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Nano Particles

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Nano Particles

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Introduction

Nanoscale materials are defined as a set of substances where at least one dimension is
less than approximately 100 nanometers. A nanometer is defined as one millionth of a
millimeter -approximately 100,000 times smaller than the diameter of a human hair.
Based on physical and chemical characteristics, some of the well-known classes of
nanoparticles are given as (1) Carbon-based nanoparticles (Fullerenes and carbon nanotubes
- CNTs), (2) Metal-based nanoparticles, (3) Ceramic, (4) Semiconductor, (5) Polymeric, and (6)
Lipid-based NPs.
Sources, Properties and Application of fullerene
Introduction and Sources of Fullerene
A fullerene is an allotrope of carbon in the form of a hollow sphere, ellipsoid, tube, and many other
shapes. Fullerenes were discovered experimentally for the first time in September 1985. The
Buckminster fullerene, named after the American architect Buckminster Fuller or buckyballs,
as its structure resembles the geodesic dome made by him. Other fullerenes were discovered
shortly afterwards with more and fewer carbon atoms; they ranged from 18 atoms to up to
hundreds of atoms. Among them, the Buckyball containing 60 carbon atoms is the most popular.
Buckminster fullerene is resembling the balls used in football. Cylindrical fullerenes are also
called carbon nanotubes (buckytubes). Fullerenes are similar in structure to graphite, which is
composed of stacked graphene sheets of linked hexagonal rings.

Structure of Fullerene
Properties of Fullerene
Oxidation of the molecule has also been observed; nevertheless, oxidation is irreversible.
Fullerenes are extremely strong molecules, able to resist great pressures—they will bounce
back to their original shape after being subject to over 3,000 atmospheric pressure. Theoretical
calculations suggest that a single C60 molecule has an effective bulk modulus of 668 GPa
when compressed to 75% its size. This property makes fullerenes become harder than steel
and diamond, whose bulk moduli are 160 GPa and 442 Gpa, respectively. An interesting
experiment shows that Fullerenes can withstand collisions of up to 15,000 mph against
stainless steel, merely bouncing back and keeping their shapes. This experiment resembles the
high stability of the molecule. Delocalized pi electrons in Fullerenes are known to provide
exceptionally large nonlinear optical responses. Fullerenes have shown particular promises in
optical limiting and intensity-dependent refractive index.

Applications of Fullerene
Due to its versile properties, it is used in various applications.
1. It has properties of high electron affinity and superior ability, so, it is used in solar cells.
2. It is used in Hydrogen gas storage
3. Fullerene is utilized to provide hardness and strength properties to metal and alloys without
seriously compromising their ambient temperature ductility.
4. With low cost, fullerene is used to convert synthetic diamond.
5. Due to its excellent optical characteristics, it is used in preparation various scientific tools such
as atomic force, scanning electron and scanning tunnelling microscope and magnetic resonance
imaging (MRI).
6. It is used in medical devices for drug delivery vehicle and also, tissue engineering and tumour
cure.
7. It is also used in preparation of electronic parts, such as biosensors, semiconductors chips,
memory card, phtonica, optoelectronics, etc.
8. Inorganic based fullerenes are used for coating to reduce friction and improve wear resistance
in various mechanical parts such as ball bearing, chain, gear, pump, screw, artificial joints, etc.
9. It is used in water purification filter, fuel cell, photovoltaic cells.
Sources, Properties and Application of Fullerol

Introduction and Sources


Compared with the pristine form, functionalized fullerenes have more potential applications due
to their enhanced water solubility. To increasing its usability, several polar groups such as
hydroxyl, carboxylic acid or amino groups are attached into fullerene. One of hydroxyl
derivative of fullerene is known as fullerol having molecular formula of C60(OH)n.

Structure of Fullerol

Properties of Fullerol
As electron donating hydroxyl group is introduced into fullerene, it reduced the electronegativity
of fullerenes and hence, reduces its toxicity to the organism and improves biocompatibility. It has
good oxidation resistance. Fullerols have high adhesion to metal, alloys, and semiconductors
surfaces. It has extreme chemical and thermal stability. The refraction index of fullerol is low. It
has also luminescence properties i.e. their transparency in visible and infrared spectrum regions is
high; light-absorption in near-by ultraviolet spectral region is strong; in the far light-spectrum
region such films are opaque.
Applications of Fullerol
1. Fullerol is used for the scavenger of water-soluble free radicals and antioxidant in biological
system.
2. Fullerol has several biomedical actions such as, bone destruction treatment via osteogenesis
enhancing, osteoclastic suppression and inflammation inhibition, vertebral bone marrow lesion
treatment, radiculopathy treatment via suppressing the inflammatory responses of DRG and
neuronal apoptosis.
3. It is also used as phase-transfer agent, anti-bacterial agent, anti-cancer agent, preventing and
treating agent for inflammatory bowel disease, in cosmetics, drug delivery, orthopaedic
research and gene probe.
4. Gd-C82(OH)n (Gadolinium- containing fullerol) is used in medical field, as fluorescent
coordination compounds of metal ions, physiological reagent,
5. Due to its luminescence properties, fullerols is used for the optical applications.

Carbon nanotubes (CNT):


Introduction
CNTs are the members of the fullerene family, which was discovered by Kroto et al. in 1985.
CNTs, also called buckytubes, are cylindrical carbon molecules with unique properties that make
them potentially useful in a wide variety of applications. These include applications in nano-
electronics, optics, and materials applications.
Structure of CNT:
CNTs, also known as tubular fullerenes, are cylindrical grapheme sheets of sp2-bonded carbon
atoms. In CNTs the grapheme sheet is rolled upon itself to form different allotropes of carbon,
including graphite, fullerenes and CNTs. CNTs can be divided into three categories on the basis
of the number of tubes present in the CNTs. These are described below.
(a) (b) (c)
Types of CNT
(a) Single-walled CNTs: Single-walled CNTs (SWCNTs) are made of a single grapheme sheet
rolled upon itself with a diameter of 1–2 nm (Figure 3.3 (a)). The length can vary depending on
the preparation methods.
(b) Double-walled CNTs: These nanotubes are made of two concentric carbon nanotubes in which
the outer tube enclose the inner tube, as shown in Figure 3.3 (b).
(c) Multi-walled CNTs (MWNT): MWNTs consist of multiple layers of graphene rolled upon
itself with diameters ranging from 2 to 50 nm depending on the number of graphene tubes. These
tubes have an approximate inter-layer distance of 0.34 nm.
Properties
CNTs exhibit extraordinary strength as well as unique electrical, mechanical and thermal
properties due to strength of Sp2 carbon-carbon bonds. CNTs reportedly have extremely high
surface areas, large aspect ratios, and remarkably high mechanical strength. The tensile strength
of CNTs is 100 times greater than that of steel, and the electrical and thermal conductivities
approach those of metals. Their densities can be as low as 1.3 g/cm3 (one-sixth of that of stainless
steel). CNTs Young’s moduli (measure of material stiffness) are superior to all carbon fibres with
values greater than 1TPa which is approximately 5x higher than steel. Carbon nanotubes are the
strongest materials ever discovered by mankind. The highest measured tensile strength or breaking
strain for a carbon nanotube was up to 63 GPa which is around 50 times higher than steel. Besides
that, CNTs have good chemical and environmental stability and high thermal conductivity
(~3000 W/m/K, comparable to diamond). These properties, coupled with the lightness of carbon
nanotubes, give them great potential in applications such as aerospace. CNTs are highly flexible
can be bent considerably without damage. CNTs have a low thermal expansion coefficient and
good electron field emitters. CNTs have excellent potential as they are the stiffest and toughest
structure.
Applications of CNTs
1. CNTs can be used in sensors, micron-scale on-chip triodes at a high frequency (>200 MHz),
vacuum microelectronics, and for X-ray generation.
2. Due to its conductivity and a high absorption capacity, it is used in fuel cells, energy
conversion, hydrogen storage and semiconductor devices.
3. It is also used as adsorbent in waste water treatment plant as it has high surface area and
porosity.
4. It is also used in batteries, transistors, membranes, catalysis, super-capacitors, etc.
5. It is utilized in electronic devices as field-emission sources.
6. Due to their large surface area as well as their high electrical conductivity, CNTs are excellent
materials for use in electrochemical devices.
7. It is also used in scanning probe tips.
8. CNTs serve as ideal non-toxic vehicles, which in some cases; increase the solubility of the
drug also, resulting in greater efficiency and safety. Therefore, it has proven their potential to
serve as safer and effective alternatives to previous drug delivery methods.
Synthesis of Nanoparticle
Various methods can be employed for the synthesis of NPs, but these methods are broadly divided
into two main classes i.e. (1) Bottom-up approach and (2) Top-down approach. These further
divide into various subclasses based on the operation, reaction condition and adopted protocols as
shown in below chart.
Synthesis of Nanoparticle

Top down Method Bottom up Method


1. Mechanical milling 1. Sol gel technique
2. Nanolithography 2. Spinning
3. Laser ablation 3. Chemical vapour decomposition (CVD)
4. Sputtering 4. Pyrolysis
5. Physical Vapor Deposition (PVD) 5. Bio-synthesis
6. Decomposition Technique
Top down Method
In this method, destructive approach is employed. Starting from larger molecule, which
decomposed into smaller units and then these units are converted into suitable Nanoparticles. The
bulk materials are converted into powder form and thereafter, changed into NPs. Examples of this
method are mechanical grinding/milling, Nanolithography, Laser ablation, Sputtering, Physical
Vapor Deposition (PVD) and other decomposition techniques.
(a) Mechanical milling: Among the various top-down methods, mechanical milling is the most
extensively used to produce various nanoparticles. The mechanical milling is used for milling and
post annealing of nanoparticles during synthesis where different elements are milled in an inert
atmosphere. High energy mills include: attrition ball mill, planetary ball mill, vibrating ball mill,
low energy tumbling mill, high energy ball mill, etc. Common drawbacks include low surface,
highly poly disperse size distribution, and partially amorphous state of the powder. These powders
are highly reactive with oxygen, hydrogen and nitrogen.
(b) Nanolithography:
Nanolithography is the study of fabricating nanometric scale structures with a minimum of one
dimension in the size range of 1 to 100 nm. There are various nanolithographic processes for
instance optical, electron-beam, multi-photon, nano-imprint and scanning probe lithography, in
which separate instruments are required. The main advantage of nanolithography is to produce
from a single nanoparticle to a cluster with desired shape and size. The disadvantages are the
requirement of complex equipment and higher cost. Gold and silver nanoparticles are examples of
nanolithography.
(c) Laser ablation: Laser Ablation Synthesis in Solution (LASiS) is a common method for
nanoparticle production from various solvents. The irradiation of a metal submerged in a liquid
solution by a laser beam condenses a plasma plume that produces nanoparticles. It is a reliable top-
down method that provides an alternative solution to conventional chemical reduction of
metals to synthesis metal based nanoparicles. Examples of laser ablation are silicon, gold,
titanium oxide, iron oxide.
(d) Sputtering: Sputtering is the deposition of nanoparticles on a surface by ejecting particles
from it by colliding with ions. Sputtering is usually a deposition of thin layer of nanoparticles
followed by annealing. The thickness of the layer, temperature and duration of annealing, substrate
type, etc. determines the shape and size of the nanoparticles. Gold, brass, copper and alunium
nanoparticles are prepared using this technique.
(e) Physical Vapor Deposition (PVD):
By using this deposition technique, thin films of different metals are deposited on different
surfaces. This technique involves condensation from the vapor phase. There are three main steps
involved in this process: 1) the sublimation of evaporating of a material corresponding vapor
phase, 2) transportation of the material to the substrate from source, and 3) formation of the thin
film and particle by nucleation and growth. Graphite and copper NPs are prepared using PVD
method.
(f) Decomposition Technique: Various decompositions such as thermal, irradiation,
photochemical methods are available for preparation of nanoparticles, in which thermal
decomposition technique is more preferable. The specific temperature at which an element
chemically decomposes is the decomposition temperature. The nanoparticles are produced by
decomposing the metal at specific temperatures undergoing a chemical reaction producing
secondary products. Example is production of lithium nanoparticles by decomposing lithium
azide (LiN3).

Bottom up Method
This approach is employed in reverse as NPs are formed from relatively simpler substances,
therefore this approach is also called building up approach. Examples of this case
are sedimentation and reduction techniques. It includes sol gel, CVD, spinning, pyrolysis and
biochemical synthesis.
(a) Sol gel technique: The sol – a colloidal solution of solids suspended in a liquid phase. The gel
– solid macromolecule submerged in a solvent. Sol-gel is the most preferred bottom-up method
due to its simplicity and as most of the nanoparticles can be synthesised from this method.
Examples are metal alkoxides and metal chloride nanoparticles.
(b) Spinning: The synthesis of nanoparticles by spinning is carried out by a spinning disc reactor
(SDR). It contains a rotating disc inside a chamber/reactor where the physical parameters such as
temperature, pressure, etc. can be controlled. The spinning causes the atoms or molecules to
fuse together and is precipitated, collected and dried. Polymers are converted to their
nanoparticles using this technique.
(c) Chemical vapour decomposition (CVD): Chemical vapour deposition is the deposition of a
thin film of gaseous reactants onto a substrate. The deposition is carried out in a reaction chamber
at ambient temperature by combining gas molecules. A chemical reaction occurs when a heated
substrate comes in contact with the combined gas. This reaction produces a thin film of product
on the substrate surface that is recovered and used. Substrate temperature is the influencing
factor in CVD. The advantages of CVD are highly pure, uniform, hard and strong
nanoparticles. The disadvantages of CVD are the requirement of special equipment and the
gaseous by-products are highly toxic. Examples of CVD are iron nanoparticles, nickel foam, and
gallium vapour.
(d) Pyrolysis: Pyrolysis is the most commonly used process in industries for large scale production
of nanoparticle. It involves burning a precursor with flame. The precursor is either liquid or vapor
that is fed into the furnace at high pressure through a small hole where it burns. The combustion
or by-product gases are then air classified to recover the nanoparticles. The advantages of
pyrolysis are simple, efficient, cost effective and continuous process with high yield. Titanium
oxide nanoparticles are prepared using this method.
(e) Bio-synthesis: Biosynthesis is a green and environmental friendly approach for the synthesis
of nanoparticles that are nontoxic and biodegradable. Biosynthesis uses bacteria, plant extracts,
fungi, etc. along with the precursors to produce nanoparticle instead of convention chemicals for
bioreduction and capping purposes. The bio-synthesized nanoparticles have unique and enhanced
properties that find its way in biomedical applications. Some examples of nanoparticle production
include using bacteria for gold, silver, cadmium, zinc, magnetite, and iron NPs.

Applications of nanomaterial
Nanomaterials have created a high interest in recent years by virtue of their unusual mechanical,
electrical, optical and magnetic properties. Some examples are given below:
Nanoparticles as potent antimicrobial agent: All metal oxides are being currently used in mostly
biomedical application, including antibacterial, antivirus and antifungal activities, due to their
excellent properties such as: large surface‐ area‐ to‐ volume ratio as compared to the bulk
equivalents
Nanoparticles in electrochemical sensors and biosensors: Nanoparticles such as oxide, metal and
semiconductor nanoparticles have been utilized for constructing electrochemical sensors and
biosensors, and these nanoparticles play diverse roles in different sensing systems
Nanoparticles in medicine and healthcare: Nanoparticles have been utilised newly to develop
the present imaging techniques for in vivo diagnosis of biomedical disorders. Metal oxides are
being used for diagnosis therapy, and increasing immunoassay system for antibodies treatment.
Nanoparticles, as drug delivery systems, are capable to uplift the several crucial properties of free
drugs, such as solubility, in vivo stability, pharmacokinetics, biodistribution and enhancing their
efficiency
Nanoparticles in agriculture: Nanoparticles are used into agriculture industries for delivery
systems for pests, nutrients and plant hormones and nano-sensors. These products are utilized in
proficient use of agricultural natural assets like water, nutrients and chemicals during precision
farming.
Nanoparticles as catalysis: Nanostructured metal clusters and colloids of mono- or plurimetallic
composition have a special impact in catalytic applications. They may serve as precursors for new
type of heterogeneous catalysts (Cortex-catalysts) and have been shown to offer substantial
advantages concerning activity, selectivity and lifetime in chemical transformations and
electrocatalysis (fuel cells).
Nanoparticles in textile: It is also used in textiles. Silver nanoparticles in fabric are used to
kill bacteria, making clothing odor- resistant. CNTs can produce waterproof and tear-resistant
fabrics. Nano-polymer is also used in plastics, paint and coatings in textile industries.
Biodegradable Polymer
Biodegradable polymers are a specific type of polymer that breaks down after its intended
purpose to result in natural byproducts such as gases (CO2, N2), water, biomass, and inorganic
salts. These polymers are found both naturally and synthetically made, and largely consist of
ester, amide, and ether functional groups. Examples are Polylactide acid (PLA), Polyglycolic
acid (PGA), copolymer of poly lactide acid and Polyglycolic acid, Nylon – 2, Nylon – 6,
Dextran, etc.

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