Nanomaterials

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.

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. 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 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.

Types of nanomaterials
This classification is based on the number of dimensions of a material, which are outside the
nanoscale (<100 nm) range.

Accordingly, in zero-dimensional (0D) nanomaterials all the dimensions are measured within the
nanoscale (no dimensions are larger than 100 nm). Most commonly, 0D nanomaterials are
quantum dots and nanoparticles.

In one-dimensional nanomaterials (1D), one dimension is outside the nanoscale. This class
includes nanotubes, nanorods, and nanowires.

In two-dimensional nanomaterials (2D), two dimensions are outside the nanoscale. This class
exhibits plate-like shapes and includes graphene, nanofilms, nanolayers, and nanocoatings.

Three-dimensional nanomaterials (3D) are materials that are not confined to the nanoscale in any
dimension. This class can contain bulk powders, dispersions of nanoparticles, bundles of
nanowires, and nanotubes as well as multi-nanolayers.
Synthesis of nanomaterials
Bottom-up and top-down methods of synthesis
 There are two approaches to the synthesis of nanomaterials: bottom-up and topdown.
In the bottom-up approach, molecular components arrange themselves into more complex
assemblies atom-by-atom, molecule-by-molecule, cluster-by cluster from the bottom (e.g.,
growth of a crystal).
 In the top-down approach, nanoscale devices are created by using larger, externally
controlled devices to direct their assembly. The top-down approach often uses the traditional
workshop or microfabrication methods in which externally-controlled tools are used to cut, mill
and shape materials into the desired shape and order. Attrition and milling for making
nanoparticles are typical top-down processes.
 Bottom-up approaches, in contrast, arrange molecular components themselves into some
useful conformation using the concept of molecular self-assembly. Synthesis of nanoparticles by
colloid dispersions is an example of the bottom-up approach. The bottom-up approach has been
well-known to the chemists for a long time. This approach plays a very important role in
preparing nanomaterials having very small size where the top-down process cannot deal with the
very tiny objects
 The bottom-up approach generally produces nanostructures with fewer defects as
compared to the nanostructures produced by the top-down approach.
 Continuous production of nanomaterials in bulk is already established up to tonnage
quantities. Among the methods used to produce them are physical and chemical vapour
deposition.
 In physical vapour deposition (PVD), the material is vaporised by heat in a furnace or by
pulsed lasers. The vapour is then condensed on a cool surface. For example, single-wall carbon
nanotubes can be prepared by vaporising a carbon target like graphite in a furnace at about 1500
K using a laser and allowing the vapour to condense on a cool surface. An inert gas is bled into
the reactor during the process to prevent oxidation of the carbon vapour.
 In chemical vapour deposition (CVD), a reaction occurs in the vapour phase between two
or more materials and/or the vapour reacts with the target material.
 This bulk production technology has been used to manufacture a wide range of materials
in 20-100 nm particle size ranges (nanopowders). For example, compounds used in the
electronics industry, such as silicon dioxide (from silicon hydride and oxygen) and silicon nitride
(from silicon hydride and ammonia), are made in this way. Some metals (for example, nickel and
tungsten) of nano size are also prepared by CVD, by reducing their chlorides with hydrogen at
high temperature.CVD is thought to show the most promise for the production of carbon
nanotubes (Figure). To initiate the growth of nanotubes, two gases are bled into the reactor: a
process gas (such as ammonia, nitrogen or hydrogen) and a carbon-containing gas (such
as acetylene, ethylene, ethanol or methane). Nanotubes grow at the sites of the metal catalyst; the
carbon-containing gas is broken apart at the surface of the catalyst particle, and the carbon is
transported to the edges of the particle, where it forms the nanotubes.

Applications of nanomaterials

(i) Catalysis
(a) Heterogeneous catalysis takes place when reactions occur on the surface of a solid
catalyst. One catalytic application already developed is the use of cerium(IV) oxide
nanoparticles which are added to diesel and bio-diesel fuels in very small amounts (5-10
ppm). When diesel fuel is combusted in an engine, it is not completely oxidized and fine
particles of carbon, carbon monoxide as well as unreacted fuel are emitted. The additive,
cerium(IV) oxide acts as a heterogeneous catalyst and ensures that the fuel is combusted
completely to carbon dioxide and water, thus leading to an improvement in fuel
efficiency by as much as 4-11% and much less pollution (about 18% less particulate
matter is emitted). Because of their size, the cerium(IV) oxide nanoparticles forms a
homogeneous solution in the fuel and are thus easily premixed with the fuel, which then
requires no special delivery equipment and does not require any modification to the
vehicle engine.
(b) Glass used as a building material is coated with a transparent film of titanium dioxide
nanoparticles. They catalyse the photodegradation of dirt by UV sunlight. The smaller
degradation products are readily washed off by rain, thus making the windows self-
cleaning and so enhancing their ability to produce a reflection.
(ii) Materials for reinforcement

The role of the reinforcement in a composite material is fundamentally one of increasing the
mechanical properties of the system. Carbon nanotubes are not only very strong but are also
flexible. They can be twisted and bent without breaking. Thus they are used in polymers and
composites to strengthen a structure, to increase the electrical conductivity of the material
and to increase heat transfer.

On the other hand, composites containing silica nanoparticles withstand the heat of a car
engine and are therefore used as engine parts. Nanocomposite materials made out of clay-
reinforced, originated by Toyota, are now being used to make panels for cars, which are as
much as 30% lighter than existing structures, and are twice as resistant to denting and
scratching as conventional polymers. This gives rise to lighter, therefore more fuel-efficient,
cars, with corresponding environmental benefits.

(iii) Textiles and fabrics

A 'fleece' fabric has been produced that contains nanoparticles of carbon, derived from
bamboo, infused into a range of fibres (rayon, polyesters and polyamides). Through the
highly absorbent, high surface areas and surface modifications of the nanoparticles, they can
be used in such products to provide properties, including anti-bacterial, anti-fungal,
deodorizing, thermal-regulating and static-free, yet soft and comfortable to wear. The
nanoparticles are embedded in the fibres rather than present as a coating, and are not
removed from the fabric when washed.

(iv) Health and personal care

Imaging probes and implant coatings can be inserted into the human body with particle sizes
from 2-10 nm. The enhanced magnetic properties of iron(III) oxide nanoparticles make them
suitable for use as contrast agents in magnetic resonance imaging (MRI). In the study and
medical treatment of cancers, nanocarriers can be used for delivering imaging agents to
cancer cells thus making it easier to locate the cancer cells precisely and making treatment
much more effective. One technique being tried is to inject the patient with certain
nanoparticles, often gold because of its resistance to corrosion. The gold nanoparticles that
are located at a site of cancer cells can be irradiated with infrared to heat them up and destroy
the nearby cancer cells.

Cosmetics are already available that contain nanoparticles, again exploiting properties arising
from their incredibly high surface areas. These include sun lotions and anti-aging creams.