department of Biotechnology, Sant Gadge Baba Amravati University,
Amravati, India
Zhugen Yang Cranfield Water Science Institute, Cranfield University, Cranfield,
Bedfordshire, UK
Maxim V. Zdorovets L.N. Gumilyov Eurasian National University, Nur-Sultan,
Kazakhstan
The Institute of Nuclear Physics, Almaty, Kazakhstan
Ural Federal University, Yekaterinburg, Russia
Introduction to Nanotechnology
1
Preeti Thakur and Atul Thakur

Abstract

Nanoscience and Nanotechnology are very vast and very old sciences that people
know from the very beginning. Life started with the big bang, where all atomic and
molecular phenomena happened, which falls under nanoscience. It is right to say
nanoscience as the science of God. Knowingly or unknowingly, we come across
many events in our daily life that are influenced by nano science and technology.
Our “Rishis” used “Bhasma” for medication, which is a classic example of
nanotechnology. 0D, 1D, 2D, and 3D nanoparticles are described and explained
in detail. In this chapter, structural, optical, chemical, electronic, mechanical,
thermal, and magnetic properties of nanoparticles in general are also discussed.

Key words

Nanoscience · Nanotechnology · Atomic · Size

1.1 Introduction

The term nanotechnology is made up of two words; in which, Greek word “nano”
means billionth and the second word is technology. Nanotechnology considers the
objects that are of the size below 100 nm. As an outcome, nanotechnology or
nanoscale technology (Ghazi et al. 2018; Wang et al. 2017; Ghaffari et al. 2012;
Gleiter 2009; Bhushan 2016; Nouailhat 2010) is generally considered to be at a size
below 100 nm (a nanometer is one billionth of a meter, 10–9 m). Nanotechnology, in

P. Thakur (*)
Department of Physics, Amity School of Applied Sciences, Amity University Haryana, Gurugram, India
A. Thakur
Centre of Nanotechnology, Amity University Haryana, Gurugram, India

# The Author(s), under exclusive license to Springer Nature Singapore Pte 1

Ltd. 2022
A. Thakur et al. (eds.), Synthesis and Applications of Nanoparticles,
https://doi.org/10.1007/978-981-16-6819-7_1
2 P. Thakur and A. Thakur

short, is called as “nanotech,” and it is defined as the study of controlling matter on

an atomic and molecular scale. In general, nanotechnology is the name of the science
which deals with structures of the size 100 nm or smaller in at least one dimension,
and also it involves developing materials or devices within that size (Baer et al. 2003;
Whitesides 2005). The range of nanotechnology is very wide, from the smallest
particles which cannot be seen by the naked eye to the food we eat and clothes we
wear. The definition of nanotechnology can be stated as:

• The development in the field of research and technology at various levels such as
atomic, molecular, or macromolecular levels, having a length scale of approxi-
mately 1–100 nm.
• Creation and use of devices and structures with novel properties due to small size.
• Controlling or manipulating matter at atomic scale.

Nanotechnology is becoming very popular with time. Firstly, Michael Faraday in

1857 mentioned during a lecture on the optical properties of gold noticeable that “a
mere variation in size of the particles gave rise to a variety of resultant colors.” The
invention of atomic force microscopy (AFM) in 1986 and first electron transistor in
1987 and then creation of carbon nanotube in 1991 depict the growth in the field of
nanotechnology. Here some of the historical contents of nanotechnology develop-
ment are listed in the flowchart below.

• Thought process was initiated by R. Feynman

1959

• Taniguchi used term nanotechnology for the first time

1974

• IBM Scanning Tunneling Microscope

1981

• Bucky ball
1985

• First book on nanotechnology published by K. Eric Drexler

1986

• IBM logo was made having individual atoms

1989

• Crabon nano tube was discovered by S. Iijima

1991

• 1st nano medicine book by “Nano medicine” by R. Freitas was published

1999

• National Nanotechnology initiative was launched for the first time

2000

• Feynman prize was awarded

2001

• First center for nano mechanical systems was established

2004

• 3D Nano systems like robotics, 3D networking and active nano products that change
till
their state during use were prepared
now
1 Introduction to Nanotechnology 3

Nanoparticles in the range 1–100 nanometer are the fundamental components of

nanotechnology and made up of metal, carbon, organic matter, or metal oxides. The
physical, chemical, and biological properties of nanoparticles are unique at nano-
scale in comparison with their respective bulk counterparts. This is due to larger
surface area to the volume ratio, high reactivity or chemical stability, increased
mechanical strength, etc. (Sui et al. 1996). Due to these properties, nanoparticles are
used in many applications. The nanoparticles are different in terms of dimensions,
shapes, and sizes. The classification of nanoparticles on the basis of dimensions can
be done as zero dimensional, one dimensional, two dimensional, and three dimen-
sional. In case of a zero-dimensional nanomaterial, the length, breadth, and height
are fixed at a single point like nanodots. In case of one-dimensional nanomaterial, it
can possess only one parameter, for example, carbon nanotubes, and for two
dimensional, it has length and breadth in nanoscale, for example, graphene. For
three-dimensional nanomaterial, it has all the parameters such as length, breadth, and
height of nanorange, for example, gold nanoparticles. The shape, size, and structure
of nanoparticles are different as it may be cylindrical, spherical, conical, tubular,
hollow core, spiral, flat, etc. The surface may have variation or it may be uniform.
Nanoparticles are classified into crystalline or amorphous based on whether the
single or multicrystal solids are loose or agglomerated (Rashad et al. 2009).
There are numerous synthesis techniques that are developed to improve the
properties of nanomaterials and to reduce the cost of production. The modification
in some methods is done to improve their optical, mechanical, physical, and chemi-
cal properties (Chandamma et al. 2017; Gao et al. 2013; Yadav et al. 2016). The
characterizations are improved due to vast development in the instrumentation. The
use of nanoparticles is in every field like in cooking vessel, electronics to renewable
energy, and aerospace industry. So, it can be said that nanotechnology is the key for
a clean and sustainable future. The nanostructured materials and nanosystems can be
invented by discovering new materials and processes at the nanoscale and the
advancement of novel theoretical and experimental techniques. There are much
current and expected advancement in nanoscale science and nanotechnology in
terms of its applications in agriculture, medicine, energy, electronics, etc. The
developments in the domain of nanotechnology are increasing day by day, and it
plays a very important role in creating new products, substituting present production
equipments, and reformulating novel materials to improve the performance and
reduce the consumption of energy and is also used for remediation of environment
(Melo et al. 2015; Mallesh and Srinivas 2019). Although it is beneficial for the
environment that consumption of matter and energy is decreased, a more sustainable
route can be offered by nanotechnology to remediate the problems. Nanotechnology
can be used to develop solutions to environmental problems, measures to address
both the ensuing problems from interactions of material and energy with the
environment and the risks associated with nanotechnology (Harris and Šepelák
2018).
Nanotechnology can be stated as the complex interdisciplinary science that
includes (Ghazi et al. 2018; Mehta 2017; Thakur and Hsu 2011; Thakur et al.
2014; Sawant et al. 2016; Manikandan et al. 2018) the study of nanophysics,
4 P. Thakur and A. Thakur

nanochemistry, nanomaterial science, nanoelectronics, nanobionics, and

nanometrology. This is illustrated as under:

• Nanophysics including spintronics, quantum physics, and photonics is destined

for assembling and fabricating nanostructures artificially and doing research
about the external size effects.
• Nanochemistry including sol-gel, nanocolloid, and quantum chemistry is destined
for the nanoparticle synthesis and doing research about their intrinsic size effects.
• Nanomaterial science including nanoceramic compounds, nanotribology,
nanopowder technology, nanosintering, etc. is about developing and producing
nanostructured materials and nanocomposites having unique properties.
• Nanobionics is the branch of nanotechnology that is about developing
nanobiochips, nanobiorobots, etc.
• Nanoelectronics is the development of nanomotors, nanodevices, ultra-large
integrated circuits (ULCI), micro-optoelectronic-mechanical systems (MEMS,
MOEMS), nanorobots, etc.
• Nanometrology is building and developing special nanotools, information,
instrumentations, and computational systems.

1.2 Classification of Nanoparticles

The classification of nanoparticles can be done in accordance with organic, inor-

ganic, and carbon based as shown in Fig. 1.1. Some organic nanoparticles or
polymers are micelles, dendrimers, ferritin, liposomes, etc. The features of these
nanoparticles are listed as:

• Biodegradable.
• Nontoxic.
• Some particles among them like micelles and liposomes have a hollow core
(Fig. 1.2), known as nanocapsules.
• Sensitive to thermal and electromagnetic radiation such as heat and light.

These features make these materials capable for application in drug delivery. The
drug carrying capacity, delivery systems, its stability, and entrapped or adsorbed
drug system decide the field of applications and their efficiency apart from their
normal characteristics like the surface morphology, size, composition, etc. The use
of these organic nanoparticles is in the field of biomedicines. In case of drug delivery
systems, these are efficiently injected on particular parts of the body called as
targeted drug delivery.
The particles that are not made up of carbon are called inorganic nanoparticles.
Inorganic nanoparticles are metal- and metal oxide-based nanoparticles. Metal-based
nanoparticles are the nanoparticles that are prepared from metals to nanometric sizes
by using either destructive or constructive methods. It is possible to synthesize
almost all the metals into their nanoparticles (Sivakumar et al. 2011). The metals
1 Introduction to Nanotechnology 5

Fig. 1.1 Classification of nanoparticles according to organic, inorganic, and carbon based

Fig. 1.2 Organic nanoparticles: (a) Dendrimers; (b) liposomes; (c) micelles

that are commonly used for the synthesis of nanoparticles are cobalt (Co), aluminum
(Al), copper (Cu), cadmium (Cd), iron (Fe), gold (Au), silver (Ag), lead (Pb), and
zinc (Zn). The nanoparticles have properties like sizes as low as 10–100 nm, high
surface area to volume ratio, surface charge, pore size, surface charge density, color,
shapes like spherical and cylindrical, crystalline and amorphous structures, and
sensitivity and reactivity to environmental factors like heat, air, sunlight, moisture,
etc. The metal oxide-based nanoparticles have modified properties in comparison to
their respective metal-based nanoparticles, for example, in the presence of oxygen,
iron nanoparticles oxidize to iron oxide (Fe2O3) at room temperature due to which its
reactivity gets increased compared to iron nanoparticles. Due to increased reactivity
6 P. Thakur and A. Thakur

Fig. 1.3 Carbon-based nanoparticles: (a) fullerenes; (b) graphene; (c) carbon nanotubes; (d)
carbon nanofibers; and (e) carbon black

and efficiency, metal oxide nanoparticles are synthesized (Baer et al. 2003). Some
commonly synthesized are aluminum oxide (Al2O3), iron oxide (Fe2O3), silicon
dioxide (SiO2), cerium oxide (CeO2), titanium oxide (TiO2), magnetite (Fe3O4), and
zinc oxide (ZnO).
The nanoparticles which are completely made of carbon are known as carbon
based nanoparticles (Whitesides 2005). These materials can be classified into
graphene, fullerenes, carbon nanofibers, carbon nanotubes (CNT), carbon black,
and activated carbon in nanosize and are illustrated in Fig. 1.3. Fullerene (C60) is
spherical in shape and is a carbon molecule that is made up of carbon atoms that are
held together by sp2 hybridization. About 28–1500 carbon atoms build the spherical
structure having diameters up to 8.2 nm for single-layered and 4–36 nm for multi-
layered fullerenes. Graphene is called as an allotrope of carbon. Graphene shape is
hexagonal having honeycomb lattice that is made up of carbon atoms in a 2D planar
surface. Graphene sheet has a thickness of 1 nm. A Carbon nanotube (CNT) is a
graphene nanofoil having a honeycomb lattice made up of carbon atoms wound into
hollow cylinders to build nanotubes with diameters of measurement 0.7 nm for
single-layered and 100 nm for multilayered carbon nanotubes and length in the range
of a few micrometers to several millimeters. The ends can be open or closed by a half
fullerene molecule. The particles have high interaction such that the bound
inaggregates and around 500 nm agglomerates are formed.
In simple words, nanotechnology may be defined as a branch of science which
deals with materials or structures in nanoscale range varying from subnanometer to
several nanometers. This field is quite similar to quantum mechanics and is a new
1 Introduction to Nanotechnology 7

105 Macro Sand

Human
particle Pollens
hair
104 Red Blood Cells Yeast
Micro cells
particle Bacteria Pet
1000 dander
Macro Paint pigment Clay
Size (nm) molecule Cooking
100 smoke
Virus Colloidal
Micro
silica
10 molecule
Pyrogen Quantum Micelles
Sugars dot
1
Gas ion salts

0.1
Size of substance

Fig. 1.4 Zero-dimensional representation of nanostructures with their typical ranges of dimensions

scientific domain. The zero-dimensional representation of nanomaterials having

typical ranges of dimensions is shown in Fig. 1.4. In the nanometer scale, the
synthesized materials or structures have some new physical properties from which
some properties are known. For example, by varying the dimension of material, band
gap of the semiconductor can be tuned. Still, there are certain properties which are
not in the knowledge till now. These new physical properties are capable of
satisfying human beings and also proved to bring new advancements in the field
of science and technology.

1.2.1 Classification of Nanomaterials on the Basis of Size

On the basis of size, the classification of nanoparticles can be done into zero, one,
two, and three dimensional as shown in Fig. 1.5. The materials which have structures
in the range 1–100 nm are called nanostructured materials. The size and nature of the
nanostructures define the properties of the nanostructured materials. Large changes
in the material properties in comparison with a non-nanostructured material can be
observed, if the characteristic length scale of the microstructure is comparable to the
associated lengths to fundamental physical phenomena. A great variety of
nanostructures can be produced using crystallites of nanometer size of elements
like sodium chloride and gold, depending on the chemical composition of the
mixture, the crystallographic orientation, and the possibility to have nonequilibrium
structures that have certain property advantages. Nanostructured materials can be
made by using nanoparticles as building blocks. The nature of nanostructured
material can vary, and these may be nanocrystallites, fullerenes, nanofibers,
nanotubes, etc. Nanomaterials are the simplest building blocks of nanostructured
8 P. Thakur and A. Thakur

Fig. 1.5 Nanostructured materials

a b c d
0D 1D 2D 3D

Carbon nanotube-based
Core-shell nanoparticle composite electrode Graphene-based composite Mesoporous composite electrode

Nanoparticles encapsulated Coaxial nanowire array Carbon-coated nanoplates Microporous composite electrode
in hollow nanosphere

Composite nanoparticle Composite nanowire array Carbon-coated nanobelts Future 3D electrode

Fig. 1.6 Different types of (a) 0D (b) 1D (c) 2D, and (d) 3D nanostructured materials

nanomaterials, and it is possible to use more complicated elementary structures to

make nanocomposites. Nanoparticles are the very simple objects which can be used
to make nanomaterials. However, it is not an easy task to self-assemble nanoparticles
according to a given template. There are only few examples such as sulfides or
selenides combining with success soft templates, oriented attachment resulting in 1D
structures, and self-alignment of nanoparticles by dipolar interactions. Different
techniques like electron lithography can be used to design hard nanotemplates.
Nanoparticles having controlled size and shape can be synthesized using soft
nanotemplates, for example, mesophases and micellar systems. Different types of
0D, 1D, 2D, and 3D nanostructured materials are shown in Fig. 1.6.
1 Introduction to Nanotechnology 9

Various types of nanostructures can be differentiated on the basis of dimension-

ality. The word “nano” is originated from a Greek word “nanos,” which means
dwarf. This word “nano” is meant for a number 10
9, i.e., one billionth of a unit.
A significant progress has been made in the field of zero-dimensional
nanostructured materials in the past 10 years. The zero-dimensional nanostructured
materials can be synthesized using a variety of physical and chemical methods.
Recently, zero-dimensional nanostructures like quantum dots, core-shell quantum
dots, hollow spheres, heterogeneous particle arrays, onions, and nanolenses have
been prepared by several research groups. Also, these materials like quantum dots
have been extensively studied in single-electron transistors (Nayak et al. 2011),
light-emitting diodes (Harzali et al. 2018), lasers (Zhang et al. 2009), and solar cells
(Saeedi Afshar et al. 2018).
Due to the importance in research and having a variety of potential applications,
in one-dimensional nanostructured materials, the interest of researchers is increasing
in these materials. A large number of novel phenomena can be explored at the
nanoscale using one-dimensional nanostructured materials. Also, these materials are
useful in investigating the size and dependence on dimensions of functional
properties. They are also used to play the role of interconnects and as a key unit in
fabrication of optoelectronic, electronic, and EEDs having nanoscale dimensions.
After useful work, significant attention has been attained by one-dimensional
nanostructured materials like nanotubes. There is a great impact of
one-dimensional nanostructured materials in nanodevices, nanoelectronics, alterna-
tive energy resources, nanosystems, nanocomposite materials, and national security.
One-dimensional nanostructured materials include hierarchical nanostructures,
nanotubes, nanowires, nanoribbons, nanorods, and nanobelts (Amer 2017; Sertkol
et al. 2010).
The two-dimensional nanostructured materials have two dimensions outside of
the nanoscale range. Also, these nanomaterials have many low-dimensional
characteristics that are different from their bulk counterparts. Some unique shape-
dependent properties are exhibited by these two-dimensional nanostructured mate-
rial geometries. Also, these materials are the key components for synthesizing
nanodevices (Chithra et al. 2017; Rafiq et al. 2015). The mechanism for the growth
of nanostructures, investigation, and developing applications in the field of
nanoreactors, sensors, photocatalysts, and nanocontainers can be easily
understandable by fabricating two-dimensional nanostructured materials (Narang
and Pubby 2021). Two-dimensional nanostructured materials include nanoprisms,
junctions (continuous islands), branched structures, nanodisks, nanoplates,
nanosheets, and nanowalls.
Due to many superior properties and large specific surface area over the bulk
materials, researchers are taking great interest in three-dimensional nanostructured
materials, and these materials are being synthesized from the past 10 years (Ling
et al. 2010; Costa et al. 2008; Pei and Wang 2018). As it is a well-known fact that the
behavior of nanostructured materials is strongly affected by size, shape, morphol-
ogy, and dimensionality which are the key factors for the applications and ultimate
performance of the nanomaterials. Hence, three-dimensional nanostructured
10 P. Thakur and A. Thakur

materials having controlled structure and morphology are being synthesized by the
researchers. The range of applications of these materials is very wide, for example, in
the area of electrode material for batteries, catalysis, and magnetic material. Due to
supply enough absorption sites for all involved molecules in a small space and
higher surface area, the three-dimensional nanostructured materials are attracting
intensive interest by researchers. Also, better transport of the molecules is possible
due to porosity of these materials in three dimensions. Some examples of three-
dimensional nanomaterials are nanocones, nanoballs, nanopillers, nanocoils, and
nanoflowers.

1.3 Properties of Nanomaterials

1.3.1 Structural Properties

The changes in the spacing between interatoms can lead to an increase in the surface
area and surface energy with a decrease in particle size. This is because of the
compressive strain caused by the internal pressure by the small radius of curvature in
the nanoparticle. It is evident that interatomic spacing increases with a decrease in
particle size for semiconductors and metal oxides. One more effect is the stability of
metastable structures in small clusters and nanoparticles, and due to this there is loss
in all traces of the usual bulk atomic arrangement. Metallic nanoparticles, for
example, gold, adopt polyhedral shapes like multiply twinned icosahedra, cube
octahedra, and multiply twinned decahedra. These nanoparticles may be considered
as multiply twinned crystalline particles (MTPs) in which understanding of shapes in
terms of surface energies of various crystallographic planes, the growth rates along
various crystallographic directions, and the energy required for the formation of
defects such as twin boundaries can be made possible. But it is evident that these
particles are crystalloids or quasiperiodic crystals. The growth of nanocluster, up to a
size where they will switch into a more regular crystalline packing, is possible by
these icosahedral and decahedral quasicrystals. Crystalline solids are different from
amorphous solids because they possess long-range periodic order and the patterns
and symmetries correspond to 230 space groups. Such long-range periodic order is
not possessed by quasiperiodic crystals, and more differently five-fold symmetry is
exhibited by them, which is forbidden in the 230 space group. In the hexagonal close
packed and cubic close packed structures, that is exhibited by many metals in which
each atom is coordinated by 12 neighboring atoms. These all coordinating atoms are
in contact, but these are not evenly distributed around the central atom. Each atom
situated at the apex of icosahedra is in contact only with the central atom in the
alternative arrangement. The body of the material gains shape and point group
symmetry of regular icosahedra by relaxing the rigid atmospheric model, allowing
the central atom to decrease in diameter by 10%, and bringing the coordinating
atoms in contact. This symmetry indicates the presence of 20 threefold, 12 fivefold,
and 30 twofold axes of symmetry. This geometry depicts a quasiperiodic crystal
nucleus which may grow in the form of pentagonal dodecahedra or icosahedra.
1 Introduction to Nanotechnology 11

These are dual solids having identical symmetry in which the apices of one are
replaced by the faces of the other. There is difficulty in understanding the
characteristics that are related to size instability of quasiperiodic crystals. The
process of multiple twinning is a frequently observed process, and such crystals
are differentiated from quasiperiodic crystals by their electron diffraction patterns.
Here, the five triangular faces of the fivefold symmetric icosahedra can be mimicked
by five twin-related tetrahedra (with a close-packed crystalline structure) through
relatively small atomic movements.

1.3.2 Optical Properties

The optical properties are greatly affected by reducing the dimension of materials.
There are two groups when the size dependence is classified. One is because of the
increase in energy level spacing as the system becomes more confined, and the other
is because of surface plasmon resonance. The band gap increases with decrease in
size due to quantum size effect in the semiconductor nanoparticles in which the
interband transition shifts to higher frequencies. In a semiconductor, there is a rapid
increase in energy separation (the energy difference between the completely filled
valence band and the empty conduction band) with a decreasing size, and this energy
separation is of the order of a few electron volts. A blue shift in the band gap is
produced by quantum confinement and also in the appearance of discrete subbands
attributed to quantization along the direction of confinement. The optical properties
of the nano semiconductors can be modified by varying the size and keeping the
same chemical composition. The variation in the nanoparticle size can lead to
luminescent emission from the semiconductor nanostructures. The nature of elec-
tronic density of states and carrier confinement of semiconductor nanostructures
make it more efficient for devices that are operating at lower threshold currents than
lasers. The size-dependent emission spectra of quantum dots, quantum wells, and
quantum wires make the lasing media attractive. The quantum dot lasers show less
dependence on temperature than conventional semiconductor lasers. The same
quantum size effect is also known in metal nanoparticles. However, in order to
observe the localization of the energy levels, there is requirement of very small size
so that the level spacing exceeds the thermal energy (~26 MeV). An in-phase
oscillation is caused by surface plasmon resonance which is the coherent collective
excitation of all the free electrons within the conduction band. A surface plasmon
resonance is generated when the size of a metal nanocrystal is smaller than the
wavelength of incident radiation. Biomedicine, photocatalysis, optical detectors,
imaging, lasers, sensors and solar cells are some of the prominent applications
based on the optical properties of the nanomaterials.
12 P. Thakur and A. Thakur

1.3.3 Chemical Properties

Chemical reactivity of the materials has a link with the size effects. Nanoscale
structures, for example, nanolayers and nanoparticles, have potentially different
crystallographic structures and very high surface area to volume ratios that causes
a radical alteration in chemical reactivity. Nanoparticles generally show new chem-
istry which are different from their particular large counterparts; for example, in the
form of micron-sized particles, there are many new medicines which are insoluble in
water, but in a nanostructure form, they get dissolved easily. Hence, it is important to
chemically identify the nanomaterials and characterize them. A few of the chemical
properties that are essential for characterizing nanomaterials are composition, struc-
ture, chemical bonding, reactivity, stability, melting and boiling points.

1.3.4 Electronic Properties

The changes in electronic properties during decrease in the system length scale are
mainly related to the increasing influence of the electrons’ wavelike property, i.e.,
quantum mechanical effects and lack of scattering centers. The discrete nature of the
energy states becomes apparent when the size of the system becomes comparable
with the de Broglie wavelength of the electrons. But to observe a fully discrete
energy spectrum, the system should be confined in all three dimensions. Below a
critical length scale, conducting materials behave as insulators due to overlapping of
the energy bands. Due to their intrinsic wavelike nature, quantum mechanical
tunneling of electrons is possible between two closely adjacent nanostructures.
Resonant tunneling occurs when a voltage is applied between two nanostructures
due to which discrete energy levels are aligned in the density of state causing
an increase in the tunneling current. The impurities, scattering with phonons, and
scattering at rough surfaces determine the electronic transport in macroscopic
systems. There is diffusive transport and path of every electron relates a random
walk. In inelastic scattering, when system has dimensions smaller than the electron
mean free path, electrons travel through the system without phase randomization of
wave functions. This gives rise to additional localization phenomena related to phase
interference. If due to small system, all scattering centers are to be eliminated
completely, and if boundary reflections are purely specular due to smooth sample
boundaries, then the electron transport is purely ballistic, and the sample acts as a
waveguide for the electron wave function. Conduction in highly confined structures
like quantum dots is very sensitive to the presence of other charge carriers and thus to
the charge state of the dot. The conduction processes involving single electrons are
caused by these Coulomb blockade effects due to which very substantial amount of
energy is required by them to operate a transistor, switch, or memory element.
Different types of components for information processing applications, electronic,
and optoelectronic can be produced by utilizing all these phenomenas.
1 Introduction to Nanotechnology 13

1.3.5 Mechanical Properties

The mechanical properties of the nanomaterials (hardness, fracture toughness,

scratch resistance, elastic modulus, fatigue strength, etc.) are different from the
bulk materials because of the nanometer size. This modification may result in an
enhancement of mechanical properties of nanomaterials that often results from
structural perfection of the materials. The small size either renders them free of
internal structural imperfections such as dislocations, impurity precipitates, and
micro twins. It is not possible to cause mechanical failure due to few defects or
impurities. The highly energetic imperfections within the nano dimension will
migrate to the surface to relax themselves under annealing, thereby causing purifica-
tion of the material and leaving perfect material structures inside the nanomaterial.
Moreover, the external surface of nanomaterials are free of defects in comparison to
the bulk materials, causing enhancement in the mechanical properties of
nanomaterials.

1.3.6 Thermal Properties

There is low progress in study of the thermal properties of nanomaterials due to the
difficulties encountered in measuring experimentally and controlling the thermal
transport in nanoscale dimensions. The introduction of atomic force microscopy
(AFM) to measure the thermal transport of nanostructures within nanometer scale
with high spatial resolution has provided a promising way to probe the thermal
properties of nanostructures. The availability of the definition of temperature is in
question when the dimensions go down into nanoscale. Phonons carry the thermal
energy in nonmetallic material system which has a wide variation in mean free path
and frequency. Generally, at room temperature, the phonons that carry heat have
large mean free path and wave vectors in nanoscale range. Due to this, the
nanostructure dimensions are comparable to the wavelength and mean free path of
phonons. However, average energy of a material system defines the temperature. In
case of macroscopic systems, a local temperature in each region within the materials
is defined by the dimension, and there is variation in this local temperature from
region to region, so that thermal transport properties based on certain temperature
distributions can be investigated. But in case of nanomaterial systems, a local
temperature sometimes can’t be defined by just the dimensions because dimensions
are too small to define. Also, the concept of temperature defined in equilibrium
conditions is difficult or problematic to use for theoretical analysis of thermal
transport in nanoscale. In nanomaterial systems, various factors like the large
interfaces, the special shape, and the small size do modification in the thermal
properties of the nanomaterials, rendering them a quite different behavior in com-
parison to the macroscopic materials. The size of the nanomaterials become compa-
rable to the mean free path and wavelength of the phonons. When the dimension
goes down to nanoscale, there is a significant change in phonon transport within the
material due to the phonon confinement and quantization of phonon transport, which
14 P. Thakur and A. Thakur

results in modified thermal properties. The thermal properties are also affected by the
special structure of nanomaterials. For example, carbon nanotubes due to their
tubular structures have extremely high thermal conductivity in axial directions,
leaving high anisotropy during the heat transport in the materials. The thermal
properties of nanomaterials are also determined by interfaces. The thermal properties
of nanomaterials have another promising application in the use of nanofluid to
enhance the thermal transport. The nanofluids consist of nanomaterials of size in
the range 1–100 nm which are suspended in a liquid generally referred to as the
solid-liquid composite materials. The increase in thermal conductivity in compari-
son to liquids not containing nanomaterials is an important feature of nanofluids.

1.3.7 Magnetic Properties

Magnetic nanoparticles have a wide range of applications, such as ferrofluids,

refrigeration, bioprocessing, and color imaging, as well as high storage density
magnetic memory media. The large surface area to volume ratio results in a
substantial proportion of atoms (those at the surface which have a different local
environment) having a different magnetic coupling with neighbouring atoms, lead-
ing to differing magnetic properties. When the particle size decreases below a certain
value, ferromagnetic particles become unstable as domains are spontaneously
switched in polarization directions by gaining surface energy; due to which, ferro-
magnetic becomes paramagnetic. However, this ferromagnetic which is nanometer-
sized ferromagnetic turned to paramagnetic has a different behavior than the con-
ventional paramagnetic and is known as superparamagnetic. While multiple mag-
netic domains are formed by bulk ferromagnetic materials, only one domain is
formed by small magnetic nanoparticles exhibiting a phenomenon known as
superparamagnetism. The overall magnetic coercivity in this case is then lowered,
and there is random distribution of magnetizations of the various particles due to
thermal fluctuations and only get aligned in the presence of an applied magnetic
field. The nanoscale multilayers show giant magnetoresistance (GMR) which consist
of a strong ferromagnet (e.g., Fe, Co) and a weaker magnetic or nonmagnetic buffer
(e.g., Cr, Cu).

1.4 Conclusions

Enormous progress is made by nanotechnology in the past decades. In summary, the

requirements of nanotechnology are the fabrication of matter on the scale of atoms
and molecules, prediction, and measurement. Hopefully, there is revolutionary
impact of the atomic scale nanotechnology in the way of doing, designing, and
producing things in the future. Nanotechnology can be defined as an atomic or
molecular approach using which physically, chemically, and biologically stable
structures can be built of one atom, or one molecule, at a time. Nanomaterials can
be classified as organic, inorganic and carbon based. According to their size 0D, 1D,
1 Introduction to Nanotechnology 15

and 2D nanostructures are defined. Due to large surface to volume ratio and size in
nanometer range, these materials exhibit unique physical, chemical, optical, thermal
and magnetic properties. The results of developments and investigations in
nanotechnological fields are entering into all areas of our lives, like aerospace,
agriculture, materials science, energy, medicine, defense, and environmental sci-
ence. There are some active research areas which include nanodevices,
nanolithography, nanopowders, nanorobotics, nanostructured catalysts,
nanocomputers, nanoporous materials and molecular nanotechnology, nanolayers,
molecular manufacturing, medicines and nanobiology (e.g., prediction, prevention,
and treatment of diseases), and some organic nanostructures. Researchers have come
to know from many years that current technologies are depending on processes
which take place at the nanoscale. Some instances of these technologies are adsorp-
tion, lithography, catalysis, plastics, drug design, composites, and ion exchange.

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Nanomaterials, their Types and Properties
2
Preeti Thakur and Atul Thakur

Abstract

In this modern era, nanotechnology may be called as an important field that deals
with the synthesis, design, and manipulation of particle structures that have
dimensions ranging from 1 to 100 nm. The classification of nanoparticles can
be done on the basis of their different properties, shapes, or sizes. Due to their
nanoscale size and high surface area, they possess unique physical and chemical
properties. Even their properties like reactivity, toughness, and some other factors
are also dependent on their unique shape, size, and structure. This is the reason of
diverse applications of nanoparticles in different areas like optoelectronics, elec-
tronics, pharmaceuticals, biomedical sciences, health care, drug delivery, envi-
ronmental health, cosmetics, chemical industries, food industry, optics, nonlinear
optical devices, space technology, and energy sciences. Ferrites are magnetic
nanoparticles of oxides of iron and are of much interest because of their biological
compatibility, chemical stability, relative ease of preparation, and various other
applications associated with them. So, various types of nanoparticles and their
properties are covered in this chapter. Also, the structure, types, applications, and
properties of ferrite nanoparticles will also be discussed.

Keywords

Nanoparticles · Properties · Applications · Ferrites

P. Thakur (*)
Department of Physics, Amity School of Applied Sciences, Amity University Haryana, Gurugram,
India
A. Thakur
Centre of Nanotechnology, Amity University Haryana, Gurugram, India

# The Author(s), under exclusive license to Springer Nature Singapore Pte 19

Ltd. 2022
A. Thakur et al. (eds.), Synthesis and Applications of Nanoparticles,
https://doi.org/10.1007/978-981-16-6819-7_2
20 P. Thakur and A. Thakur

2.1 Introduction to Nanomaterials

Nanotechnology (Mathew and Juang 2007) is defined as the engineering, science,

and technology conducted at nanoscale (1–100 nanometers) in which the word
“nanometer” refers to one billionth of meter or 10
9 m in size, and expressed as
1 nm.

2.1.1 Starting of Nanotechnology

A renowned physicist Richard Feynman’s talk entitled “There’s Plenty of Room at

the Bottom” at the American Physical Society meeting at the California Institute of
Technology (CalTech) on December 29, 1959, includes the ideas and concepts
behind nanoscience and nanotechnology. Feynman explained a mechanism,
how individual atoms and molecules can be manipulated and controlled by
scientists. After a decade, Professor Norio Taniguchi coined the term nanotechnol-
ogy in his explorations of ultra-precision machining. In 1981, scanning tunneling
microscope was developed, and it was made possible to “see” individual atoms, with
that modern nanotechnology began. The meaning of prefix “nano” is one billionth
which originated from the Greek word “dwarf” and is about 1 ten thousandths (10
4)
the diameter of a human hair. One nanometer (1 nm) is defined as 1/1000,000,000 of
a meter. To get a sense of the nanoscale, a human hair measures 50,000 nanometers
across, and a bacterial cell measures a few hundred nanometers across. The unaided
human eye can see smallest things which measure 10,000 nanometers across. One
nanometer can be made with ten hydrogen atoms arranged in a line, and really it is
very small. Many atoms and molecules are of diameter of a few nanometers or less.
As an example, the smallest atom of hydrogen has a diameter of 0.078 nm.
Thousands of atoms are consisted by some biological molecules that have a diameter
in 10’s of nm or more. For instance, the diameter of RBC is about 7000 nm and of
water molecule is about 0.3 nm. Nanotechnology may be defined as the “Engineer-
ing of functional systems at the molecular scale.” In simple words, “Nanotechnology
is the creation, use or manipulation of matter on the atomic scale.” Nanotechnology
is an emerging, interdisciplinary field that combines principles of physics and
chemistry with the engineering principles of electrical engineering, mechanical
design, computer science, structural analysis, and system engineering. Nanotechnol-
ogy is the technology of preference to make things small, light, and cheap.
Nanomaterials are materials with morphological features smaller than a micron in
at least one dimension. The term nanotechnology includes nano particles, nano
powders, nano clusters, and nano crystals. Nanotechnology refers to a field of
applied science and technology whose theme is construction and fabrication of
matter or devices or materials on the atomic and molecular scale in the range of
1–100 nm.
2 Nanomaterials, their Types and Properties 21

2.1.2 Classification of Nanomaterials

Nanomaterial size is extremely small, that is, materials in the nanoscale exist in one
dimension, two dimensions, and three dimensions. Nanomaterials can also occur in
different shapes and phases. Generally, nanomaterials are categorized into four
types on the basis of their origin, dimensions, and structure.

2.1.2.1 Zero-Dimensional Nanomaterials

In zero-dimensional nanomaterials, the electron movement is confined in all the
three dimensions, for example, quantum dots, gold spheres, and silver clusters.
These types of nanomaterials generally have spherical morphology (average diame-
ter in the range of 1–50 nm), cubic structures, and polygon-shaped materials.

2.1.2.2 One-Dimensional Nanomaterials

In one-dimensional nanomaterials, free electron movement is confined only in one
dimension. Nanotubes, nanorods, nanowires, and nanofibers are a few examples.
The diameter of such materials falls in the nanoscale range, whereas the length is out
of nanoscale range in several micrometers.

2.1.2.3 Two-Dimensional Nanomaterials

In two-dimensional nanomaterials, free electron movement is confined in two
dimensions, for example, thin films, nanosheets, multilayer film, nanowalls, etc.
Such nanomaterials may have larger surface area and may be of several micrometers,
and the thickness is in the nanoscale range.

2.1.2.4 Three-Dimensional Nanomaterials

In three-dimensional nanomaterials, the free electrons can move in all the three
dimensions, for example, bulk materials, particles, and hollow spheres consisting of
materials of nanoscale range as building blocks.

2.1.3 Synthesis of Nanoparticles

The two bottom-up and top-down approaches are used in nanotechnology. In

bottom-up approach, material and devices are built from molecular atoms which
assemble themselves chemically, and in top-down approach, nano objects are
constructed from larger entities without atomic level control. Nanotechnology
allows the generation of a great variety of matters, devices, and products with
properties unobtainable by usual invention techniques. Top-down approach creates
smaller objects using the larger objects, begins with a pattern generated on a larger
scale and then reduced to nanoscale, and is relatively an expensive and time-
consuming technique, whereas bottom-up approach arranges smaller components
into more complex, and fabrication is much less expensive (Fig. 2.1).
22 P. Thakur and A. Thakur

Bulk Powder Nanoparticles Clusters Atoms

Top-down approach Bottom-up approach

Fig. 2.1 Synthesis approaches for nanoparticles

2.2 Properties of Nanomaterials

Nanomaterials are different from other materials on the basis of various factors like
quantum effects, reduced imperfections, surface area, surface energy, surface atoms,
etc. which are responsible for the enhancement or alteration of the characteristic
properties of the materials like optical, mechanical, electrical, and magnetic
properties. The major advantage of nanomaterials is that many atoms are available
on the material’s surface with the decrease in particle size. Different properties of
nanomaterials are discussed below:

2.2.1 Optical Properties

The study of nanomaterials is very important due to their novel optical properties in
comparison with their bulk counterparts. The optical properties of the nanomaterials
are dependent on several parameters like shape, dimensions, doping, surface
properties, etc. Also, the surface to volume ratio increases with a decrease in the
size of the materials.

2.2.2 Magnetic Properties

The magnetic materials are the materials that exhibit permanent magnetization in
the absence of an external magnetic field. The terms used to measure the strength of
the magnets are coercivity and saturation magnetization. There is an increase in the
saturation and decrease in coercivity, with the decrease in size of nanoparticles. For
example, in the bulk form, Au, Pt, and Pd are nonmagnetic, but in nano size, they
behave as magnetic materials.
2 Nanomaterials, their Types and Properties 23

2.2.3 Size-Dependent Properties

Under a certain condition, how the material acts is described by properties of a

material which are often measured by looking at large (~1023) aggregation of atoms
or molecules. The properties that often change are electrical (e.g., conductivity),
chemical (e.g., reactivity, reaction rates), optical (e.g., color, transparency), and
physical (e.g., hardness, boiling point) among others.

2.2.4 Chemical Properties

The nanoscience and nanotechnology have a great impact on the chemical properties
of nanomaterials. In case of nanomaterials, due to large surface area and small size,
chemical activity is very high that make these materials useful for a wide range of
practical applications. Hence, these materials can be used as catalysts for water
decomposition and thereby produce energy, which is clean, efficient, and
environmental-friendly preventing pollution.

2.3 Ferrites

The history of ferrites, that is, magnetic oxides, began with the discovery of stones
that would attract iron, centuries before the birth of Christ. In the district of Magnesia
in Asia Minor, the most plentiful deposits of these stones were found, and thus the
mineral’s name became magnetite (Fe3O4). Much later, the first application of
magnetite was to locate magnetic North as “Lodestones” used by early navigators.
In 1600, William Gilbert published the foremost scientific study on magnetism and
called it De Magnete. In 1819 Hans Christian Oersted observed that a magnetic
compass needle affects an electric current in a wire. Later Faraday, Hertz, Maxwell,
and many others developed the new science of electromagnetism. Naturally occur-
ring magnetite is a weak “hard” ferrite. Permanent magnetism is possessed by “hard”
ferrites. After that, hard ferrites that were man-made were developed with superior
properties, but producing an analogous “soft” magnetic material in the laboratory
proved elusive. During the 1930s research on “soft” ferrites continued in Japan and
the Netherlands. However, it was not until 1945 that a “soft” ferrite for commercial
applications was produced by J. L. Snoek from the Philips Research Laboratories of
the Netherlands. Originally manufactured soft ferrites for a multitude of uses have
proliferated into countless sizes and shapes for inductor and antenna applications.
Ferrites are used in power applications, multilayer inductor chip (MLIC)
applications, and electromagnetic interference (EMI) suppression. In 1956, garnet
ferrite class of materials was discovered by Neel. This type of ferrite material has
three sub-lattices and is also referred to as rare-earth iron garnets. These materials
have a magnetization lower than spinel ferrite. The application range of ferrites in
24 P. Thakur and A. Thakur

electronic circuitry has been continuously growing. This continuing improvement in

material characteristics, a wide range of possible geometries, and their relative cost-
effectiveness make ferrite components the choice for both innovative and conven-
tional applications.
The term “ferrites” has a different meaning for the different scientific community.
For metallurgists, the meaning of ferrite is pure iron. For geologists, the term ferrites
stand for a set of iron oxide-based minerals. For an electrical engineer also, ferrite
means a group of iron oxide-based materials having some specific magnetic as well
as dielectric properties. The meaning of magnetic properties is that iron-based
materials are attracted by a piece of ferrite, and magnets of opposite polarity are
attracted and magnets of like polarity are repelled. Both geologists and engineers
consider magnetite or lodestone a ferrite that is a naturally occurring iron oxide. The
strange properties of lodestone were recognized over 2000 years ago by the ancient
Greeks, and Chinese used it to invent the magnetic compass almost 1000 years ago.
The meaning of dielectric properties is that ferrites do not readily conduct electricity
even though electromagnetic waves can pass through them. So, they are advanta-
geous over nickel, iron, and other transition metals that show useful magnetic
properties in several applications as these metals are found to also conduct electric-
ity. Ferrites are termed as magnetic materials due to magnetic moments of the
molecules of the material. The magnetic field is produced when they all line
up. There is a distinctive arrangement of parallel and perpendicular magnetic
moments in “ferrimagnetic” ferrites as compared to “ferromagnetic” metals. This
effect can be achieved through several different crystal structures. Both the ferro-
magnetic and ferrimagnetic materials are found to lose their magnetism when heated
at a very high temperature or are subjected to mechanical stresses. This is due to the
fact that their magnetism depends on an orderly crystal structure.
Ferrites are found to exhibit diverse uses. Ferrites are used whensoever a fixed
magnet, instead of an electromagnet, is required. The use of ferrites is in electric
generators and electric motors, transformer, and inductor cores. Ferrite coating on
top of the plastic base for recording of the signal was used in videotapes and
cassettes. And many computers up to the 1970s employed magnetic core memory
with ferrite cores (ferrite core memories were even used in the Space Shuttle until
1990 due to their dependability). Ferrites have recently been used as a medium for
transmitting microwaves, which is perhaps their most important application. This is
because some ferrites display a nonreciprocal effect at very high frequencies
(starting at 500 MHz and very strongly in the microwave range of 1–30 GHz).
That implies electromagnetic waves flowing through them go in different directions
and react differently. One-way transmission allows for the creation of structures that
can manage microwave “traffic” and other microscopic traffic and other microwave
control devices. Without ferrites, our contemporary telecommunications system
would not be conceivable. In 1956, discovery of garnet ferrite class of materials is
done by Neel. This ferrite substance is also known as rare-earth iron garnets because
it has three sub-lattices. Despite having a lower magnetism than spinel ferrite, these
materials are useful.
2 Nanomaterials, their Types and Properties 25

2.3.1 Soft Ferrites

Soft ferrites with a low coercivity are ferrites that contain nickel, zinc, and/or
manganese compounds and are utilized in transformer or electromagnetic cores.
Low coercivity means that the direction of a material’s magnetization can be easily
reversed without wasting a lot of energy (hysteresis losses). These materials have
high resistivity which is another source of energy loss that prevents eddy currents in
the core. Because of their low losses at high frequencies, they are commonly
employed in RF transformers and inductors cores, as well as in applications such
as switched mode power supply. Manganese-zinc ferrite is the most prevalent soft
ferrite (MnZn, with the formula MnxZn1-xFe2O4). MnZn has higher permeability and
saturation induction than NiZn. Nickel-zinc ferrite (NiZn, with the formula
NiaZn(1-a)Fe2O4). NiZn ferrites have a higher resistivity than MnZn ferrites, making
them better suited to frequencies beyond 1 MHz.

2.3.2 Hard Ferrites

In contrast, hard ferrites are used in making permanent ferrite magnets having high
coercivity and high remanence magnetization. These are made up of iron and barium
or strontium oxides. The materials are very resistant to becoming demagnetized due
to their high value of coercivity, which is an essential characteristic for a permanent
magnet. Also the magnetic permeability is high, and they also conduct magnetic flux
well. Hence, stronger magnetic fields than iron can be stored in these so-called
ceramic magnets. They are widely used in household products and are very cheap.
The value of maximum magnetic field B is about 0.35 Tesla and of magnetic field
strength H is about 30–160 kilo ampere turns per meter (400–2000 Oersted). The
value of density of ferrite magnets is about 5 g/cm3. The examples of most common
hard ferrites are barium ferrite, BaFe12O19 (BaO6Fe2O3), which is a common
material for permanent magnet applications, and strontium ferrite, SrFe12O19
(SrO6Fe2O3), a common material for permanent magnet applications. Barium

Fig. 2.2 Hysteresis loop of B

soft and hard ferrites
Soft ferrite

Hard ferrite

H
26 P. Thakur and A. Thakur

ferrites are corrosion resistant and stable to moisture. They are used in, for example,
subwoofer magnets and as a medium for magnetic recording, on magnetic stripe
cards; cobalt ferrite, CoFe2O4 (CoOFe2O3), is used in some media for magnetic
recording (Fig. 2.2).

2.4 Ferrite Structure

Ferrites contain iron oxide and metal oxides as their main constituents. Ferrites are
classified into the following types depending upon the crystal structure.

2.4.1 Spinel Ferrite

Spinel ferrites are also called cubic ferrite as shown in Fig. 2.3. It is the most widely
used family of ferrite. These materials are ideal for use at microwave frequencies due
to high values of electrical resistivity and low eddy current losses. Bragg and
Nishikawa determined the spinel structure of ferrite firstly as possessed by mineral
spinel MgAl2O4 in 1915. The formula of a spinel ferrite can be written in general as
MFe2O4 where M is a divalent metal ion such as Zn2+, Co2+, Mg2+, Fe2+, Cu2+, Ni2+,
Cd2+, or a combination of these ions. The structure of unit cell of spinel ferrite is
FCC having eight formula units per unit cell. The formula can be written as
M8Fe16O32. The anions form an FCC lattice and are the greatest. There are two
types of interstitial positions within these lattices, and metallic cations occupy these
positions. One unit cell has 96 interstitial sites in which 64 are tetrahedral (A) and
32 are octahedral (B) sites as depicted in Fig. 2.4. Ni-Cu-Zn is the class of soft ferrite
and chemically symbolized as MFe2O4. NiFe2O4 and CuFe2O4 are inverse spinel
and ZnFe2O4 ferrite has a normal spinel structure. Ni2+ and Cu2+ ions show their
strong preference to the octahedral B site because of favorable fit of charge

Fig. 2.3 Spinel unit cell

structure
2 Nanomaterials, their Types and Properties 27

Fig. 2.4 (a) Spinel structure, (b) octahedral interstice (B site, 32 per unit cell, 16 occupied) and (c)
tetrahedral interstice (A site, 64 per unit cell, 8 occupied)

distribution. Zn2+ions show a strong preference for tetrahedral A site because of its
electronic configuration. These ferrites are used in the surface-mount devices (SMD)
and multilayer chip inductors (MLCI) due to their excellent soft magnetic properties
at high frequencies and their high electrical resistivity. The spinel ferrite has been
classified into three categories based on the distribution of cations on tetrahedral
(A) and octahedral (B) sites: normal spinel ferrite, inverse spinel ferrite, and random
spinel ferrite.

2.4.1.1 Normal Spinel

The spinel is normal if there is only one kind of cations on octahedral [B] site. In
these ferrites the tetrahedral (A) sites are occupied by divalent cations while
the octahedral [B] sites by trivalent cations. To indicate the ionic distribution of
the octahedral [B] sites, square brackets are used. The formula for representing the
normal spinel is (M2+)A[Me3+]BO4 (M represents divalent ions and Me for trivalent
ions). Bulk ZnFe2O4A is a typical example of normal spinel ferrite. The cation
disorder is defined in terms of a “normal” spinel structure, for example, for ideal
MgAl2O4, all the Mg resides on tetrahedral sites coordinated with oxygen, and all the
Al resides on octahedral sites coordinated with oxygen. The inversion parameter is
defined as the ratio of the atomic fraction of Al on tetrahedral sites to the atomic
fraction of Al on octahedral sites. The inversion parameter is 0.0 for a perfect normal
spinel. Normal spinel structures are usually cubic closed-packed oxides having one
octahedral and two tetrahedral sites per oxide. The tetrahedral points are smaller than
the octahedral points. The octahedral holes are occupied by B3+ ions because of a
charge factor but can only occupy half of the octahedral holes. 1/eighth of the
tetrahedral holes are occupied by A2+ ions. If the ions are similar in size, this
maximizes the lattice energy. A common example of a normal spinel is MgAl2O4.
28 P. Thakur and A. Thakur

Fig. 2.5 Inverse spinel

2.4.1.2 Inverse Spinel

In inverse spinel structure, tetrahedral (A) sites and half octahedral [B] sites are
occupied by half of the trivalent ions; the remaining cations are randomly distributed
among the octahedral [B] sites as shown in Fig. 2.5. This formula for representing
these ferrites is given by (Me3+)A [M2+Me3+]BO4. Fe3O4 is a typical example of
inverse spinel ferrite which has divalent cations of Fe occupied at the octahedral
[B] sites. In an ideal “inverse” spinel structure (e.g., MgFe2O4), octahedral sites have
all of the Mg ions, and Fe is distributed equally over all of the tetrahedral sites and
the remaining octahedral sites. The inversion parameter would be 1.0 in this case.
Due to the crystal field stabilization energies (CFSE), of the transition metals
present, inverse spinel structures are slightly different. Some ions dependent on
the d-electron count may have a distinct preference on the octahedral site. If the A2+
ions have a strong preference for the octahedral site, they will force their way into it,
and displacement of half of the B3+ ions from the octahedral sites to the tetrahedral
sites takes place. If the B3+ ions have no preference if they have a low or zero
octahedral site stabilization energy (OSSE), then they will adopt the tetrahedral site.
A common example of an inverse spinel is Fe3O4, if the Fe2+ (A2+) ions are d6 high-
spin and the Fe+3 (B+3) ions are d5 high-spin.

2.4.1.3 Random Spinel

The spinel which has ionic distribution intermediate between normal and inverse is
called mixed spinel structure. The cations are equally distributed over the two sites in
ratios [M2+x Fe3+1-x]A[M2+1-x Fe3+1 + x]B O2
4 for a “random” spinel structure,
proportional to their stoichiometry and the site ratios. The inversion parameter is
(2/3), or 0.667 for a random spinel structure. The spinel ferrite is called random
spinel if the divalent metal ions and trivalent Fe3+ions are distributed randomly over
the tetrahedral and octahedral B sites.
2 Nanomaterials, their Types and Properties 29

2.4.2 Garnet Structure

The trivalent cations (including rare earth and Fe3+) occupy tetrahedral (d), octahe-
dral (a), or dodecahedral—a 12-sided deformed polyhedron—(c) sites in garnets,
which have an orthorhombic crystal structure (oxygen polyhedra encircling the
cations). The tetrahedral and octahedral sites interact in an antiparallel manner,
and the net magnetic moment is oriented in the opposite direction as the rare-earth
ions on the c sites. It’s the most intricate crystal structure, and drawing it in
2 dimensions with all 160 ions visible in the unit cell is difficult. The garnet structure
is composed of a combination of octahedral (trivalent cation surrounded by 6 oxygen
ions), tetrahedral (trivalent cations surrounded by 4 oxygen ions), and
12-sidedpolyhedral—dodecahedral—(trivalent cations surrounded by 8 oxygen
atoms) sites. 3Me2O3・5Fe2O3 is the chemical formula for garnets in which Me
represents the trivalent rare-earth ions like nonmagnetic yttrium or a magnetic rare
earth such as from lanthanum through ytterbium.

2.4.3 Orthoferrites

Rare-earth orthoferrites are classified as ferrites, although they are called

antiferromagnets. The magnetic oxides having perovskite structure are an exception
in the group of oxides. The figure shown below depicts the perovskite structure. The
corners of a cube are occupied by large divalent or trivalent ions (A), and small
trivalent or tetravalent metal ions (B) occupy the center of the cube. The oxygen ions
are situated centrally on the faces of the cube. The chemical formula of orthoferrites
is ABO3, where A represents yttrium or a rare earth. The inside of a sub-lattice is
usually collinear ferromagnetic structure, but the different sub-lattices are coupled
antiferromagnetically. Because of the different number of magnetic ions in different
sub-lattices, there is a net resulting magnetic moment, giving rise to ferrimagnetism.
The nature of the superexchange interaction depends not only on the type of the
magnetic ion but rather strongly on the bond length and bonding angle (Fig. 2.6).

Fig. 2.6 An orthoferrite with

perovskite structure
30 P. Thakur and A. Thakur

2.4.4 Hexagonal Ferrites

The crystal structure of regular barium hexaferrite is of the mineral

magnetoplumbite. It belongs to the group of M-type hexagonal ferrite. The crystal-
lographic unit cell is related to the space group P63/mmc and has two molecules with
chemical composition BaFe12O19. The dimensions of the unit cell are approximately
a ¼ b ¼ 6 Å and c ¼ 23 Å. The unit cell has the basic structure made up of ten layers
of oxygen ions that are formed by alternate close packing of cubic or hexagonal
stacked layers. In every fifth layer, one O
2 ion is replaced by barium. The crystal
structure of M-type barium can be divided into various blocks. The symbolic
representation of M-type barium ferrite structure is described as RSR*S*, where R
is a one-layer block having composition Ba2+Fe33+O32
and S is a four-O4
layer
block which has composition Fe93+O162
, where the asterisk means that the
corresponding block has been turned 180̊ around the hexagonal c-axis. The
interstices of oxygen atom have all the metal ions arranged in it. There are in total
five Fe sites: two ions have tetrahedral surroundings (4f1), and one Fe ion is located
in a trigonal bipyramid (2b) with fivefold coordination (Ishino and Narumiya 1987);
three octahedral positions (2a, 4f1, and 12k) are occupied by one, two, and six
Fe ions.

2.5 Properties of Ferrites

From the application point of view, the structural, electrical, and magnetic properties
of ferrite are very much important. By using proper method of preparation, sintering
temperature, choosing appropriate type and amount of dopant, etc., the electrical and
magnetic properties of ferrites can be modified.

2.5.1 Magnetic Properties

The magnetic characteristics of ferrite are determined by the distribution of metal

cations over the available sites. Magnetic characteristics of ferrite are classified as
intrinsic or structure-insensitive and extrinsic or structure-sensitive. Two prominent
structure-insensitive properties are saturation magnetization and Curie temperature.
On the other hand, there are a number of structure-sensitive properties, and the
attribute can be characterized as static or dynamic depending on whether or not it has
frequency dependence. Structure-dependent static qualities include induction, per-
meability, coercive force, hysteresis loop and associated energy loss, and remanence.
Structure-sensitive dynamic features include spin resonance, eddy current loss, and
domain barriers (Mathew and Juang 2007).
The properties which are unaffected by the microstructure are called as intrinsic
properties, for example, grain size and crystal orientation of grains. The saturation
2 Nanomaterials, their Types and Properties 31

magnetization (MS) of ferromagnetic material is defined as the maximum attainable

intensity of magnetization per unit volume. It is dependent on the strength of the
dipole moment on the atom that makes the material and how densely they are packed
together. The nature of the atom and the overall electronic structure within the
compound affect the atomic dipole moment. The crystal structure, i.e., the spacing
of the moments and the presence of any nonmagnetic elements within the structure,
determine the packing density of the atomic moments. MS will also depend on how
well these moments are aligned at finite temperatures in case of ferromagnetic
materials, as thermal vibration of the atoms causes misalignment of the moments
and MS is reduced. All of the moments are not aligned parallel for ferromagnetic
materials even at zero Kelvin, and hence relative alignment of the moments and the
temperature affect the MS. Curie temperature is the characteristic temperature
exhibited by ferromagnetic materials. The magnetic moments are partially aligned
within magnetic domains in ferromagnetic materials at temperatures below the Curie
point. Thermal fluctuations increasingly destroy this alignment as the temperature is
increased from below the Curie point, until the net magnetization reached zero at and
above the Curie point. The material is purely paramagnetic above the Curie point
(Beatrice et al. 2008). An applied magnetic field has a paramagnetic effect on the
magnetization, at temperatures below the Curie point, but the combination of
paramagnetism with ferromagnetism leads to the magnetization followed by a
hysteresis curve with the applied field strength. The destruction of magnetization
at the Curie temperature is a second-order phase transition and a critical point where
the magnetic susceptibility is theoretically infinite.
The extrinsic properties or structure-sensitive properties are listed under:

(a) Static properties.

(b) Dynamic properties.

Static properties include magnetic induction. If the performance of a magnetic

component or device is determined by the magnetization of the ferromagnetic
material involved, magnetization is used to evaluate the performance instead of
induction.
This is because of the definition of induction, B ¼ μ0 (H + M).
Because the μ0, H term has inherently made it a structure-sensitive static feature,
induction is more beneficial than magnetization in practice. Magnetic permeability
(μ) is defined as the ratio of magnetic induction (B) to magnetic field (H) or applied
field strength. The ratio of flux density to applied field is known as absolute
permeability. The closed B-H curve is called hysteresis loop because B lags behind
H in the B-H curve. As illustrated in the diagram below, this loop appears in the four
quadrants (Fig. 2.7).
In the B-H plot, an energy is given by W ¼ ʃ H. dB is represented by the area
enclosed by hysteresis loop. This magnetic energy in the form of heat dissipates
immediately into the lattice upon generation and lost permanently. Thus, hysteresis
loss is designated by having units of Joules per m3 per cycle. Hysteresis loss is very
undesirable in soft magnetic materials, not only because it wastes energy, but
32 P. Thakur and A. Thakur

Fig. 2.7 Typical hysteresis loop

problems are also created due to heat involved in the application of the material. The
ability of a ferromagnetic material to withstand an external magnetic field without
being demagnetized is called as coercive force and coercivity. Coercivity is the
criterion to determine whether a ferromagnetic material is soft or hard. A hard ferrite
and a soft ferrite are differentiated based on their respective coercive force. Hc is
large (~100 Oe) for a hard ferrite and small (<20 Oe) for a soft ferrite. The major
goal of soft magnetic material preparation is to keep coercivity to a minimum.
Coercivity is intimately related to magnetic properties that are structure-sensitive,
as evidenced by experimental data. Remanence or retentivity is the amount of
induction that remains after the field H is made zero. Remanence or retentivity is
the name for this type of induction.
Eddy currents and the energy losses they cause, are examples of dynamic
characteristics. An electromagnetic force (e.m.f.) is induced in a ferromagnetic
body when it is magnetized by an alternating field. If the material is a good conductor,
such as metals and alloys, the induced e.m.f. produces a significant quantity of
currents in various places; these currents are known as eddy currents, and their
presence causes energy loss (W). At high frequency, the resonance of Bloch walls
is a prominent phenomenon found in ferrites. It plays an important role in the
application of soft magnetic materials. It is found that the eddy current power loss
is proportional to the square of the velocity of the domain walls. Thus, we must try to
keep the wall velocity at the lowest possible value to minimize the loss. Some
applications of ferrites at microwave frequency also involve the resonance of domain
walls.
2 Nanomaterials, their Types and Properties 33

2.5.2 Electrical Properties

Due to their high electrical resistivity, ferrites play a useful role in many technologi-
cal applications. Electrical properties of ferrites are dependent on the chemical
composition as well as on the various heat treatments during the course of prepara-
tion. The method of preparation also affects these properties (Coey 2009). The
Verwey hopping mechanism explained the variation in dc electrical resistivity
(Jonker 1959) according to which, the electrical conduction in ferrites is due to the
hopping of electrons between the ions of different valence states present at the
octahedral sites but of the same element. The hopping of electrons between Fe3+
and Fe2+ ions present at octahedral sites causes the conduction in ferrites (Elwell
et al. 1966). Generally, with the increase of temperature, the electrical resistivity of
ferrites decreases. This shows semiconductor-like behavior of ferrites (Verwey et al.
1950). Ferrites are applicable for microwave applications due to their very high
resistivity (Snoek 1947). For ferrites, resistivity values vary from 10
2 ohm-cm to
1011 ohm-cm depending on chemical composition of the material at room tempera-
ture (Mathew and Juang 2007).

2.5.3 Dielectric Properties

Many factors decide the dielectric properties such as the method of preparation,
grain structure or size, and chemical composition. The valence state changes when a
ferrite is sintered under slightly reducing condition, and the individual cation found
in the sample leads to high conductivity. When cooling of such a material is done in
an oxygen atmosphere, films of high resistivity are formed over the constituent grain.
Such ferrites behave as inhomogeneous dielectric material in which the individual
grains are separated by air gaps or low-conducting layers. This piqued people’s
curiosity in ferrite’s dielectric behavior in the low-frequency region (102 Hz–
105 Hz).

2.6 Application of Ferrites

Due to lower cost, high resistivity, superior magnetization properties, and easier
manufacture, ferrites are considered as better magnetic materials as compared to pure
metals. The application area of ferrites includes radar, bubble devices, audio-video
and digital recording, microwave devices, satellite communication, and memory
cores (Mathew and Juang 2007; Beatrice et al. 2008; Coey 2009). Application area
of ferrites is very vast ranging from microwave to radio frequencies. They are used in
flyback transformer in TV picture tube, mechanical filter, antenna cores in radio
receivers, moderators, broadband transformer, phase shift, ultrasonic generators, and
isolators. Ferrites are used in computers, telephone exchange, and control
equipments nowadays. Ferrites are generally of two types—soft ferrite and hard
ferrite. Soft ferrites are a class of magnetic materials used in telecommunication
computer, transformer cores primarily in television, medical, and also in electronics.
34 P. Thakur and A. Thakur

Hard ferrites are being used in making permanent magnets, in loudspeakers and
micromotors. The use of low loss polycrystalline ferrites should be in a high
frequency range. For the good performance in application area and classified by
the initial permeability, for the low and high-frequency applications, the most
important technological properties are coercive force (HC), initial permeability,
saturation magnetization (MS), and losses. It is generally impossible to get the best
combination of these properties for any specific application. Most of the parameters
can be controlled either by varying the compositions or by varying the synthesis
technique or adding additives. Thin films of defect spinel ferrites have application as
write-once read many media working with blue wavelengths. Also, due to the
metastable nature of nonstoichiometric ferrites, they can be transformed by a laser
spot into corundum phases at moderate temperatures. In contrast to the starting
ferrite film, the transformed regions have different optical indices from which
makes the readout process possible (Jonker 1959). Temperature is controlled by
using magnetic sensors which are prepared by using ferrite materials having definite
and sharp Curie temperature. Proximity switches can also be fabricated using
ferrites. Also, ferrites are used to control pollution in which precipitation of ferrite
precursors is used to scavenge pollutant materials such as lead and cadmium from
waste streams. In addition, the produced ferrites are easily magnetically separated
along with the pollutant. Due to their high resistance to corrosion, ferrites which
have suitable conductivities can be used as electrode in applications, for example,
chromium plating. Ferrites have applications in radio and television circuits such as
flyback transformers, SMPS transformer for power applications, and deflection
Yokes. Soft ferrites are used for computer memory hard disc, floppy disc audio-
video cassette, high-frequency transformer core, and recorder head. Hard ferrites are
used in permanent magnets in motor, generator, telephone, and loudspeaker.

2.6.1 Some Technically Important Ferrites

Due to high permeability at high frequency, mechanical hardness, remarkably high

electrical resistivity, reasonable cost, and chemical stability, Ni-Zn ferrites having
spinel crystal structure are extensively used in a number of electronic devices
(Yamashita and Kurusawa 1958). Ni ferrite is a model inverse ferrite, and Zn ferrite
is a model normal ferrite because of strong preferences of Zn and Ni for the
tetrahedral and octahedral sites, respectively (Ishino and Narumiya 1987). The
cation distribution of Ni-Zn ferrite is represented by (ZnxFe1-x)[Ni1-xFe1 + x]O4.
This system has been extensively studied for various properties including structural
issues. The studies on magnetic and dielectric properties in Ni-Zn ferrites
synthesized by conventional technique have been reported by many researchers
(Smit and Wijn 1959; Murthy and Ramaiah 2000; Ajmal and Maqsood 2008;
Yadoji et al. 2003; Akther Hossaina et al. 2007). The most common method for
preparing ferrites is conventional method from so decades. The dielectric properties
of nickel-zinc ferrites NixZn1-xFe2O4, where x changed from 0.2 to 1.0 were
investigated by Mohan et al. (Abdeen 1998) using standard ceramic technique for
2 Nanomaterials, their Types and Properties 35

synthesis. The investigation of frequency, temperature, and composition dependence

of NiZn ferrites was done. The dielectric constant and loss tangent were found to
decrease with an increase in zinc content up to x ¼ 0.4. Beyond x ¼ 0.4, these
parameters increased progressively. This was due to the reason that the variation of
dielectric constant depends linearly on the variation of available ferrous ions on
octahedral sites. With increasing frequency dielectric constant declined. Maximum
dielectric dispersion was seen at x ¼ 0.8, which can be explained by the availability
of ferrous ions on octahedral sites. The electron exchange between Fe2+ and Fe3+ in
an n-type semiconducting ferrite and hole exchange between Ni3+ and Ni2+ in a
p-type semiconducting ferrite explained the difference in dispersion for mixed
nickel-zinc ferrites. The dielectric constant and DC resistivity are inversely propor-
tional to one another. Additionally, the dielectric loss reflected in resistivity that the
lower loss exhibited higher resistivity and vice versa. With an increase in tempera-
ture up to a particular temperature, there is gradual increase in dielectric constant,
which is designated as the dielectric transition temperature Ts. However, there was a
continuous decrease in the values of the dielectric constant for all the samples
beyond this temperature. The conductivity of Ni1-xZnxFe2O4 as a function of
composition and temperature was studied by Ranga and Ravinder (Ranga et al.
1999). They observed an increase in conductivity with zinc content and temperature.
The charge carrier concentration was calculated, and the higher charge carrier in
higher temperature up to magnetic transition temperature was observed. There is a
decrease in the concentration of charge carrier beyond this temperature. El-Sayed
(El-Sayed et al. 2003) did further research on the electrical conductivity of Ni1-
xZnxFe2O4 (x ¼ 0.1, 0.3, 0.5, 0.7, and 0.9) prepared by using ceramic processing
technique. For x ¼ 0.3, they found the lowest conductivity and higher activation
energy in nickel-zinc ferrite. The substitution of Zn in the Ni1-xZnxFe2O4 system was
investigated by Ajmal and Maqsood (Ajmal et al. 2007), and they checked the effect
on the physical properties. The variation of zinc content on DC resistivity, dielectric
constant, and loss factor was observed. The dielectric constant was found to increase
with the increase in Zn concentration. The resistivity values were calculated in the
range of 1.629  106–3.0  103 Ω-cm. With the variation in frequency from 80 Hz
to 1 MHz, loss factor remained in the range of 9.057–0.456. It is observed by various
workers that the magnetization having the highest values for x ¼ 0.3 /0.4 in Ni1-
xZnxFe2O4 (Murthy and Ramaiah 2000; Ajmal and Maqsood 2008; Ajmal and
Maqsood 2007; Jadhav et al. 2008; Kakatkar et al. 1996). So it was decided to
conduct further research with different ion substitution by keeping Ni0.7Zn0.3Fe2O4
as a parent compound. There are some inherent drawbacks in conventional methods,
for example, poor compositional control, coarser particle, chemical inhomogeneity,
and introduction of some impurities during milling. Thus, some voids and
low-density areas are formed in the green compact due to the coarser and nonuni-
form particles (Li et al. 2000). However, a variety of wet methods such as ball
milling, sol-gel, hydrothermal, coprecipitation, and microemulsions have been used
to synthesize ferrite materials. There are unique advantages of each method. But, still
it is a matter of interest to try to improve the physical properties of ferrites by new
designing in synthesize. Recently sol-gel methods have been used to prepare
36 P. Thakur and A. Thakur

ultrafine, reproducible, and homogenous powder (Kumar et al. 2011; Patil et al.
2002; Popovici et al. 2003; VijayaBhasker Reddy et al. 2010; Shirsath et al. 2010).
In recent years, it has been discovered that the sol-gel approach has considerable
advantages over traditional dry processing. The ultimate goal is to create ferrites with
improved physical and magnetic properties that can be used in a range of industrial
applications. The synthesis of nickel-zinc ferrites was done by Elsa E. Sileo (Mane
et al. 2011) using citrate precursor method. The combustion method was used for the
preparation of Ni1-xZnxFe2O4 (0.2, 0.4, 0.5, 0.6, and 0.7). Metal nitrates and citric
acid were used to obtain precursors by sol process and then heated at 200  C. The
heating of residues was done at 1000  C for 2 h. Insertion of small amounts of
different R (III) cations (R ¼ yttrium, ruthenium, and rare-earth cations) into
Ni0.5Zn0.5 Fe2O4 has also been studied. The structure and magnetic properties of
Ni-Zn ferrites can be modified from rare-earth addition. The auto-combustion
method was used to prepare Ni0.5 Zn0.5 Fe2-yRYO4 samples. Different proportions
of nickel and zinc oxalates and iron nitrates were weighed by authors and then
diluted in water ([Fe (III)] + [Ni (II)] + [Zn (II)] ¼ 1 M) followed by addition of 3 M
citric acid solution (50 ml) to each metal solution. The heating was done at 40  C
with continuous stirring for 30 min. A highly viscous gel formation took place after
evaporation which was heated at approx. 200  C. Then calcination of the final
residue was done at 1000  C for 2 h. For the preparation of R-inserted sample,
Ni0.5 Zn0.5Fe2O4 was used as reference compound. For XRD analysis, D5000
diffractometer was used, keeping 2-theta collection range 16. 125 with scan-
ning time of 15 s and step size 0.02 with CuKα radiation. The gel was heated in
the temperature range 25–450  C for the characterization of auto-combustion pro-
cess at a heating rate of 10  C min
1. It was observed from XRD analysis that the
only product in auto-combustion method was nanometer-sized spinels. There is an
increment in crystallite size (10.1–12.0–13.6–24.7–33.4 nm) for Ni0.5 Zn0.5 Fe2O4
sample calcined for 1 h at temperatures (300, 500, 700, 1000  C). There is a regular
increase in lattice constant for Zn-substituted Ni ferrites with Zn(II) content. The
decomposition range for the citrate precursor was found in the range of 197–369  C
for NiFe2O4 and 178–328  C for Ni0.5Zn0.5Fe2O4. Pure ferrites were obtained for Ru
(y ¼ 0.01 and 0.02), Eu (y ¼ 0.02), and Y (y ¼ 0.01 and 0.02) preparations. There are
many applications of Ni-Zn ferrites, and they are commercially used as high-
frequency ferrites for radio-frequency coils and transformer cores.
Coprecipitation method was used by S.J. Azhagushanmugam
(Azhagushanmugam et al. 2013) to synthesize nanoferrite powder followed by
heat treatment at different sintering temperatures (130, 600, and 900 C). The
structural, SEM, and FTIR investigations were done on the sintered Ni-Zn ferrite
powders. From the line broadening in XRD pattern, the average crystallite was
calculated. XRD patterns confirmed the single-phase cubic spinel structure of
Ni-Zn ferrite. Particle size increased with an increase in sintering temperature from
45.59 nm at 130  C to 47.21 nm at 600  C and 50.47 nm at 900  C.With increase in
sintering temperature, lattice parameter also increased (at 130 it is found to be 8.359,
at 600  C is 8.360 and at 900  C is 8.364). With increase of temperature, all the XRD
peaks become sharper and narrower indicating an increase in particle size and
2 Nanomaterials, their Types and Properties 37

enhancement of crystallinity. IR spectra were measured in the range of

400–4000 cm
1. The characteristic bands at intensities (3400 cm
1, 1500 cm
1
and 1380 cm
1 approx.) were observed. This is due to O-H stretching vibration.
There is drastic increase in intensities of the bands with increase in sintering
temperature due to the loss of residual water in the sample. From SEM it was
observed that the microstructure consisted of clusters of about 1 μm in size.
Nickel ferrite is a very attracting class because of its interesting and important
properties. This class of soft ferrite is also useful in many technical applications, like
in catalysis, sensor, and so on. In the referred paper (Nejati and Zabihi 2012),
NiFe2O4 nanoparticles were synthesized by the hydrothermal method, and investi-
gation of the inhibition of surfactant (glycerol or sodium dodecyl sulfate) on the
particle growth was done. The samples were prepared in the presence of glycerol and
sodium dodecyl sulfate, for investigation of the inhibition effect of surfactant
NiFe2O4 particle growth. The samples were characterized using X-ray diffraction
(XRD), Fourier-transform infrared spectroscopy (FTIR), transmission electron
microscopy (TEM), vibrating sample magnetometer, and inductively coupled
plasma atomic emission spectroscopy (ICP-AES) techniques. The author obtained
that the products were pure NiFe2O4 from XRD and ICP-AES and with increasing
the temperature (from 30 nm at 100  C to 53 nm at 150  C), the growth in
nanoparticles was also noticed, while under the same condition, surfactant prevents
the particle growth. The Scherrer equation was used to calculate the average particle
size, and TEM micrographs revealed the size of nanoparticles in the range of
50–60 nm in the presence of surfactant decreased up to 10–15 nm. The nanoparticle
at the room temperature exhibited a superparamagnetic behavior.
The assisted hydrothermal methods were used for nanosized nickel ferrite particle
synthesis with and without surfactant. The results show that the crystallinity of
nanoparticles is increased with increasing of temperature. In comparison with
surfactant-free prepared samples, the crystallinity of NiFe2O4 nanoparticles
decreased in the presence of surfactant. At room temperature, all of the nickel ferrite
nanoparticles were superparamagnetic. In his research Binu P Jacob (Jacob et al
2011) synthesized nickel ferrites by sol-gel and coprecipitation techniques. Attrac-
tive properties were shown by nanosized nickel ferrites for the application of soft
magnets, core materials in power transformers, and low loss material at high
frequencies. High permeability in the radio-frequency region, high Curie tempera-
ture, high electrical resistivity, and low eddy current loss are important properties of
nickel ferries due to which these ferrites are suitable for many applications. XRD
patterns of NiFe2O4 confirmed the formation of single-phase cubic NiFe2O4
nanoparticles with hematite phase. It is observed that nanoparticles with less crys-
tallite size were obtained as compared with the sol-gel synthesis and the crystallite
size was found to increase with the temperature in both processes. EDX analysis was
done to check the stoichiometry of the powdered sample. In the samples prepared by
coprecipitation, Ni deficiency and excess of oxygen were observed, while in the case
of sol-gel-derived sample, expected stoichiometry was shown. The particle size and
morphology of the sample were estimated by using TEM samples, and slightly
agglomerated particles with almost spherical shape were observed in case of
sol-gel annealed at 400  C, and a particle size of 18–25 nm was obtained. An
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*** START OF THE PROJECT GUTENBERG EBOOK COUNTRY LUCK

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 Country Luck.
BY
J O H N H A B B E R T O N,
AUTHOR OF “BRUETON’S BAYOU,” ETC.

PHILADELPHIA:
J. B. LIPPINCOTT COMPANY.
1887.

All Rights Reserved.

———
Copyright, 1887, by J. B. Lippincott Company.
———
 CONTENTS.
CHAPTER PAGE
I. —How it came about 5
II. —Family Councils 16
III. —“Down to York” 27
IV. —The Tramlay Reception 36
V. —Not so Dreadful after all 44
VI. —Reconstruction 52
VII. —At her Side 62
VIII. —Himself for Company 74
IX. —News, yet no News 80
X. —Agnes Dinon’s Party 88
XI. —Drifting from Moorings 101
XII. —Iron looks up 109
XIII. —“While yet afar off” 117
XIV. —Going Home 126
XV. —The Fatted Calf,—but the Neighbors, too 135
XVI.—More News that was not enough 142
XVII. —Father and Son 149
XVIII. —The New Clerk 158
XIX.—Hopes and Fears 168
XX. —An Old Question repeated 178
XXI.—Haynton rouses itself 186
XXII. —Several Green-eyed Monsters 196
XXIII. —E. & W. 205
XXIV. —Iron looks still higher 212
XXV. —E. & W. again 220
XXVI. —Some Minds relieved 229
XXVII. —Among the Ruins 240
XXVIII. —“And e’en the Fates were Smiling” 249
XXIX. —So they were Married 257
C O U N T R Y L U C K.
 CHAPTER I.

HOW IT CAME ABOUT.

“Be sure to look us up when you come to the city.”

This invitation was extended with that delightful affectation of heartiness
that a man can assume when he believes that the person invited will never
avail himself of the courtesy. Fortunately for the purpose of this story,
Master Philip Hayn, whom Mr. Tramlay had asked to call, was too young
and too unaccustomed to the usages of polite society to regard the remark in
any but its actual sense.
It would have seemed odd to any one knowing the two men and their
respective stations in life. Tramlay was a New York merchant, well known
and of fair standing in the iron trade; Hayn was son of the farmer at whose
house the Tramlay family had passed the summer. When the Tramlays
determined to exchange the late summer dust of the country for the early
autumn dust of the city, it was Philip who drove the old-fashioned carryall
that transported them from the farm to the railway-station. The head of the
merchant’s family was attired like a well-to-do business-man; Philip’s coat,
vest, and trousers were remnants of three different suits, none of recent cut.
The contrast was made sharper by the easy condescension of the older man
and the rather awkward deference of Philip, and it moved Mrs. Tramlay to
whisper, as her husband helped her aboard the train,—
“Suppose he were to take you at your word, Edgar?”
The merchant shrugged his shoulders slightly, and replied, “Worse men
have called upon us, my dear, without being made to feel unwelcome.”
“I think ’twould be loads of fun,” remarked Miss Lucia Tramlay.
Then the three, followed by smaller members of the family, occupied as
many seats near windows, and nodded smiling adieus as the train started.
Philip returned their salutations, except the smiles: somehow, the
departure of all these people made him feel sober. He followed the train
with his eyes until it was out of sight; then he stepped into the old carryall
and drove briskly homeward, declining to rein up and converse with the
several sidewalk-loungers who manifested a willingness to converse about
the departed guests. When he reached the outer edge of the little village he
allowed the horses to relapse into their normal gait, which was a slow walk;
he let the reins hang loosely, he leaned forward until his elbows rested upon
his knees and his hat-brim seemed inclined to scrape acquaintance with the
dash-board, then he slowly repeated,—
“ ‘Be sure to look us up when you come to the city.’ You may be sure
that I will.”
The advent of the Tramlays at Hayn Farm had been productive of new
sensations to all concerned. The younger members of the Tramlay family
had at first opposed the plan of a summer on a farm: they had spent one
season at Mount Desert, and part of another at Saratoga, and, as Lucia had
been “out” a year, and had a sister who expected early admission to a
metropolitan collection of rosebuds, against a summer in the country—the
rude, common, real country—the protests had been earnest. But the head of
the family had said he could not afford anything better; trade was dull, a
man had to live within his income, etc. Besides, their mother’s health was
not equal to a summer in society: they would find that statement a
convenient excuse when explaining the family plans to their friends.
Arrived at Hayn Farm, the objections of the juvenile Tramlays quickly
disappeared. Everything was new and strange; nothing was repellent, and
much was interesting and amusing: what more could they have hoped for
anywhere,—even in Paris? The farm was good and well managed, the
rooms neat and comfortable though old-fashioned, and the people
intelligent, though Miss Lucia pronounced them “awfully funny.” The head
of the family was one of the many farmers who “took boarders” to give his
own family an opportunity to see people somewhat unlike their own circle
of acquaintances,—an opportunity which they seemed unlikely ever to find
in any other way, had he been able to choose. The senior Hayn would have
put into his spare rooms a Union Theological Seminary professor with his
family, but, as no such person responded to his modest advertisement, he
accepted an iron-merchant and family instead.
Strawberries were just ripening when the Tramlays appeared at Hayn
Farm, and the little Tramlays were allowed to forage at will on the
capacious old strawberry-bed; then came other berries, in the brambles of
which they tore their clothes and colored their lips for hours at a time. Then
cherries reddened on a dozen old trees which the children were never
reminded had not been planted for their especial benefit. Then the
successive yield of an orchard was theirs, so far as they could absorb it.
Besides, there was a boat on a pond, and another on a little stream that
emptied into the ocean not far away; and although the Hayn boys always
seemed to have work to do, they frequently could be persuaded to
accompany the children to keep them from drowning themselves.
For Mrs. Tramlay, who really was an invalid, there were long drives to
be taken, over roads some of which were well shaded and others
commanding fine views, and it was so restful to be able to drive without
special preparation in the way of dress,—without, too, the necessity of
scrutinizing each approaching vehicle for fear it might contain some
acquaintance who ought to be recognized.
As for the head of the family, who spent only Saturdays and Sundays
with his family, he seemed to find congenial society in the head of the
house,—a fact which at first gave his wife great uneasiness and annoyance.
“Edgar,” Mrs. Tramlay would say, “you know Mr. Hayn is only a
common farmer.”
“He’s respectable, and thoroughly understands his own business,” the
husband replied,—“two reasons, either of which is good enough to make
me like a man, unless he happens to be disagreeable. ‘Common farmer’!
Why, I’m only a common iron-merchant, my dear.”
“That’s different,” protested Mrs. Tramlay.
“Is it? Well, don’t try to explain how, little woman: ’twill be sure to give
you a three days’ headache.”
So Tramlay continued to devote hours to chat with his host, pressing
high-priced cigars on him, and sharing the farmer’s pipes and tobacco in
return. He found that Hayn, like any other farmer with brains, had done
some hard thinking in the thousands of days when his hands were employed
at common work, and that his views of affairs in general, outside of the iron
trade, were at least as sound as Tramlay’s own, or those of any one whom
Tramlay knew in the city.
The one irreconcilable member of the family was the elder daughter,
Lucia. She was the oldest child, so she had her own way; she was pretty, so
she had always been petted; she was twenty, so she knew everything that
she thought worth knowing. She had long before reconstructed the world
(in her own mind) just as it should be, from the stand-point that it ought to
exist solely for her benefit. Not bad-tempered, on the contrary, cheerful and
full of high spirits, she was nevertheless in perpetual protest against
everything that was not exactly as she would have it, and not all the
manners that careful breeding could impart could restrain the unconscious
insolence peculiar to young and self-satisfied natures. She would laugh
loudly at table at Mrs. Hayn’s way of serving an omelet, tell Mrs. Hayn’s
husband that his Sunday coat looked “so funny,” express her mind freely,
before the whole household, at the horrid way in which the half-grown
Hayn boys wore their hair, and had no hesitation in telling Philip Hayn, two
years her senior, that when he came in from the field in his brown flannel
shirt and gray felt hat he looked like an utter guy. But the Hayns were
human, and, between pity and admiration, humanity long ago resolved to
endure anything from a girl—if she is pretty.
Slowly the Hayns came to like their boarders; more slowly, but just as
surely, the Tramlays learned to like their hosts. Mutual respect began at the
extremes of both families. Mrs. Tramlay, being a mother and a housekeeper,
became so interested in the feminine half of the family’s head that she
ceased to criticise her husband’s interest in the old farmer. The Tramlay
children wondered at, and then admired, the wisdom and skill of their
country companions in matters not understood by city children. Last of all,
Lucia found herself heartily respecting the farmer’s son, and forgetting his
uncouth dress and his awkwardness of manner in her wonder at his general
courtesy, and his superior knowledge in some directions where she
supposed she had gone as far as possible. She had gone through a finishing-
school of the most approved New York type, yet Philip knew more of
languages and history and science than she, when they chanced—never
through her fault—to converse on such dry subjects; he knew more flowers
than she had ever seen in a florist’s shop in the city; and once when she had
attempted to decorate the rather bare walls of the farm-house parlor he
corrected her taste with a skill which she was obliged to admit. There was
nothing strange about it, except to Lucia; for city seminaries and country
high schools use the same text-books, and magazines and newspapers that
give attention to home decorations go everywhere; nevertheless, it seemed
to Lucia that she had discovered a new order of being, and by the time she
had been at Hayn Farm a month she found herself occasionally surprised
into treating Philip almost as if he were a gentleman.
 Philip’s interest in Lucia was of much quicker development. He had had
no prejudices to overcome; besides, the eye is more easily approached and
satisfied than the intellect, and Lucia had acceptably filled many an eye
more exacting than the young farmer’s. There were pretty girls in homes
near Hayn Farm, and more in the village near by, but none of them were
——well, none were exactly like Lucia. Philip studied her face; it was
neither Roman nor Grecian, and he was obliged to confess that the
proportions of her features were not so good as those of some girls in the
neighborhood. Her figure suggested neither perfect grace nor perfect
strength; and yet whatever she did was gracefully done, and her attire,
whether plain or costly, seemed part of herself,—a peculiarity that he had
never observed among girls born in the vicinity. He soon discovered that
she did not know everything, but whatever she did know she talked of so
glibly that he could not help enjoying the position of listener. She did not
often show earnestness about anything that to him was more than trifling,
but when she did go out of her customary mood for a moment or two she
was saintly: he could think of no other word that would do it justice. He had
not liked her manner to his own mother, for at first the girl treated that
estimable woman as a servant, and did it in the manner which makes most
servants detest most young ladies; but had she not afterward, with her own
tiny fingers, made a new Sunday bonnet for Mrs. Hayn, and had not his
mother, in genuine gratitude, kissed her? Should he bear malice for what his
mother had forgiven?
The young man merely admired and respected Lucia: of that he was very
sure. Regard more tender he would have blamed himself for, first, because
love implied matrimony, which he did not intend to venture into until he
had seen more of the world and perhaps gone to college; secondly, because
he did not imagine that any such sentiment would be reciprocated. He came
of a family that through generations of hard experience had learned to count
the cost of everything, even the affections, like most of the better country-
people in the older States. He had also an aversion to marriage between
persons of different classes. Lucia was to him an acquaintance,—not even a
friend,—whom he highly esteemed; that was all.
His father thought differently, and one day when the two were in the
woodland belonging to the farm, loading a wagon with wood to be stored
near the house for winter use, the old man said, abruptly,—
“I hope you’re not growin’ too fond of that young woman, Phil?”
 “No danger,” the youth answered, promptly, though as he raised his head
his eyes did not meet his father’s.
“You seem to know who I mean, anyhow,” said the old man, after
throwing another stick of wood upon the wagon.
“Not much trouble to do that,” Phil replied. “There’s only one young
woman.”
The father laughed softly; the son blushed violently. Then the father
sighed.
“That’s one of the signs.”
“What’s a sign?—sign of what?” said Phil, affecting wonder not quite
skilfully.
“When ‘there’s only one young woman’ it’s a sign the young man who
thinks so is likely to consider her the only one worth thinkin’ about.”
“Oh, pshaw!” exclaimed Phil, attacking the wood-pile with great
industry.
“Easy, old boy; ’twasn’t the wood-pile that said it. Brace up your head;
you’ve done nothing to be ashamed of. Besides, your old father can see
through the back of your head, anyhow: he’s been practisin’ at it ever since
you were born.”
Phil seated himself on the wood-pile, looked in the direction where his
father was not, and said,—
“I like Lucia very much. She’s a new face; she’s different from the girls
about here. She’s somebody new to talk to, and she can talk about
something beside crops, and cows, and who is sick, and last Sunday’s
sermon, and next month’s sewing-society. That’s all.”
“Yes,” said the old man. “It doesn’t seem much, does it? Enough to have
made millions of bad matches, though, and spoiled millions of good ones.”
Phil was silent for a moment; then he said, with a laugh,—
“Father, I believe you’re as bad as old Mrs. Tripsey, whom mother’s
always laughing at because she thinks a man’s in love if he sees her
daughter home from prayer-meeting.”
“P’r’aps so, my boy,—p’r’aps,—and maybe as bad as you, for every
time there’s a bad thunder-storm you’re afraid the lightning’ll strike the
barn. Do you know why? It’s because your finest colt is there. Do you see?”
 Phil did not reply, so the old man continued:
“I’ll make it clearer to you. You’re my finest colt; there’s more
lightnings in a girl’s eyes than I ever saw in the sky, you don’t know when
it’s going to strike, and when it hits you you’re gone before you know it.”
“Much obliged. I’ll see to it that I keep myself well insulated,” said Phil.
Nevertheless, Phil studied Lucia whenever he had opportunity,—studied
her face when she read, her fingers when they busied themselves with fancy
work, her manner with different persons, as it changed according to her idea
of the deservings of those with whom she talked. At church he regarded her
intently from the beginning of the service to its end, analyzing such portions
of prayer, hymn, or sermon as did not seem to meet her views. He even
allowed his gaze to follow her when she looked more than an instant at
other young women, in the ignorance of his masculine heart wondering
which of the features of these damsels specially interested her; his mother
could have told him that Lucia was merely looking at bonnets and other
articles of attire, instead of at their wearers. He wondered what she thought;
he told himself where her character was at fault, and how it might be
improved. In short, he had ample mental leisure, and she was the newest
and consequently the least understood of his various subjects of
contemplation.
It is impossible to devote a great deal of thought to any subject without
becoming deeply interested, even if it be unsightly, tiresome, and
insignificant. Lucia was none of these, for she was a pretty girl. It is equally
impossible to see a familiar subject of thought in the act of disappearance
without a personal sense of impending loneliness, and a wild desire to
snatch it back or at least go in search of it. Therefore Philip Hayn needed
not to be in love, or even to think himself so, to be conscious of a great
vacancy in his mind as the train bore the Tramlay family rapidly toward
their city home, and to determine that he would avail himself of the
invitation which the head of the family had extended.
 CHAPTER II.

FAMILY COUNCILS.

“Husband,” said Mrs. Hayn to her husband one night, when the person
addressed was about to drop asleep, “something’s the matter with Phil.”
“A touch of malaria, I suppose,” said the farmer. “He’s been gettin’ out
muck earlier than usual, and spreadin’ it on the ridge of the pasture. The
sun’s been pretty hot, though it is October, and hot sun on that sort of stuff
always breeds malaria.”
“I wasn’t talkin’ of sickness,” said the wife. “The dear boy’s health is as
good as ever. It’s his mind that’s out o’ sorts.”
A long soft sigh was the farmer’s only reply for a moment. It was
followed by the remark,—
“That city gal, I s’pose,—confound her!”
“I don’t see what you want her confounded for: she hasn’t done anythin’.
They don’t correspond.”
“I should hope not,” said Hayn, with considerable vigor: he now was
wide awake, “What could they write about? You don’t s’pose Phil could
write anythin’ about our goin’s-on that would interest her, do you?”
“No, but young people sometimes do find somethin’ to exchange letters
about. You and I didn’t, when we were boy and girl, because we lived
within a stone’s throw of each other, an’ you couldn’t keep away from our
house after dark; but Philip and——”
“For goodness sake, old lady,” interrupted the husband, “don’t you go to
settin’ yourself down, at your time of life, by gettin’ the match-makin’ fever.
There isn’t the slightest chance that——”
“I didn’t say there was; but boys will be boys.”
“It doesn’t follow that they should be fools, does it?—not when they’re
our boys?”
“ ‘Tisn’t bein’ a fool to be interested in a rich man’s daughter. I’ve often
thought how different your life might have been if I’d had anything besides
myself to give you when you married me.”
“I got all I expected, and a thousand times more than I deserved.” This
assertion was followed by a kiss, which, though delivered in the dark, was
of absolutely accurate aim.
“Don’t put it into Phil’s head that he can get more than a wife when he
marries; ’twill do him a great deal more harm than good.”
“I’d like to see the dear boy so fixed that he won’t have to work so hard
as you’ve had to do.”
“Then you’ll see him less of a man than his father, when he ought to be
better. Isn’t that rather poor business for a mother in Israel to be in, old
lady?”
“Well, anyhow, I believe Phil’s heart is set on makin’ a trip down to
York.”
“Oh, is that all? Well, he’s been promised it, for some day, this long
while. Something’s always prevented it, but I s’pose now would be as good
a time as any. He deserves it; he’s as good a son as man ever had.”
Mrs. Hayn probably agreed with her husband as to the goodness of their
son, but that was not the view of him in which she was interested just then.
Said she,—
“If he goes, of course he’ll see her.”
Again the farmer sighed; then he said, quite earnestly,—
“Let him see her, then; the sooner he does it the sooner he’ll stop
thinkin’ about her. Bless your dear foolish old heart, her ways and his are as
far apart as Haynton and heaven when there’s a spiritual drought in this
portion of the Lord’s vineyard.”
“I don’t think the Tramlays are so much better than we, if they have got
money,” said Mrs. Hayn, with some indignation. “I always did say that you
didn’t set enough store by yourself. Mrs. Tramlay is a nice enough woman,
but I never could see how she was any smarter than I; and as to her
husband, I always noticed that you generally held your own when the two
of you were talking about anything.”
“Bless you!” exclaimed the farmer, “you are rather proud of your old
husband, aren’t you? But Phil will soon see, with half an eye, that it would
be the silliest thing in the world for him to fall in love with a girl like that.”
 “I can’t for the life of me see why,” said the mother. “He’s just as good
as she, and a good deal smarter, or I’m no judge.”
“See here, Lou Ann,” said the farmer, with more than a hint of
impatience in his voice, “you know ’twon’t do either of ’em any good to
fall in love if they can’t marry each other. An’ what would Phil have to
support his wife on? Would she come out here an’ ’tend to all the house-
work of the farm, like you do, just for the sake of havin’ Phil for a husband?
Not unless she’s a fool, even if Phil is our boy an’ about as good as they
make ’em. An’ you know well enough that he couldn’t afford to live in New
York: he’s got nothin’ to do it on.”
“Not now, but he might go in business there, and make enough to live in
style. Other young fellows have done it!”
“Yes,—in stories,” said the old man. “Lou Ann, don’t you kind o’ think
that for a church-member of thirty years’ standin’ you’re gettin’ mighty
worldly-minded?”
“No, I don’t,” Mrs. Hayn answered. “If not to want my boy to drudge
away his life like his father’s done is bein’ worldly, then I’m goin’ to be a
backslider, an’ stay one. I don’t think ’twould be a bit bad to have a married
son down to York, so’s his old mother could have some place to go once in
a while when she’s tired to death of work an’ worry.”
“Oho!” said the old man: “that’s the point of it, eh? Well, I don’t mind
backslidin’ enough myself to say the boy may marry one of Satan’s
daughters, if it’ll make life any easier for you, old lady.”
“Much obliged,” the mother replied, “but I don’t know as I care to do
visitin’ down there.”
The conversation soon subsided, husband and wife dropping into revery
from which they dropped into slumber. In one way or other, however, the
subject came up again. Said Mrs. Hayn one day, just as her husband was
leaving the dinner-table for the field in which he was cutting and stacking
corn,—
“I do believe Phil’s best coat is finer stuff than anything Mr. Tramlay
wore when they were up here. I don’t believe what he wore Sundays could
hold a candle to Phil’s.”
“Like enough,” said the farmer; “and yet the old man always looked
better dressed. I think his clothes made him look a little younger than Phil,
too.”
 “Now, husband, you know it isn’t fair to make fun of the dear boy’s
clothes in that way. You know well enough that the stuff for his coat was cut
from the same bolt of broadcloth as the minister’s best.”
“Yes,” drawled the farmer through half a dozen inflections, any one of
which would have driven frantic any woman but his own wife.
“It’s real mean in you to say ‘Yes’ in that way, Reuben!”
“ ‘Tisn’t the wearer that makes the man, old lady; it’s the tailor.”
“I’m sure Sarah Tweege cut an’ made Phil’s coat, an’ if there’s a better
sewin’-woman in this part of the county I’d like to know where you find
her.”
“Oh, Sarah Tweege can sew, Lou Ann,” the old man admitted.
“Goodness! I wish she’d made my new harness, instead of whatever fellow
did it. Mebbe, too, if she’d made the sacks for the last oats I bought I
wouldn’t have lost about half a bushel on the way home. Yesm’, Sarah
Tweege can sew a bedquilt up as square as an honest man’s conscience. But
sewin’ ain’t tailorin’.”
“Don’t she always make the minister’s clothes?” demanded Mrs. Hayn.
“I never thought of it before, but of course she does. I don’t believe
anybody else could do it in that way. Yet the minister ain’t got so bad a
figure, when you see him workin’ in his garden, in his shirt-sleeves.”
“It’s time for you to go back to the cornfield,” suggested Mrs. Hayn.
“Yes, I reckon ’tis,” said the farmer, caressing what might have been nap
had not his old hat been of felt. “ ‘Tain’t safe for an old farmer to be givin’
his time an’ thought to pomps an’ vanities,—like the minister’s broadcloth
coat.”
“Get out!” exclaimed Mrs. Hayn, with a threatening gesture. The old
man kissed her, laughed, and began to obey her command; but as, like
countrymen in general, he made his exit by the longest possible route,
wandering through the sitting-room, the hall, the dining-room, and the
kitchen, his wife had time to waylay him at the door-step and remark,—
“I was only goin’ to say that if Phil does make that trip to York I don’t
see that he’ll need to buy new clothes. He’s never wore that Sunday coat on
other days, except to two or three funerals an’ parties. I was goin’ it over
this very mornin’, an’ it’s about as good as new.”
 “I wonder how this family would ever have got along if I hadn’t got such
a caretakin’ wife?” said the old man. “It’s the best coat in the United States,
if you’ve been goin’ it over.”
Phil was already in the corn,—he had left the table some minutes before
his father,—and as the old man approached, Phil said,—
“Father, don’t you think that wind-break for the sheep needs patching
this fall?”
“It generally does, my son, before cold weather sets in.”
“I guess I’ll get at it, then, as soon as we get the corn stacked.”
“What’s the hurry? The middle of November is early enough for that.”
“Oh, when it’s done it’ll be off our minds.”
“See here, old boy,” said the father, dropping the old ship’s cutlass with
which he had begun to cut the corn-stalks, “you’re doin’ all your work a
month ahead this fall. What are you goin’ to do with all your time when
there’s no more work to be done?”
“I can’t say, I’m sure,” said Phil, piling an armful of stalks against a
stack with more than ordinary care.
“Can’t, eh? Then I’ll have to, I s’pose, seein’ I’m your father. I guess I’ll
have to send you down to New York for a month, to look aroun’ an’ see
somethin’ of the world.”
Phil turned so quickly that he ruined all his elaborate work of the
moment before, almost burying his father under the toppling stack.
“That went to the spot, didn’t it?” said the old man. “I mean the
proposition,—not the fodder,” he continued, as he extricated himself from
the mass of corn-stalks.
“It’s exactly what I’ve been wanting to do,” said Phil, “but——”
“But you didn’t like to say so, eh? Well, ’twasn’t necessary to mention it;
as I told you t’other day, I can see through the back of your head any time,
old boy.”
“ ‘Twouldn’t cost much money,” said Phil. “I could go down on Sol
Mantring’s sloop for nothing, some time when he’s short-handed.”
“Guess I can afford to pay my oldest son’s travellin’ expenses when I
send him out to see the world. You’ll go down to York by railroad, an’ in the
best car, too, if there’s any difference.”
 “I won’t have to buy clothes, anyhow,” said the younger man.
“Yes, you will,—lots of ’em. York ain’t Haynton, old boy; an’ as the
Yorkers don’t know enough to take their style from you, you’ll have to take
yours from them. I was there once, when I was ’long about your age: I
didn’t have to buy no more meetin’-clothes after that until I got married,—
nigh on to ten years.”
“If it’s as expensive as that, I’m not going,” said Phil, looking very
solemn and beginning to reconstruct the demolished stack.
“Yes, you are, sir. I’ll have you understand you’re not much over age yet,
an’ have got to mind your old father. Now let that corn alone. If it won’t
stay down, sit on it,—this way,—see.” And, suiting the action to the word,
the old man sprawled at ease on the fallen fodder, dragged his son down
after him, and said,—
“You shall have a hundred dollars to start with, and more afterward, if
you need it, as I know you will. The first thing to do when you get to the
city is to go to the best-looking clothing-store you can find, and buy a suit
such as you see well-dressed men wearing to business. Keep your eyes open
on men as sharply as if they were hosses and clothes were their only points,
and then see that you get as good clothes as any of them. It don’t matter so
much about the stuff; but have your clothes fit you, an’ cut like other
people’s.”
“I don’t want to put on city airs,” said Phil.
“That’s right,—that’s right; but city clothes and city airs aren’t any more
alike than country airs an’ good manners. You may be the smartest,
brightest young fellow that ever went to York,—as of course you are, bein’
my son,—but folks at York’ll never find it out if you don’t dress properly,—
that means, dress as they do. I’ll trade watches with you, to trade back after
the trip: mine is gold, you know. You’ll have to buy a decent chain,
though.”
“I won’t take your watch, father. I can’t; that’s all about it.”
“Nonsense! of course you can, if you try. It isn’t good manners to wear
silver watches in the city.”
“But your watch——” Phil could get no further; for his father’s gold
watch was venerated by the family as if it were a Mayflower chair or the
musket of a soldier of the Revolution. Once while old farmer Hayn was
young Captain Hayn, of the whaling-ship Lou Ann, he saved the crew of a
sinking British bark. Unlike modern ship-captains (who do not own their
vessels), he went in the boat with the rescuing-party instead of merely
sending it out, and he suffered so much through exposure, strain, and the
fear of the death which seemed impending that he abandoned the sea as
soon thereafter as possible. Nevertheless he thought only of the work before
him, until he had rescued the imperilled crew and stowed them safely in his
own ship. The circumstances of the rescue were so unusual that they formed
the subject of long columns in foreign newspapers; and in a few months
Captain Hayn received through the State Department at Washington a gold
watch, with sundry complimentary papers from the British Admiralty. The
young seaman never talked of either; his neighbors first learned of the
presentation by conning their favorite weekly newspapers; nevertheless the
papers were framed and hung in the young captain’s bedchamber, and,
however carelessly he dressed afterward, nobody ever saw him when he
had not the watch in his pocket.
“Father,” said Phil, after some moments spent in silence and facial
contortion, “I can’t take your watch, even for a little while. You’ve always
worn it: it’s your—the family’s—patent of nobility.”
“Well,” said the old farmer, after contemplating the toes of his boots a
few seconds, “I don’t mind ownin’ up to my oldest son that I look at the old
watch in about the same light; but a patent of nobility is a disgrace to a
family if the owner’s heir isn’t fit to inherit it. See? Guess you’d better
make up your mind to break yourself into your comin’ responsibilities, by
carryin’ that watch in New York. Wonder what time ’tis?”
The question was a good pretext on which to take the “patent of
nobility” from his fob-pocket and look at it. He did it in a way which
caused Phil quickly to avert his face and devote himself with great industry
to stacking corn. Half a minute later the old man, cutlass in hand, was
cutting corn as if his life depended upon it.
 CHAPTER III.

“DOWN TO YORK.”

Despite his father’s expressed desire, Phil went to New York on Sol
Mantring’s sloop. The difference in time promised to be a day or two days,
but the difference in cash outlay was more than five dollars,—a sum which
no one in the vicinity of Hayn Farm had ever been known to spend
needlessly without coming to grief. Between cash in hand and its nominal
equivalent in time, Phil, like most other prudent young countrymen, had
learned to distinguish with alacrity and positiveness: besides, he knew how
small was the amount of ready money that his father, in spite of care and
skill at his business, was able to show for more than a quarter of a century
of hard work.
The young man’s departure was the occasion for quite a demonstration
by the neighbors. Other young men of the vicinage had been to New York,
but generally they were those whom their neighbors did not hope to see
again; Phil, on the contrary, was a general favorite. His family intended that
no one should know of the journey until Phil was fairly off, for they knew
by experience, in which sometimes they had been the offenders, how
insatiable is rural curiosity about any doings out of the ordinary. But when
Sol Mantring told his wife that Phil was to go down with him as a “hand,”
Mrs. Mantring straight-way put on her best things and went out to tell all
her neighbors that Phil Hayn was going down to York, and, being a woman
who never did anything by halves, she afterward plodded the dusty road
that led to the little village at the railway-station, where she consumed
several hours in doing petty shopping at the several stores, varying this
recreation by industrious gossip with every acquaintance who dropped in.
As each person who heard the news wondered what Phil was going for, and
as Mrs. Mantring was sure she didn’t know any better than dead-and-gone
Adam, there was developed a wealth of surmise and theory that should have
forever dispelled the general impression that Americans are not an
imaginative people.
 For the remainder of Phil’s time at home the family and its eldest son
had scarcely enough time to themselves to attend to their daily devotions.
People came to borrow something, to bring news, to ask advice,—anything
that would be an excuse to see what might be going on and to learn why
Phil was going to the city. Phil’s parents had prepared what they supposed
would be sufficient explanation: the farm and the house needed some things
that could better be selected from large stocks and variety than bought
nearer home. But they had underrated the persistency of local curiosity:
numberless pointed questions were asked, and if in the course of a week
there had been any visitor who did not ask, in one way or other, whether
Phil would go to see the Tramlays, the family did not know who it had
been; they were sure they would have gratefully noted such a considerate
person at the time, and remembered him—or her—forever after.
There were scores, too, who wanted Phil to do them small services in the
city. Farmer Blewitt had heard that the car-companies often sold for almost
nothing the horses that broke down at their hard work and needed only
plenty of rest and pasturage to make them as good as new: wouldn’t Phil
look about and see if he couldn’t get him a bargain?—and bring it back oil
the sloop, if he wouldn’t mind feeding and watering it on the home trip! Old
Mrs. Wholley had been finding her spectacles so young that she didn’t
know but she needed stronger glasses, or maybe a Bible with larger print: if
Phil would price both and write her, she would try to make up her mind
what she ought to do. Samantha Roobles had been telling her husband
James for the last five years that their best-room carpet was too shabby for
people who might have a funeral in the family at any time, James’s
stepmother being very old and sickly, but James wouldn’t do anything but
put off, and as for her, she wasn’t going to be cheated out of her eye-teeth at
the stores at the dépôt, when year before last she saw in a York newspaper,
that the wind blew out of the hand of somebody leaning out of a train
window, that good ingrains were selling in New York at thirty-five cents a
yard: she wished Phil would pick her out one.
Besides many requests like these, Phil had to make promises to dozens
of young men and women whose wants were smaller, but none the easier to
attend to: so the prospective traveller and his parents had the pains of
parting alleviated by the thought that not until Phil departed would any of
them have peace. The day of sailing brought a great throng of visitors,—so
many that the minister, who was of the number, extemporized a
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