INTRODUCTION TO NANOMATERIALS

1. Introduction

Nanomaterials are cornerstones of nanoscience and nanotechnology. Nanostructure

science and technology is a broad and interdisciplinary area of research and development activity
that has been growing explosively worldwide in the past few years. It has the potential for
revolutionizing the ways in which materials and products are created and the range and nature
of functionalities that can be accessed. It is already having a significant commercial impact, which
will assuredly increase in the future.

Figure 1. Evolution of science and technology and the future

1.1. What are nanomaterials?

Nanoscale materials are defined as a set of substances where at least one dimension is
less than approximately 100 nanometers. A nanometer is one millionth of a millimeter -
approximately 100,000 times smaller than the diameter of a human hair. Nanomaterials are of
interest because at this scale unique optical, magnetic, electrical, and other properties emerge.
These emergent properties have the potential for great impacts in electronics, medicine, and
other fields.

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 Figure 2. Nanomaterial (For example: Carbon Nanotube)

1.2. Where are nanomaterials found?

Some nanomaterials occur naturally, but of particular interest are engineered

nanomaterials (EN), which are designed for, and already being used in many commercial products
and processes. They can be found in such things as sunscreens, cosmetics, sporting goods, stain-
resistant clothing, tires, electronics, as well as many other everyday items, and are used in
medicine for purposes of diagnosis, imaging and drug delivery.

Engineered nanomaterials are resources designed at the molecular (nanometre) level to

take advantage of their small size and novel properties which are generally not seen in their
conventional, bulk counterparts. The two main reasons why materials at the nano scale can have
different properties are increased relative surface area and new quantum effects. Nanomaterials
have a much greater surface area to volume ratio than their conventional forms, which can lead
to greater chemical reactivity and affect their strength. Also at the nano scale, quantum effects
can become much more important in determining the materials properties and characteristics,
leading to novel optical, electrical and magnetic behaviours.

Nanomaterials are already in commercial use, with some having been available for several
years or decades. The range of commercial products available today is very broad, including stain-
resistant and wrinkle-free textiles, cosmetics, sunscreens, electronics, paints and varnishes.
Nanocoatings and nanocomposites are finding uses in diverse consumer products, such as
windows, sports equipment, bicycles and automobiles. There are novel UV-blocking coatings on
glass bottles which protect beverages from damage by sunlight, and longer-lasting tennis balls
using butylrubber/nano-clay composites. Nanoscale titanium dioxide, for instance, is finding

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applications in cosmetics, sun-block creams and self-cleaning windows, and nanoscale silica is
being used as filler in a range of products, including cosmetics and dental fillings.

2. Advances in Nanomaterials

The history of nanomaterials began immediately after the big bang when Nanostructures
were formed in the early meteorites. Nature later evolved many other Nanostructures like
seashells, skeletons etc. Nanoscaled smoke particles were formed during the use of fire by early
humans. The scientific story of nanomaterials however began much later. One of the first
scientific report is the colloidal gold particles synthesised by Michael Faraday as early as 1857.
Nanostructured catalysts have also been investigated for over 70 years. By the early 1940’s,
precipitated and fumed silica nanoparticles were being manufactured and sold in USA and
Germany as substitutes for ultrafine carbon black for rubber reinforcements.

Nanosized amorphous silica particles have found large-scale applications in many every-
day consumer products, ranging from non-diary coffee creamer to automobile tires, optical fibers
and catalyst supports. In the 1960s and 1970’s metallic nanopowders for magnetic recording
tapes were developed. In 1976, for the first time, nanocrystals produced by the now popular
inert- gas evaporation technique was published by Granqvist and Buhrman. Recently it has been
found that the Maya blue paint is a nanostructured hybrid material. The origin of its color and its
resistance to acids and biocorrosion are still not understood but studies of authentic samples
from Jaina Island show that the material is made of needle-shaped palygorskite (clay) crystals
that form a superlattice with a period of 1.4 nm, with intercalates of amorphous silicate substrate
containing inclusions of metal (Mg) nanoparticles. The beautiful tone of the blue color is obtained
only when both these nanoparticles and the superlattice are present, as has been shown by the
fabrication of synthetic samples.

Today nanophase engineering expands in a rapidly growing number of structural and

functional materials, both inorganic and organic, allowing to manipulate mechanical, catalytic,
electric, magnetic, optical and electronic functions. The production of nanophase or cluster-
assembled materials is usually based upon the creation of separated small clusters which then
are fused into a bulk-like material or on their embedding into compact liquid or solid matrix
materials. e.g. nanophase silicon, which differs from normal silicon in physical and electronic

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properties, could be applied to macroscopic semiconductor processes to create new devices. For
instance, when ordinary glass is doped with quantized semiconductor ''colloids,'' it becomes a
high performance optical medium with potential applications in optical computing.

3. Classification of Nanomaterials

Nanomaterials have extremely small size which having at least one dimension 100 nm or
less. Nanomaterials can be nanoscale in one dimension (eg. surface films), two dimensions (eg.
strands or fibres), or three dimensions (eg. particles). They can exist in single, fused, aggregated
or agglomerated forms with spherical, tubular, and irregular shapes. Common types of
nanomaterials include nanotubes, dendrimers, quantum dots and fullerenes. Nanomaterials
have applications in the field of nano technology, and displays different physical chemical
characteristics from normal chemicals (i.e., silver nano, carbon nanotube, fullerene,
photocatalyst, carbon nano, silica).

According to Siegel, Nanostructured materials are classified as Zero dimensional, one

dimensional, two dimensional, three dimensional nanostructures.

Figure 3. Classification of Nanomaterials (a) 0D spheres and clusters, (b) 1D nanofibers, wires,
and rods, (c) 2D films, plates, and networks, (d) 3D nanomaterials.

Nanomaterials are materials which are characterized by an ultra fine grain size (< 50 nm)
or by a dimensionality limited to 50 nm. Nanomaterials can be created with various modulation
dimensionalities as defined by Richard W. Siegel: zero (atomic clusters, filaments and cluster
assemblies), one (multilayers), two (ultrafine-grained overlayers or buried layers), and three
(nanophase materials consisting of equiaxed nanometer sized grains) as shown in the above
figure 3.

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4. Why are nanomaterials important?

These materials have created a high interest in recent years by virtue of their unusual
mechanical, electrical, optical and magnetic properties. Some examples are given below:

(i) Nanophase ceramics are of particular interest because they are more ductile at elevated
temperatures as compared to the coarse-grained ceramics.

(ii) Nanostructured semiconductors are known to show various non-linear optical properties.
Semiconductor Q-particles also show quantum confinement effects which may lead to special
properties, like the luminescence in silicon powders and silicon germanium quantum dots as
infrared optoelectronic devices. Nanostructured semiconductors are used as window layers in
solar cells.

(iii) Nanosized metallic powders have been used for the production of gas tight materials, dense
parts and porous coatings. Cold welding properties combined with the ductility make them
suitable for metal-metal bonding especially in the electronic industry.

(iv) Single nanosized magnetic particles are mono-domains and one expects that also in magnetic
nanophase materials the grains correspond with domains, while boundaries on the contrary to
disordered walls. Very small particles have special atomic structures with discrete electronic
states, which give rise to special properties in addition to the super paramagnetism behaviour.
Magnetic nanocomposites have been used for mechanical force transfer (ferrofluids), for high
density information storage and magnetic refrigeration.

(v) 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). Enantioselective catalysis was also achieved using chiral modifiers on the surface of
nanoscale metal particles.

(vi) Nanostructured metal-oxide thin films are receiving a growing attention for the realization of
gas sensors (NOx, CO, CO2, CH4 and aromatic hydrocarbons) with enhanced sensitivity and
selectivity. Nanostructured metal-oxide (MnO2) finds application for rechargeable batteries for

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cars or consumer goods. Nanocrystalline silicon films for highly transparent contacts in thin film
solar cell and nano-structured titanium oxide porous films for its high transmission and significant
surface area enhancement leading to strong absorption in dye sensitized solar cells.

(vii) Polymer based composites with a high content of inorganic particles leading to a high
dielectric constant are interesting materials for photonic band gap structure.

5. Examples of Nanomaterials

Nanomaterials (gold, carbon, metals, meta oxides and alloys) with variety of
morphologies (shapes) are depicted in Fig. 4.

Au Nanoparticle Buckminsterfullerene FePt nanosphere

Titanium nanoflower Silver nanocubes SnO2 nanoflower

Figure 4. Nanomaterials with a variety of morphologies

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6. Nanomaterial - synthesis and processing

Nanomaterials deal with very fine structures: a nanometer is a billionth of a meter. This
indeed allows us to think in both the ‘bottom up’ or the ‘top down’ approaches (Fig. 5) to
synthesize nanomaterials, i.e. either to assemble atoms together or to dis-assemble (break, or
dissociate) bulk solids into finer pieces until they are constituted of only a few atoms. This domain
is a pure example of interdisciplinary work encompassing physics, chemistry, and engineering
upto medicine.

Figure 5. Schematic illustration of the preparative methods of nanomaterials.

7. Properties of Nanomaterials

Nanomaterials have the structural features in between of those of atoms and the bulk
materials. While most microstructured materials have similar properties to the corresponding
bulk materials, the properties of materials with nanometer dimensions are significantly different
from those of atoms and bulks materials. This is mainly due to the nanometer size of the materials
which render them: (i) large fraction of surface atoms; (ii) high surface energy; (iii) spatial
confinement; (iv) reduced imperfections, which do not exist in the corresponding bulk materials.

Due to their small dimensions, nanomaterials have extremely large surface area to
volume ratio, which makes a large to be the surface or interfacial atoms, resulting in more
“surface” dependent material properties. Especially when the sizes of nanomaterials are
comparable to length, the entire material will be affected by the surface properties of
nanomaterials. This in turn may enhance or modify the properties of the bulk materials. For
example, metallic nanoparticles can be used as very active catalysts. Chemical sensors from

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nanoparticles and nanowires enhanced the sensitivity and sensor selectivity. The nanometer
feature sizes of nanomaterials also have spatial confinement effect on the materials, which bring
the quantum effects.

The energy band structure and charge carrier density in the materials can be modified
quite differently from their bulk and in turn will modify the electronic and optical properties of
the materials. For example, lasers and light emitting diodes (LED) from both of the quantum dots
and quantum wires are very promising in the future optoelections. High density information
storage using quantum dot devices is also a fast developing area. Reduced imperfections are also
an important factor in determination of the properties of the nanomaterials. Nanosturctures and
Nanomaterials favors of a selfpurification process in that the impurities and intrinsic material
defects will move to near the surface upon thermal annealing. This increased materials perfection
affects the properties of nanomaterials. For example, the chemical stability for certain
nanomaterials may be enhanced, the mechanical properties of nanomaterials will be better than
the bulk materials. The superior mechanical properties of carbon nanotubes are well known. Due
to their nanometer size, nanomaterials are already known to have many novel properties. Many
novel applications of the nanomaterials rose from these novel properties have also been
proposed.

7.1. Optical properties

One of the most fascinating and useful aspects of nanomaterials is their optical
properties. Applications based on optical properties of nanomaterials include optical detector,
laser, sensor, imaging, phosphor, display, solar cell, photocatalysis, photoelectrochemistry and
biomedicine.

The optical properties of nanomaterials depend on parameters such as feature size,

shape, surface characteristics, and other variables including doping and interaction with the
surrounding environment or other nanostructures. Likewise, shape can have dramatic influence
on optical properties of metal nanostructures. Fig. () exemplifies the difference in the optical
properties of metal and semiconductor nanoparticles. With the CdSe semiconductor
nanoparticles, a simple change in size alters the optical properties of the nanoparticles. When
metal nanoparticles are enlarged, their optical properties change only slightly as observed for the

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different samples of gold nanospheres in fig. (). However, when an anisotropy is added to the
nanoparticle, such as growth of nanorods, the optical properties of the nanoparticles change
dramatically.

Figure 7. Fluorescence emission of (CdSe) ZnS quantum dots of various sizes and absorption
spectra of various sizes and shapes of gold nanoparticles.

7.2. Electrical properties

Electrical Properties of Nanoparticles discuss about fundamentals of electrical

conductivity in nanotubes and nanorods, carbon nanotubes, photoconductivity of nanorods,
electrical conductivity of nanocomposites. One interesting method which can be used to
demonstrate the steps in conductance is the mechanical thinning of a nanowire and
measurement of the electrical current at a constant applied voltage. The important point here is
that, with decreasing diameter of the wire, the number of electron wave modes contributing to
the electrical conductivity is becoming increasingly smaller by well-defined quantized steps.

In electrically conducting carbon nanotubes, only one electron wave mode is observed
which transport the electrical current. As the lengths and orientations of the carbon nanotubes
are different, they touch the surface of the mercury at different times, which provides two sets
of information: (i) the influence of carbon nanotube length on the resistance; and (ii) the
resistances of the different nanotubes. As the nanotubes have different lengths, then with
increasing protrusion of the fiber bundle an increasing number of carbon nanotubes will touch
the surface of the mercury droplet and contribute to the electrical current transport.

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7.3. Mechanical properties

“Mechanical Properties of Nanoparticles” deals with bulk metallic and ceramic materials,
influence of porosity, influence of grain size, superplasticity, filled polymer composites, particle-
filled polymers, polymer-based nanocomposites filled with platelets, carbon nanotube-based
composites. The discussion of mechanical properties of nanomaterials is, in to some extent, only
of quite basic interest, the reason being that it is problematic to produce macroscopic bodies
with a high density and a grain size in the range of less than 100 nm. However, two materials,
neither of which is produced by pressing and sintering, have attracted much greater interest as
they will undoubtedly achieve industrial importance.

These materials are polymers which contain nanoparticles or nanotubes to improve their
mechanical behaviors, and severely plastic-deformed metals, which exhibit astonishing
properties. However, because of their larger grain size, the latter are generally not accepted as
nanomaterials. Experimental studies on the mechanical properties of bulk nanomaterials are
generally impaired by major experimental problems in producing specimens with exactly defined
grain sizes and porosities. Therefore, model calculations and molecular dynamic studies are of
major importance for an understanding of the mechanical properties of these materials.

Filling polymers with nanoparticles or nanorods and nanotubes, respectively, leads to

significant improvements in their mechanical properties. Such improvements depend heavily on
the type of the filler and the way in which the filling is conducted. The latter point is of special
importance, as any specific advantages of a nanoparticulate filler may be lost if the filler forms
aggregates, thereby mimicking the large particles. Particulate filled polymer-based
nanocomposites exhibit a broad range of failure strengths and strains. This depends on the shape
of the filler, particles or platelets, and on the degree of agglomeration. In this class of material,
polymers filled with silicate platelets exhibit the best mechanical properties and are of the
greatest economic relevance. The larger the particles of the filler or agglomerates, the poorer are
the properties obtained. Although, potentially, the best composites are those filled with
nanofibers or nanotubes, experience teaches that sometimes such composites have the least
ductility. On the other hand, by using carbon nanotubes it is possible to produce composite fibers
with extremely high strength and strain at rupture. Among the most exciting nanocomposites are

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the polymerceramic nanocomposites, where the ceramic phase is platelet-shaped. This type of
composite is preferred in nature, and is found in the structure of bones, where it consists of
crystallized mineral platelets of a few nanometers thickness that are bound together with
collagen as the matrix. Composites consisting of a polymer matrix and defoliated phyllosilicates
exhibit excellent mechanical and thermal properties.

7.4. Magnetic properties

Bulk gold and Pt are non-magnetic, but at the nano size they are magnetic. Surface atoms
are not only different to bulk atoms, but they can also be modified by interaction with other
chemical species, that is, by capping the nanoparticles. This phenomenon opens the possibility
to modify the physical properties of the nanoparticles by capping them with appropriate
molecules. Actually, it should be possible that non-ferromagnetic bulk materials exhibit
ferromagnetic-like behavior when prepared in nano range. One can obtain magnetic
nanoparticles of Pd, Pt and the surprising case of Au (that is diamagnetic in bulk) from non-
magnetic bulk materials. In the case of Pt and Pd, the ferromagnetism arises from the structural
changes associated with size effects.

However, gold nanoparticles become ferromagnetic when they are capped with
appropriate molecules: the charge localized at the particle surface gives rise to ferromagnetic-
like behavior.

Surface and the core of Au nanoparticles with 2 nm in diameter show ferromagnetic and
paramagnetic character, respectively. The large spin-orbit coupling of these noble metals can
yield to a large anisotropy and therefore exhibit high ordering temperatures. More surprisingly,
permanent magnetism was observed up to room temperature for thiol-capped Au nanoparticles.
For nanoparticles with sizes below 2 nm the localized carriers are in the 5d band. Bulk Au has an
extremely low density of states and becomes diamagnetic, as is also the case for bare Au
nanoparticles. This observation suggested that modification of the d band structure by chemical
bonding can induce ferromagnetic like character in metallic clusters.

8. Selected Application of nanomaterials

Nanomaterials having wide range of applications in the field of electronics, fuel cells,
batteries, agriculture, food industry, and medicines, etc... It is evident that nanomaterials split
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their conventional counterparts because of their superior chemical, physical, and mechanical
properties and of their exceptional formability.

8.1. Fuel cells

A fuel cell is an electrochemical energy conversion device that converts the chemical energy from
fuel (on the anode side) and oxidant (on the cathode side) directly into electricity. The heart of
fuel cell is the electrodes. The performance of a fuel cell electrode can be optimized in two ways;
by improving the physical structure and by using more active electro catalyst. A good structure
of electrode must provide ample surface area, provide maximum contact of catalyst, reactant gas
and electrolyte, facilitate gas transport and provide good electronic conductance. In this fashion
the structure should be able to minimize losses.

8.2. Catalysis

Higher surface area available with the nanomaterial counterparts, nano-catalysts tend to
have exceptional surface activity. For example, reaction rate at nano-aluminum can go so high,
that it is utilized as a solid-fuel in rocket propulsion, whereas the bulk aluminum is widely used
in utensils. Nano-aluminum becomes highly reactive and supplies the required thrust to send off
pay loads in space. Similarly, catalysts assisting or retarding the reaction rates are dependent on
the surface activity, and can very well be utilized in manipulating the rate-controlling step.

8.3. Phosphors for High-Definition TV

The resolution of a television, or a monitor, depends greatly on the size of the pixel. These
pixels are essentially made of materials called "phosphors," which glow when struck by a stream
of electrons inside the cathode ray tube (CRT). The resolution improves with a reduction in the
size of the pixel, or the phosphors. Nanocrystalline zinc selenide, zinc sulfide, cadmium sulfide,
and lead telluride synthesized by the sol-gel techniques are candidates for improving the
resolution of monitors. The use of nanophosphors is envisioned to reduce the cost of these
displays so as to render highdefinition televisions (HDTVs) and personal computers affordable to
be purchase.

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8.4. Next-Generation Computer Chips

The microelectronics industry has been emphasizing miniaturization, whereby the

circuits, such as transistors, resistors, and capacitors, are reduced in size. By achieving a
significant reduction in their size, the microprocessors, which contain these components, can run
much faster, thereby enabling computations at far greater speeds. However, there are several
technological impediments to these advancements, including lack of the ultrafine precursors to
manufacture these components; poor dissipation of tremendous amount of heat generated by
these microprocessors due to faster speeds; short mean time to failures (poor reliability), etc.
Nanomaterials help the industry break these barriers down by providing the manufacturers with
nanocrystalline starting materials, ultra-high purity materials, materials with better thermal
conductivity, and longer-lasting, durable interconnections (connections between various
components in the microprocessors).

8.5. Elimination of Pollutants

Nanomaterials possess extremely large grain boundaries relative to their grain size.
Hence, they are very active in terms of their chemical, physical, and mechanical properties. Due
to their enhanced chemical activity, nanomaterials can be used as catalysts to react with such
noxious and toxic gases as carbon monoxide and nitrogen oxide in automobile catalytic
converters and power generation equipment to prevent environmental pollution arising from
burning gasoline and coal.

8.6. Sun-screen lotion

Prolonged UV exposure causes skin-burns and cancer. Sun-screen lotions containing

nano-TiO2 provide enhanced sun protection factor (SPF) while eliminating stickiness. The added
advantage of nano skin blocks (ZnO and TiO2) arises as they protect the skin by sitting onto it
rather than penetrating into the skin. Thus they block UV radiation effectively for prolonged
duration. Additionally, they are transparent, thus retain natural skin color while working better
than conventional skin-lotions.

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8.7. Sensors

Sensors rely on the highly active surface to initiate a response with minute change in the
concentration of the species to be detected. Engineered monolayers (few Angstroms thick) on
the sensor surface are exposed to the environment and the peculiar functionality (such as change
in potential as the CO/anthrax level is detected) is utilized in sensing.

9. Disadvantages of Nanomaterials

(i) Instability of the particles - Retaining the active metal nanoparticles is highly challenging, as
the kinetics associated with nanomaterials is rapid. In order to retain nanosize of particles, they
are encapsulated in some other matrix. Nanomaterials are thermodynamically metastable and
lie in the region of high-energy local-minima. Hence they are prone to attack and undergo
transformation. These include poor corrosion resistance, high solubility, and phase change of
nanomaterials. This leads to deterioration in properties and retaining the structure becomes
challenging.

(ii) Fine metal particles act as strong explosives owing to their high surface area coming in direct
contact with oxygen. Their exothermic combustion can easily cause explosion.

(iii) Impurity - Because nanoparticles are highly reactive, they inherently interact with impurities
as well. In addition, encapsulation of nanoparticles becomes necessary when they are
synthesized in a solution (chemical route). The stabilization of nanoparticles occurs because of a
non-reactive species engulfing the reactive nano-entities. Thereby, these secondary impurities
become a part of the synthesized nanoparticles, and synthesis of pure nanoparticles becomes
highly difficult. Formation of oxides, nitrides, etc can also get aggravated from the impure
environment/ surrounding while synthesizing nanoparticles. Hence retaining high purity in
nanoparticles can become a challenge hard to overcome.

(iv) Biologically harmful - Nanomaterials are usually considered harmful as they become
transparent to the cell-dermis. Toxicity of nanomaterials also appears predominant owing to
their high surface area and enhanced surface activity. Nanomaterials have shown to cause
irritation, and have indicated to be carcinogenic. If inhaled, their low mass entraps them inside
lungs, and in no way they can be expelled out of body. Their interaction with liver/blood could
also prove to be harmful (though this aspect is still being debated on).
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(v) Difficulty in synthesis, isolation and application - It is extremely hard to retain the size of
nanoparticles once they are synthesized in a solution. Hence, the nanomaterials have to be
encapsulated in a bigger and stable molecule/material. Hence free nanoparticles are hard to be
utilized in isolation, and they have to be interacted for intended use via secondary means of
exposure. Grain growth is inherently present in nanomateirals during their processing. The finer
grains tend to merge and become bigger and stable grains at high temperatures and times of
processing.

(vi) Recycling and disposal - There are no hard-and-fast safe disposal policies evolved for
nanomaterials. Issues of their toxicity are still under question, and results of exposure
experiments are not available. Hence the uncertainty associated with affects of nanomaterials is
yet to be assessed in order to develop their disposal policies.

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