Nano Technology

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UNIT– I:

INTRODUCTION: History and Scope, Classification of Nano structured Materials,


Fascinating Nanostructures, and applications of nano-materials, challenges and future
prospects.
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History of nanotechnology
A noscience and nanotechnology are the study and application of extremely small
things and can be used across all the other science fields, such as chemistry, biology,
physics, materials science, and engineering.
How It Started
The ideas and concepts behind nanoscience and nanotechnology started with a talk
entitled “There’s Plenty of Room at the Bottom” by physicist Richard Feynman at an American
Physical Society meeting at the California Institute of Technology (CalTech) on December 29,
1959, long before the term nanotechnology was used. In his talk, Feynman described a
process in which scientists would be able to manipulate and control individual atoms and
molecules. Over a decade later, in his explorations of ultraprecision machining, Professor
Norio Taniguchi coined the term nanotechnology. It wasn't until 1981, with the development
of the scanning tunneling microscope that could "see" individual atoms, that modern
nanotechnology began.
Feynman’s 1959 talk is often cited as a source of inspiration for Nanoscience, but it
was virtually unknown outside of his small audience at the time and only published as a
scientific paper in 1992.1 Nanoscience really sprang into the public consciousness sometime
after the invention of the scanning tunnelling microscope (STM) in 1981.2 Here was an
amazing tool that could image and manipulate atoms. Atomic scale imaging had been
possible in the past with multimillion-dollar transmission electron microscopes, but the STM
was a benchtop tool that a graduate student could assemble for a few hundred dollars.
The First International Conference on Scanning Tunneling Microscopy was held in
Santiago De Compostela, Spain, July 14–18, 1986 (becoming a yearly fixture thereafter with
an exponential growth in the number of papers presented). The impact of the STM on surface
science was already so great at this time that the 1986 Nobel Prize in physics was awarded
to Gerd Binning and Heinrich Rohrer for their invention of the STM. (It was shared with Ernst
Ruska, one of the inventors of the electron microscope.) Fueled by the low cost and ease of
building atomic resolution microscopes, interest in Nanoscience spread like wildfire
Scanning Tunneling Microscopy, papers were presented that reported images of
biological molecules. The invention of the atomic force microscope (AFM) in 19865 greatly
extended the reach of these tools. Now insulating materials could be imaged with atomic
resolution and new types of direct measurement and manipulation on the atomic scale were
made possible. The chemists could image directly some of the fantastic structures they had
only dreamed of making, and a bright young biochemist in NewYork, Ned Seeman, was able
to realize his dream6 of building nanoscale machines with self-assembly of DNAmolecules.
Thus was born the field of DNA nanotechnology. Major government
funding of Nanoscience as a separate discipline began in the 1990s, with considerable
subsequent impact on inventions in the development of technology.8 Those of us who were
swept up in this field found biologists, engineers, chemists, and materials scientists (and
even geologists) knocking on the doors of our physics labs. The days of research within the
narrow confines of one traditional discipline were over.
Nanoparticles and structures have been used by humans in fourth century AD, by
the Roman, which demonstrated one of the most interesting examples of nanotechnology in
the ancient world. The Lycurgus cup, from the British Museum collection, represents one of
the most outstanding achievements in ancient glass industry. It is the oldest famous example
of dichroic glass. Dichroic glass describes two different types of glass, which change color in
certain lighting conditions. This means that the Cup have two different colors: the glass
appears green in direct light, and red-purple when light shines through the glass
In 1990, the scientists analyzed the cup using a transmission electron microscopy
(TEM) to explain the phenomenon of dichroism. The observed dichroism (two colors) is due
to the presence of nanoparticles with 50–100 nm in diameter. X-ray analysis showed that
these nanoparticles are silver-gold (Ag-Au) alloy, with a ratio of Ag:Au of about 7:3, containing
in addition about 10% copper (Cu) dispersed in a glass matrix. The Au nanoparticles produce
a red color as result of light absorption (~520 nm). The red-purple color is due to the
absorption by the bigger particles while the green color is attributed to the light scattering
by colloidal dispersions of Ag nanoparticles with a size > 40 nm. The Lycurgus cup is
recognized as one of the oldest synthetic nanomaterials. A similar effect is seen in late
medieval church windows, shining a luminous red and yellow colors due to the fusion of Au
and Ag nanoparticles into the glass. shows an example of the effect of these nanoparticles
with different sizes to the stained glass windows.
Scope of nanotechnology
It has a huge scope in the upcoming generations. It is the third highest booming field
when compared with IT and Internet. In India, Bangalore and Chennai are the manufacturing
hub for IT and Medicine. The Indian government has already started Nanoscience and
Nanotechnology initiatives and various funding agencies like the Department of Science and
Technology.
Nanotechnology opens up an almost unlimited field of research activity.
Especially in medicine, nanotechnology offers exciting opportunities. Novel diagnostic
procedures and therapies promise wide-ranging development potential. For example, novel
drugs can be developed. Supported by the progressive miniaturization in the electronics
industry, interdisciplinary research teams are researching so-called nanobots. Prototypes
already available today should continue to shrink below the size of blood cells and be able to
move in the human organism. These nanobots could then transport drugs and dose them
specifically to the disease centers.
The development of long fibrous devices that can be introduced into the human
organism would be the consequent continuation of minimally invasive surgery. Substances
could be more specifically administered and, for example, tissue samples.
Classic mechanical and plant engineering also wants to benefit from innovative
materials whose structures show improved properties during machining and in use. So today
the rotors of wind turbines are designed with a special coating, which has a positive effect
on efficiency.
The ever-focused area of power generation and storage is developing new systems to
quench the hunger for energy from previously unused sources. Novel concepts for energy
generation, for example from ambient temperature or air movement combined with the
optimized capacity of the storage media, promise a more efficient use of the energy available
in nature.
The food industry is researching foods that, for example, have a longer shelf life due
to the nanoparticles or, depending on their temperature and duration, have different flavors
in the domestic oven. But also in agriculture, nanotechnology is used for developments in
the field of biological crop protection.
According to the surveys conducted in Sweden and UK it came to know
nanotechnology has been emerged as a promising technology in the construction industry.
More importantly its influence is very much significant in concrete products. It was also
identified that construction industry is one of the important sectors which will be influenced
by nanotechnology. A lot of research and development initiations are being organized to bring
out many more innovations in nanotechnology relevant to construction industry. A lot of
investments were made by venture capitalist and industrial corporations to unleash the
potential in construction sector by the applications of nanotechnology. By identifying those
potential European commission in late 2002 allotted huge funds for initiating research by
name GMA1-2002-72160 “NANOCONEX”. Nanotechnology is identified as a vital application
to the advancement of Civil Engineering field. Its applications are very much significant in
the construction portfolio of Civil Engineering.
Nanotechnology in Concrete Compared to the other form of materials used in
construction concrete is one of the most common and predominantly used constructional
materials. Concrete is a heterogeneous, nano structured, multi phase, construction material
consist of various sizes of small crystals. It is widely used in almost all construction activities.
We can’t assume any construction without concrete. It occupies nearly 70% of the volume of
the structure. Cement is one of the vital components used in manufacturing of concrete, but
cement has some disadvantages. A lot of research has been carried out in order to reduce
the proportion of cement in the concrete. Nanotechnology has been emerged as a best tool to
address many problems associated with ingredients of concrete.
Nanotechnology is used to study many properties of concrete like heat of hydration,
alkali aggregate reaction particularly alkali silicate reaction. The presence of alkali and silica
in cement and aggregates causes ASR. If the amount of cement content is replaced by the
use of Pozzolona it reduces the occurring and severity of alkali silicate reaction. The
properties of concrete may be altered in so many ways, one of the best ways is the
incorporation of nano particles. Nano particles in terms of nano silica, nano clays, nano
titanium Oxide (TiO2), Nano Iron (Fe2 O3), Nano alumina (Al2 O3), Cuo, ZnO2 and ZrO2.
Nanomaterials in concrete will improve the pore structure of concrete, speed up the C-S-H
gel formation and improve the concrete mechanical and durability properties. More
particularly fly ash improves durability and strength of the concrete to the maximum extent
but due to the addition of fly ash the early strength of the concrete may be reduced. The
problem of low strength at early stage may be overcome by the incorporation of Nano-Silica
which improves the density and structure of the concrete.
The addition of Nano- Silica improves resistance to segregation and also auguments
the strength of hardened concrete and offers more repulsion towards water absorption and
prevents calcium leaching. Nano iron imparts the ability of self sensing and also improves
its compressive and Flexural strength. Nano titanium helps the concrete for self cleaning. It
is experimentally proved that how nanotechnology enhanced the life span of bridges. As per
the study conducted by National Institute of Standards and technology, US, in 2007,
Nanotechnology is found best suitable in making pavements. Pavements should be
very strong, durable, resistant to weathering, wearing and skid resistant. The pavements
with all these features were successfully possible with the applications of ZnO2 nano silica
particles. Water logging on roads causes weathering it can be avoided by means of proper
drainage and quick run-off. Hydrophobic roads, made of nano particles facilitate fast run-
off. Nanotechnology is also used for water purification. The quality and availability of water
can also be improved by nanotechnology. By using advanced methods and materials water
can be made fit for reuse.
The salinity of water can also be reduced. With the application of nanotechnology
carbon fibre reinforced plastics are also made. As they are very light in weight they don’t
exhibit good electric properties. Plastic solar cells are also made to produce solar energy
which is very cheaper than conventional silicon semi conductors. By using these cells energy
can be saved and they are also eco friendly since they reduce emission of carbon particles.
Almost all developed countries are trying to use LED lamps instead of conventional lamps.
Many more smart materials are produced with the application of nanotechnology. Smart
materials have the influence of external stimuli like temperature, moisture, electric and
magnetic fields etc.
CLASSIFICATION OF NANOMATERIALS
The classification of nanomaterials is based on the number of dimensions as shown in Fig.
1. According to Siegel, nanostructured materials are classified as:
Zero dimensional (0D),
One dimensional (1D),
Two dimensional (2D)
Three dimensional (3D)
(i) Zero-dimensional nanomaterials: Here, all dimensions (x, y, z) are at nanoscale, i.e., no
dimensions are greater than 100 nm. It includes nanospheres and nanoclusters.
(ii) One-dimensional nanomaterials: Here, two dimensions (x, y) are at nanoscale and the
other is outside the nanoscale. This leads to needle shaped nanomaterials. It includes
nanofibres, nanotubes, nanorods, and nanowires.
(iii) Two-dimensional nanomaterials: Here, one dimension (x) is at nanoscale and the other
two are outside the nanoscale. The 2D nanomaterials exhibit platelike shapes. It includes
nanofilms, nanolayers and nanocoatings with nanometre thickness.
(iv) Three-dimensional nanomaterials: These are the nanomaterials that are not confined to
the nanoscale in any dimension. These materials have three arbitrary dimensions above 100
nm. The bulk (3D) nanomaterials are composed of a multiple arrangement of nanosize
crystals in different orientations. It includes dispersions of nanoparticles, bundles of
nanowires and nanotubes as well as multinanolayers (polycrystals) in which the 0D, 1D and
2D structural elements are in close contact with each other and form interfaces.
Fascinating nanostructures
Nanoparticle research is a fascinating branch of science. The strongly size-related
properties of nanoparticles offer uncountable opportunities for surprising discoveries. The
often unexpected and unprecedented behavior of nanoparticles bears great potential for
innovative technological applications, but also poses great challenges to the scientists. They
have to develop highly controllable synthesis approaches, more sensitive characterization
tools and finally new models and theories to explain the experimental observations. In this
review, we discuss a personal selection of papers dedicated to nanoparticle research, which
we believe provide an illustrative overview of current research directions in this rapidly
developing field. We have structured the text in five sections: introduction, nanoparticle
synthesis, formation mechanisms, nanoparticle assembly, and applications. The chosen
examples within these sections are not directly related to each other, but reflect the
remarkable broadness of nanoparticle research covering historical aspects, basic and applied
science as well as commercial applications.
Applications of Nanomaterials
The efficient progress in nanotechnology has transformed many aspects of food
science and the food industry with enhanced investment and market share. Recent advances
in nanomaterials and nanodevices such as nanosensors, nano-emulsions, nanopesticides or
nanocapsules are intended to bring about innovative applications in the food industry. In
this review, the current applications of nanotechnology for packaging, processing, and the
enhancement of the nutritional value and shelf life of foods are targeted. In addition, the
functionality and applicability of food-related nanotechnologies are also highlighted and
critically discussed in order to provide an insight into the development and evaluation of the
safety of nanotechnology in the food industry

Nature the best of nanotechnologist


You wake up in the morning and put on your nature influenced clothes. You do not
have to worry that it is raining outside today because water and dirt just roll off like drops
on a lotus leaf. You do not have to worry that the electricity is out because your clothes can
create its own light through firefly-inspired bioluminescence which can also keep your smart
phone charged. No need for pockets. Anything you need to carry you can just stick to your
clothes with the same Van der Waals forces that a gecko uses. Do you think this is all a
dream? No, this is all possible and we have nanotechnology to thank along with some very
important chemistry.
Nanomaterials abound in the living systems of nature and nanoscientists are
examining the properties and potential uses of these natural nanostructures in an area of
research called biomimicry. What types of nanostructures are found in nature? They include
inorganic materials such as clays, carbonaceous soot (think carbon black), and natural
inorganic thin films to a variety of organic nanostructures such as proteins and chitin (insect
and crustacean shells) to organic structures such as wing ribs and epidermal projections.
These structures lead to a variety of behaviors in nature including the wettability of surfaces,
the iridescence of butterfly wings, and the adhesive properties of the gecko foot. Let’s examine
a few examples of these biomimetic structures.
Nanotechnology deals with the understanding and control of matter at dimensions
between approximately 1 and 100 nanometers, where unique phenomena enable novel
applications.
Challenges Future Prospects
Nanotechnology is an emerging and rapidly growing field whose dynamics and
prospects pose many great challenges not only to scientists and engineers but also to society
at large. This volume includes the state-of-the-art philosophical, ethical, and sociological
reflection on nanotechnology, written by leading scholars from the humanities and social
sciences in North America and Europe. It unravels the philosophical underpinnings of
nanotechnology, its metaphysical and epistemological foundations, and its conceptual
complexity. It explores the ethical issues of nanotechnology, its impact on human,
environmental, and social conditions, and the options for reasonable risk management. It
examines the public discourse on nanotechnology and its related visions and provides both
lessons from the past and outlooks for the future.
UNIT– II:
UNIQUE PROPERTIES OF NANO MATERIALS: Microstructure and Defects in Nano
crystalline Materials: Dislocations, Twins, stacking faults and voids, Grain Boundaries,
triple and declinations. Effect of Nano-dimensions on Materials Behavior: Elastic
properties, Melting Point, Diffusivity, Grain growth characteristics, enhanced solid
solubility. Magnetic Properties: Soft magnetic nanocrystalline alloy, Permanent magnetic
nanocrystalline materials, Giant Magnetic Resonance, Electrical Properties, Optical
Properties, Thermal Properties and Mechanical Properties.
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Microstructure and Defects in Nano crystalline Materials
If we have the ability to construct matter, atom by atom, we would be able to perform
wonders. For example, we know that both graphite and diamond are made of pure carbon.
Thus, in belief, if we are able to rearrange the atoms (carbon) in graphite at our discretion,
it would be possible to make diamond! Or, if we could rearrange the atoms (silicon and
oxygen) in sand (and add a few other trace elements), it should be possible to make a
computer chip.

Engineering at the nano-level can bring about large changes in the properties of the
products. Also, the high defect concentration in nanomaterials results in novel and unique
physical, chemical and mechanical properties of this class of materials.
MICROSTRUCTURE AND DEFECTS IN NANOCRYSTALLINE MATERIALS
In order to understand the novel properties of nanostructured materials, we need to
understand the structure and its inter-relationship with properties. The microstructural
features of importance in nanomaterials include:
Grain size, distribution and morphology
• The nature of grain boundaries and interphase interfaces
• Nature of intra-grain defects
• Composition profiles across grains and interfaces
• Residual impurities from processing
Crystal lattice imperfections, such as point, linear, planar and volume defects, lead to the
structure-sensitive properties of materials. The atomic structure of nanostructured
materials

Crystals are three-dimensional, periodic arrangements of atoms/molecules in space.


Any imperfection leading to disruption of periodicity is referred to as a ‘crystalline defect’.
These defects are usually classified based on their dimensionality, namely, point defects
(0D), line defects (1D), surface defects (2D) and volume defects (3D).
Vacancies, substitutional and interstitial solutes are the common point defects observed
in metals and alloys. In case of ionic solids, Schottky (anion–cation vacancy pairs) and
Frenkel (vacancy-interstitial pairs of the same ions) defects may also be observed.
Dislocations are the most observed line defects and refer to a missing plane of atoms.
Among the surface defects, grain boundaries, twins, stacking faults and free surfaces

Among the surface defects, grain boundaries, twins, stacking faults and free surfaces are
the most common. Inclusions, voids and micro cracks constitute the volume defects.
Missing rows of atoms in a crystal are regions of high energy and stress due to
disruption of the atomic bonds in the plane. This provides a heavy force for dislocations
to be done at surfaces or grain boundaries to minimize the strain energy of the crystal.
In effect, this may be treated as equivalent to an attractive force applied by the surface on
dislocations in the crystal. This force is inversely proportional to the distance of separation
and hence becomes negligible for dislocations farther than a critical distance. However,
for dislocations close to the surface or grain boundary, the attractive force can be large
enough to result in applying the dislocations. Hence, for a small distance from the surface
and grain boundaries, one would not expect to find any dislocations.
Dislocations
Dislocations are, in general, stable in conventional microcrystalline materials,
though not thermodynamically stable defects. However, when the magnitude of the critical
distance becomes comparable with that of the grain size, as in nanomaterials, the stability
of dislocations is changed significantly. Hence, with decreasing grain size of nanograined
materials, dislocation stability is reduced, due to the large grain boundary area.
It is well known that dislocation mobility and interactions play a large role in
determining the deformation and plastic flow behaviour of conventional crystalline
materials. Hence, it is expected that the deformation behaviour of nanocrystalline
materials is significantly different from that of conventional microcrystalline materials.
The typical dislocation density in annealed (hardened) crystalline materials is about
10¹º/cm. As the grain size is reduced to about 10 nm, the dislocation density can reduce
by 2–3 orders or more and finally, below a critical grain size, dislocations are no longer
stable, i.e., there will be no dislocations in the nanocrystalline materials below the critical
grain size.
In contrast to whiskers (single crystals without dislocations), nanomaterials have a
large number of grain boundaries as defects. Hence, the plastic deformation behaviour of
the material cannot be governed by dislocation mechanisms. This can result in
significantly different mechanical properties in nanomaterials below the critical sizes. The
effect of decreasing dislocation density on the deformation mechanism is an area of
significant scientific curiosity.
Twins, stacking faults and voids
planar defects are often observed, even after annealing, in many faceted nanomaterials,
including nano rods and nanowires. These planar defects include twins and stacking
faults (intrinsic or extrinsic), and are usually neglected by most analytical models.
For example, many bulk metals have the face-centred cubic structure, but
nanocrystals and nanorods of the same material often exhibit various structural
modifications such as single or multiple symmetric twinning, as well as five-fold cyclic
twinning, resulting in decahedral and truncated decahedral nanostructures below critical
sides.

Twins are generally observed in crystals subjected to deformation under high strain
rate or at low temperatures. During crystallization of liquid metal, it is expected that
volume misfit strains can be easily accommodated in the liquid phase, and hence one does
not expect the formation of twins in the nucleating crystals.

Voids in nanocrystallites may be located at either


Triple junctions
Large porosities
Due to insufficient compaction and sintering of nanocrystallites synthesized from
the powder method. Although both types of voids influence the behaviour of the
nanocrystallites, the first is structurally more important. It is suggested that triple
junction voids arise as a result of relaxation of nanocrystalline grain boundaries.

Grain boundaries, triple junctions and disclinations


A schematic representation of a hard-sphere mode of an equiaxed nanocrystalline metal
as shown in Figure.
Two types of atoms can be distinguished:
Crystal atoms with nearest-neighbour configurations
corresponding to the lattice (black circles) .
Boundary atoms with a variety of interatomic spacings (white circles).
Nanocrystalline materials typically contain a high number of interfaces with random
orientation relationships, so, a substantial fraction of atoms lies in the interfaces.

Assuming that the grains have the shape of spheres or cubes, the volume fraction
of nanocrystalline materials associated with the boundaries (Vi) is estimated to be:

where δ is the average interface thickness and d is the average grain diameter. Thus,
the volume fraction of interfaces can be as much as 60% for 5 nm grains, 30% for 10 nm
grains, and about 3% for 100 nm grains, for a grain boundary thickness of 1 nm.
According to the phase mixture model, many properties of nanocrystalline materials
can be estimated by a simple rule of mixtures,

where subscripts cr and ῐc refer to the crystalline and intercrystallite components


of nanocrystalline materials, and X and V denote the property and volume fraction of the
respective components. Intercrystallite components include the grain boundaries, triple
lines and quadruple nodes. Taking a cubic unit cell or a regular polyhedron unit cell of
nanocrystalline materials, the volume fraction of each component can be expressed as
follows:

Where the subscribes cr, gb, tj and qn refer to crystallite, grain boundary, triple
lines and quadruple nodes, respectively; d and δ represent the grain size and grain
boundary thickness.
When the grain size is smaller than about 20 nm, the total volume of the
intercrystallite region (grain boundary and triple junctions) becomes significant. The
density of grain boundaries in nanocrystals is very large (~ 1019 cm–3) and there is wide
distribution of interatomic spacing at these grain boundaries.
It has been suggested that the triple junctions can be
described based on the disclination defect model.
Disclinations (as Figure) are line defects
characterised by a rotation vector ω in contrast to
the translational vector b for dislocations.
The triple junctions may be considered to form a network of disclinations.
Theoretical calculations have shown that triple junction energies are comparable to
dislocation energies, and that compensating disclinations play a significant role in the
properties of nanocrystalline metals with grain size less than about 10 nm. These triple
junctions are linear defects that play a significant role in the mechanical, thermodynamic
and kinetic properties of polycrystals. This role may be particularly important in
nanocrystalline materials, where the grain boundaries are short and contain a small
number of structural units.
Effect of Nano-dimensions on Materials Behavior
As with decrease in size the surface area increases ,so nanostructure have more
surface area for reaction . Hence reactivity increases with decrease in particle size.
Effect of Nano-dimensions on Elastic properties:
Size effects decisively influence the properties of materials at small length scales. In
the context of mechanical properties, the trend of ‘smaller is stronger’ has been well
established. This statement refers to an almost universal trend of increased strength with
decreasing size. A strong influence of size on the elastic properties has also been widely
reported, albeit without a clear trend. However, the influence of nanostructure shape on
the mechanical properties has been critically neglected.
Here, profound influence of shape and size on the elastic properties of materials on
the example of gold nanowires. The elastic properties are determined using in-situ
mechanical testing in scanning and transmission electron microscopy by means of
resonance excitation and uniaxial tension. The combination of bending and tensile load
types allows for an independent and correlative calculation of the Young's modulus. We
find both cases of softening as well as stiffening, depending critically on the interplay
between size and shape of the wires.
Effect of Nano-dimensions on Melting Point:
By considering the surface effects, the melting temperature of nanosolids
(nanoparticles, nanowires and nanofilms) has been predicted based on size-dependent
cohesive energy. It is shown that the melting temperature of free standing nanosolids
decreases with decrease in the solid size, and the melting temperature variation for
spherical nanoparticle, nanowire and nanofilm of a material in the same size is 3:2:1.
A model for size- and shape-dependent specific heat was introduced. The specific
heat of nanosolids was found to increase with decrease of the particle size for spherical,
nanowire and nanofilm shapes. Moreover, the model was applied to determine the shape
and size dependence of the melting entropy and enthalpy of nanosolids. The prediction of
the present model for specific heat, melting entropy and enthalpy was found to be in good
agreement with the molecular dynamics results and the available experimental data,
indicating that our present model at nanoscale can be applied for a wide range of surface-
related phenomena. The present model has the potential to be applied for calculation of
the thermodynamical properties of nanomaterials.
Effect of Nano-dimensions on Diffusivity
Diffusion in nanostructures has many challenging features even if the role of
structural defects (dislocations, phase- or grain-boundaries) can be neglected. This can be
the case for diffusion in amorphous materials, in epitaxial, highly ideal thin films or
multilayers, in dissolution of thin films or in kinetics of surface segregation, where
diffusion along short circuits can be ignored and ìonlyî fundamental difficulties, related to
nanoscale effects, raise. Different examples for diffusion in such materials will be given
with special emphasis on the validity limit of the continuum approach especially if the
diffusion coefficient depends strongly on composition (non-linearity).
It was shown recently by us that even for ideal systems (like Cu/Ni) this non-
linearity leads to linear shift of an originally sharp interface (instead of the parabolic
behaviour) and to sharpening of an initially diffuse interface. The sharpening takes place,
even if the effects of stresses(built in mismatch, thermal and diffusional stresses) are taken
into account. Furthermore, deviations from the parabolic law are present in phase
separating systems as well, but here the interplay of the strong composition dependence
and the phase separation tendency results in a more complex behaviour. These deviations
are typical nano effects i.e. they diminish with time; in the examples investigated here
after dissolution of several hundred atomic planes the parabolic law already fulfils.
Effect of Nano-dimensions on Grain growth characteristics
The hardness measured by the nanosize indenter under atomic indentation is
examined for the cases of nanocrystalline nickel by means of molecular dynamics (MD)
simulations. The grain size effect observed is different from the one by uniform
deformation or deep indentation. The results show that hardness can only show inverse
Hall–Petch (H-P) effect, no H-P effect is observed with the grain size up to 40 nm. Grain
boundary (GB) absorption of the localized strain is the main deformation mechanism when
the indenter size and the depth both come to nano size. The area of plastic zone generated
beneath the tip is strongly dependent on the GB density, sample with small grain size
results in larger plastic area, which leads to the softer response of hardness.
In atomic depth indentation on nanocrystalline nickel with grain size from 5
nm to 40 nm using indenters with various sizes have revealed that only inverse H-P effect
appears. Following can be concluded.
1.The inverse H-P effect could be explained by the strain contributions from GBs
and grain interior. The larger grain size results in large portion of strain in grain interior,
producing higher hardness under ultra shallow indentation. The H-P relation does not
hold even the crystal size is above the conventional transition size. Our observation
indicates the GB absorption and GB sliding comes to play an important role in the ultra
shallow contact, few generated dislocations can be easily absorbed by GBs.
2.The area of plastic zone generated beneath the tip is size dependent; larger GB
density induces larger plastic area from GB mediation, and thus causes softer response.
Effect of Nano-dimensions on enhanced solid solubility
The effects of particle size on their solubility, dissolution, and oral bioavailability
were investigated. Solubility and dissolution testing were performed in three types of
dissolution medium, and the studies demonstrated that the equilibrium solubilities of
coenzyme Q10 nanocrystals and bulk drugs were not affected by the dissolution media
but the kinetic solubilities were. Kinetic solubility curves and changes in particle size
distribution were determined and well explained by the proposed solubilization model for
the nanocrystals and bulk drugs.
The particle size effect on dissolution was clearly influenced by the diffusion
coefficients of the various dissolution media, and the dissolution velocity of coenzyme Q10
increased as particle size decreased. The bioavailability of coenzyme Q10 after oral
administration in beagle dogs was improved by reducing the particle size. For 700 nm
nanocrystals, the AUC0–48 was 4.4-fold greater than that for the coarse suspensions, but
a further decrease in particle size from 700 nm to 120 nm did not contribute to
improvement in bioavailability until the particle size was reduced to 80 nm, when
bioavailability was increased by 7.3-fold.
Magnetic properties of nanoparticles
Magnetic properties of nanoparticles are used for drug delivery, therapeutic
treatment, contrast agents for MRI imaging, bio separation, and in-vitro
diagnostics. These nano meter-sized particles are superparamagnetic, a property
resulting from their tiny size—only a few nanometers—a fraction of the width of a human
hair (nanoparticles are approximately 1/1,000 thinner than human hair).
Superparamagnetic nanoparticles are not magnetic when located in a zero magnetic field,
but they quickly become magnetized when an external magnetic field is applied. When
returned to a zero magnetic field they quickly revert to a non-magnetized state. Super para
magnetism is one of the most important properties of nanoparticles used for bio magnetic
separation.
Soft magnetic nanocrystalline alloy

Magnetic materials permeate numerous daily activities in our lives.1 They are
essential components of a diversity of products including hard drives that reliably store
information on our computers, decorative magnets that keep the shopping list attached to
the refrigerator door, electric bicycles that speed our commute to work, as well as wind
turbines for conversion of wind energy to electrical power. While permanent magnets
require materials that maintain their magnetization even under the influence of external
stimuli, soft magnetic materials can easily change their magnetization when external
conditions require it.
Permanent magnets require the magnetization vs. field hysteresis loop, M(H), to be
broad, with a large coercive field in order to allow energy to be stored in the material. In
contrast, soft magnetic materials require a narrow hysteresis loop, which implies the use
of small amounts of energy to magnetize the material. As the area of the loop is related to
energy losses during the cyclic magnetization of the material, a low coercive field implies
better energy efficiency of the final application in which the soft magnetic material is used.
As indicated in the previous section, obtaining materials in which the exchange
correlation length is much larger than the structural correlation length will lead to effective
magnetic anisotropies that are negligible when compared to the magneto crystalline
anisotropy of the bulk material. In practice, this can be achieved by controlled
crystallization of a precursor amorphous alloy.
Soft magnetic nanocrystalline alloys have been used to study the super para
magnetism of nanocrystals embedded in the matrix in order to develop models of the
dipolar interactions between superparamagnetic nanoparticle or to propose procedures
for the determination of critical exponents of multiphase magnetic systems.
Nanocrystalline alloys are among the softest magnetic materials known to science,
and different alloy families have been optimized for unique applications and operating
conditions. In addition to compositional effects that will affect intrinsic magnetic
properties, the use of different processing methods enables the optimization of extrinsic
properties such as coercivity.
The physical reason for the extremely low values of magnetic anisotropy and coercive
field can be explained using the random anisotropy model: the two characteristic length
scales of nanocrystalline alloys (grain size and magnetic correlation length) are very
different, and anisotropy cannot be detected macroscopically, even if each nanocrystal is
anisotropic.
Soft magnets are currently used in a variety of applications, ranging from energy
conversion to sensors. Remaining challenges in the development of soft magnetic
nanocrystalline alloys include the optimization of material properties for specific
applications and the enhancement of their usability by decreasing brittleness and
increasing thermal stability of the metastable phases. These goals can be achieved by a
combination of compositional changes and appropriate processing of the alloys.
Tuning the hysteresis loops by processing the materials under the simultaneous
influence of magnetic field, stress, and temperature is a promising route to broadening
the applications of nanocrystalline soft magnets. In addition, the design of exchange-
coupled hard-soft magnetic nanocomposites is an area of significant interest in which
ultrasoft nanocrystalline alloys may play a role. Moreover, the interest in soft
nanocrystalline alloys is not limited to technological applications as these materials are
also a good testing ground for developing fundamental models of multiphase magnetic
materials.
Permanent magnetic nanocrystalline materials
Recent developments in nanocrystalline rare earth–transition metal magnets are
reviewed and emphasis is placed on research work at IFW Dresden. Principal synthesis
methods include high energy ball milling, melt spinning and hydrogen assisted methods
such as reactive milling and hydrogenation-disproportionation-desorption-recombination.
These techniques are applied to NdFeB-, PrFeB- and SmCo-type systems with the aim to
produce high remanence magnets with high coercivity. Concepts of maximizing the energy
density in nanostructured magnets by either inducing a texture via anisotropic HDDR or
hot deformation or enhancing the remanence via magnetic exchange coupling are
evaluated
In recent developments in research in nanostructured permanent magnets (hard
magnetic materials) with emphasis on bottom-up approaches to fabrication of hard/soft
nanocomposite bulk magnets. Theoretical and experimental findings on the effects of soft
phase and interface conditions on interphase exchange interactions are given. Synthesis
techniques for hard magnetic nanoparticles, including chemical solution methods,
surfactant-assisted ball milling and other physical deposition methods are reviewed.
Processing and magnetic properties of warm compacted and plastically deformed bulk
magnets with nanocrystalline morphology are discussed. Prospects of producing bulk
anisotropic hard/soft nanocomposite magnets are presented.
Giant Magnetic Resonance of nano materials
The discovery of giant magnetoresistance (GMR) occurred in the late 1980s,1,2 at
the dawn of the age of the modern computing. This discovery, and its fortuitous timing,
resulted in the rapid commercial deployment of GMR-based devices in the read heads of
hard disk drives, accelerating the miniaturization of data storage and driving the digital
revolution. The immediate impact of GMR won Albert Fert and Peter Grünberg, the
discoverers of this phenomenon, the Nobel Prize in Physics. Today, giant (GMR), tunnelling
(TMR), and anisotropic (AMR) magnetoresistance are still instrumental in spin valve
devices for reading and writing data. Of further interest is that within emerging areas of
research there is tremendous promise for application of MR devices in areas requiring
sensitive magnetic field sensors, including navigation,3 biomedical sensing,4 and more
complex applications in spintronics.5 Creating new magneto resistive materials is vitally
important to developing these new areas.
Despite the overwhelming need for new materials, the vast phase space of magnetic
materials remains unexplored for MR applications. Reporting in ACS Central Science,
Zhou and Rinehart demonstrate a novel approach to the creation of magneto resistive
materials with an intriguing report of tunnelling magnetoresistance (TMR) in colloidally
prepared CoFe2O4 nanoparticles.6 Leveraging advances in nanoparticle preparation
techniques, Rinehart and co-workers demonstrate how commonly held assumptions
about the nature and limitations of nanoparticle-based magnetoresistance need to be
questioned. Chief among these assumptions are the defining importance of (1) highly
crystalline interfaces and (2) magnetically ordered materials.
TMR arises within conductive ferro- or ferrimagnetic materials at the interface
between different magnetic domains. If the magnetization vectors of adjacent magnetic
domains are aligned, then electrons can move between them relatively unimpeded. If the
domains’ magnetization vectors are oppositely aligned, then electron flow between those
domains is impeded, resulting in decreased conductivity across the interface. This
phenomenon underpins spin valve magnetic field sensors used in many different devices.
An extension of this phenomenon arises in granular solids which are composed of many
independent ferro- or ferrimagnetic single-domain particles which align upon exposure to
an external magnetic field.
PROPERTIES OF MATERIALS
The mechanical and physical properties of materials are
determined by their chemical composition and their internal structure, like grain size or
crystal structure. Mechanical properties may be greatly affected by processing due to the
rearrangement of the internal structure. Metalworking processes or heat treatment might
play a role in affecting some physical properties like density and electrical conductivity,
but those effects are usually insignificant.
Mechanical and physical properties are a key determinant for which
alloy is considered suitable for a given application when multiple alloys satisfy the service
conditions. In almost every instance, the engineer designs the part to perform within a
given range of properties. Many of the mechanical properties are interdependent – high
performance in one category may be coupled with lower performance in another. Higher-
strength, as an example, maybe achieved at the expense of lower ductility. So a broad
understanding of the product’s environment will lead to the selection of the best material
for the application.
Electrical properties of nanomaterials
The electrical properties of the nanomaterials or nanoparticles. The
properties like conductivity or resistivity are come under category of electrical properties.
These properties are observed to change at nanoscale level like optical properties. The
examples of the change in electrical properties in nanomaterials are:
1. Conductivity of a bulk or large material does not depend upon dimensions like diameter
or area of cross section and twist in the conducting wire etc. However it is found that in
case of carbon nanotubes conductivity changes with change in area of cross section.
2. It is also observed that conductivity also changes when some shear force (in simple
terms twist) is given to nanotube.
3. Conductivity of a multiwalled carbon nanotube is different than that of single nanotube
of same dimensions.
4. The carbon nanotubes can act as conductor or semiconductor in behaviour but we all
know that large carbon (graphite) is good conductor of electricity.
Dielectric properties of nanomaterials
The small grain size of nanomaterials has significant effect due to
drastic change in the physical properties of the materials used for their interconnects and
components. The issue of the dielectric property for nanomaterials is very important and
attractive for their potential applications as capacitor, memory device and sensor. The
dielectric property of nanomaterials interestingly exhibits unusual property which will give
rise to develop new materials2. The frequency behaviour of dielectric materials gives the
valuable information about the conduction phenomena of nanostructures materials with
their cappants. It is to be noted that the dielectric properties in nanomaterials have some
interesting aspects especially for metal nanoparticles in which the cappants are basically
insulating and the core is metallic. However, when they form such complex system of
nanoparticles, the basically insulating cappants would change their insulating state into
more conductive phase, due their ionic form, while those of the metal turning into
insulating phase as the particle size is reduced to that of a few atoms big(~1 nm), due to
quantum size effect. How this situation influences their overall dielectric properties is of
fundamental importance.
Optical properties of nanomaterial
Optical properties of nanomaterial such as absorption, transmission, reflection, and
light emission are dynamic and may differ significantly from properties exhibited by the
same bulk material. A wide range of optical effects may be produced for a variety of
applications by simply manipulating its shape, size, and surface functionality. This
manipulation may be achieved via different means, depending on the composition, size,
and orientation. The optical property of nanomaterial is very important in a variety of
ways. They are capable of confining their electrical properties to produce quantum effect
with the possibility of the variation in shape, size, or type having effect on the color they
produce. For example, spherical gold nanomaterial of 25-nm diameter appears green while
those in the range of 100 nm appear orange. In the same vein, spherical gold nanomaterial
of 100-nm diameter appears orange while a similar size of spherical silver nanomaterial
appears yellow.
The optical properties of nanomaterials are some of the most important, and can be
identified using various spectroscopic techniques. In small nanoclusters, reduced
dimensionality in their electronic structure has the most profound effect on the energies
of the highest occupied molecular orbital, which is a valence band, and the lowest
unoccupied molecular orbital, which is essentially the conduction band. Optical properties
such as emission and adsorption occur when electron transition occurs between these two
states. Semiconductors and many metals show large changes in optical properties as a
function of particle size. A simple example is the color of various nanoparticle solutions .
As the size increases, the color of the colloidal suspension of gold changes its color from
red to yellow.
Nanoparticles’ color is due to the surface plasmon resonance effect, which is a
resonance of the outer electron bands of the particles with light wavelengths. When light
photons excite the outer electrons of the particles, the outer electrons on the metal
particles jiggle at certain wavelengths and absorb light corresponding to that resonance.
The relationship of particle size to color is well known and is mathematically quantified by
the Mies and Rayleigh scattering theories . Properties
like photocatalysis, photoconductivity, photoemission, electroluminescence, etc., are also
affected by reduced dimensionality of nanoparticles.
Optoelectronic properties of nanomaterials
Electronic and optoelectronic devices, from computers and smart
cell phones to solar cells, have become a part of our life. Currently, devices with featured
circuits of 45 nm in size can be fabricated for commercial use. However, further
development based on traditional semiconductor is hindered by the increasing thermal
issues and the manufacturing cost. During the last decade, nanocrystals have been widely
adopted in various electronic and optoelectronic applications. They provide alternative
options in terms of ease of processing, low cost, better flexibility, and superior
electronic/optoelectronic properties. By taking advantage of solution-processing, self-
assembly, and surface engineering, nanocrystals could serve as new building blocks for
low-cost manufacturing of flexible and large area devices.
Tunable electronic structures combined with small exciton
binding energy, high luminescence efficiency, and low thermal conductivity make
nanocrystals extremely attractive for FET, memory device, solar cell, solid-state
lighting/display, photodetector, and lasing applications. Efforts to harness the
nanocrystal quantum tunability have led to the successful demonstration of many
prototype devices, raising the public awareness to the wide range of solutions that
nanotechnology can provide for an efficient energy economy. This special issue aims to
provide the readers with the latest achievements of nanocrystals in electronic and
optoelectronic applications, including the synthesis and engineering of nanocrystals
towards the applications and the corresponding device fabrication, characterization and
computer modeling.
Thermal properties of nanomaterials
The recent advances of nanotechnologies in the past decades have
resulted in the burst of promising synthesis, processing and characterization technologies,
which enables the routine production of a variety of nanomaterials with highly controlled
structures and related properties. By controlling the structures of nanomaterials at nano
scale dimensions, the properties of the nanostructures can be controlled and tailored in a
very predictable manner to meet the needs for a variety of applications. Examples of the
engineered nanostructures include metallic and non-metallic nanoparticles, nanotubes,
quantum dots and superlattices, thin films, nano composites and nano electronic and
optoelectronic devices which utilize the superior properties of the nanomaterials to fulfill
the applications.
Mechanical properties of nanomaterials
The special mechanical properties of nanoparticles allow for novel
applications in many fields, e.g., surface engineering, tribology and
nanomanufacturing/nanofabrication. In this review, the basic physics of the relevant
interfacial forces to nanoparticles and the main measuring techniques are briefly
introduced first. Then, the theories and important results of the mechanical properties
between nanoparticles or the nanoparticles acting on a surface, e.g., hardness, elastic
modulus, adhesion and friction, as well as movement laws are surveyed. Afterwards,
several of the main applications of nanoparticles as a result of their special mechanical
properties, including lubricant additives, nanoparticles in nanomanufacturing and
nanoparticle reinforced composite coating, are introduced. A brief summary and the future
outlook are also given in the final part.
Magnetic properties of nanomaterials
Interstellar space, lunar samples, and meteorites have inclusive
magnetic nanoparticles. The geomagnetic navigational aids in all migratory birds, fishes
and other animals contain magnetic nanoparticles. The most common iron storage protein
ferritin ([FeOOH]n containing magnetic nanoparticle) is present in almost every cell of
plants and animals including humans. The human brain contains over 108 magnetic
nanoparticles of magnetite–maghemite per gram of tissue. Denis G. Rancourt has written
a nice survey of magnetism of Earth, planetary and environmental nanomaterials.
Effect of size reduction on properties
Size-dependent effects in nanostructured (nanocrystalline, nanophase
or nanocomposite) materials are of great importance both for fundamental considerations
and modern technology. The effect of the nanoparticle/nano crystallite size on surface
energy, melting point, phase transformations, and phase equilibriums is considered as
applied to nanostructured materials. The role of size-dependent effects in phonon,
electronic, superconducting, magnetic, and partly mechanical properties is also analyzed
in detail. Special attention is paid to the contribution of other factors such as the grain
boundary segregations, interface structure, residual stresses and pores, non-uniform
distribution of grain sizes, and so on.
UNIT– III:
SYNTHESIS ROUTES: Bottom up approaches: Physical Vapor Deposition, Inert Gas
Condensation, Laser Ablation, Chemical Vapor Deposition, Molecular Beam Epitaxy, Sol-
gel method, Self-assembly. Top down approaches: Mechanical alloying, Nano-lithography.
Consolidation of Nano powders: Shock wave consolidation, Hot iso-static pressing and
Cold iso-static pressing, Spark plasma sintering.
***************************************************************************************************
SYNTHESIS ROUTES BOTTOM-UP APPROACH
Synthesis of nanomaterials and nanostructures are the important aspect of
nanoscience and nanotechnology. New physical properties and applications of
nanomaterials are only possible when nanostructured materials are made available with
desired size, shape, morphology, crystal structure and chemical composition. These notes
provide a clear and concise understanding on Top-down and Bottom-up approaches for
synthesis of nanomaterials.
Nanostructure materials have attracted a great deal of attention because their
physical, chemical, electronic and magnetic properties show dramatic change from higher
dimensional counterparts and depend on their shape and size. Many techniques have
been developed to synthesize and fabricate nanostructure materials with controlled shape,
size, dimensionality and structure. The performance of materials depends on their
properties. The properties in tern depend on the atomic structure, composition,
microstructure, defects and interfaces which are controlled by thermodynamics and
kinetics of the synthesis.
Classification of Techniques for synthesis of Nanomaterials There are two general
approaches for the synthesis of nanomaterials Top- down approach, Bottom–up approach.
Top-down approach Top-down approach involves the breaking down of the bulk
material into nanosized structures or particles. Top-down synthesis techniques are
extension of those that have been used for producing micron sized particles. Top-down
approaches are inherently simpler and depend either on removal or division of bulk
material or on miniaturization of bulk fabrication processes to produce the desired
structure with appropriate properties. The biggest problem with the top-down approach is
the imperfection of surface structure. For example, nanowires made by lithography are not
smooth and may contain a lot of impurities and structural defects on its surface. Examples
of such techniques are high-energy wet ball milling, electron beam lithography, atomic
force manipulation, gas-phase condensation, aerosol spray, etc.

Bottom-up approach The alternative approach, which has the potential of creating
less waste and hence the more economical, is the ‘bottom- up’. Bottom-up approach refers
to the build up of a material from the bottom: atom-by-atom, molecule-by-molecule, or
cluster-by cluster. Many of these techniques are still under development or are just
beginning to be used for commercial production of nanopowders. Oraganometallic
chemical route, revere-micelle route, sol-gel synthesis, colloidal precipitation,
hydrothermal synthesis, template assisted sol-gel, electrodeposition etc, are some of the
well- known bottom–up techniques reported for the preparation of luminescent
nanoparticals.
PHYSICAL VAPOR DEPOSITION
Evaporation technique
Thermal deposition inside a vacuum chamber where the material, usually in a boat
is heated typically to its melting point and the substrate to be deposited on is positioned
facing the source. A high current flowing through the boat heats it up and causes
evaporation. A crystal monitor is mounted close to the substrate, which provides an
estimate of how much and how fast the material is being deposited.
Limitations-
High temperature process ( 500-1200oC)
Ultra high vacuum(10-6 torr)
High cost
ELECTRON-BEAM EVAPORATION
This technique is based in the heat produced by high energy electron beam bombardment
on the material to be deposited. A high dc voltage is applied to a tungsten filament that
causes electrons to be emitted out. These emitted electrons are accelerated to excites the
target solid and produces vapors, which travels to the substrate. As they reach the surface,
they condense and form a thin film coating.
Used for depositing materials with high melting point (W, Ta, C, etc.)
As electrons can be focalized, it is possible to obtain a very localized heating on the material
to evaporate, with a high density of evaporation power (several kW)

INERT GAS CONDENSATION


Inert-gas condensation: The inert gas evaporation–condensation (IGC) technique,
in which nanoparticles are formed via the evaporation of a metallic source in an inert gas,
has been widely used in the synthesis of ultrafine metal particles In this process, a metal
is evaporated inside an ultrahigh vacuum (UHV) chamber filled with inert gas (He). The
vaporized species collide with Helium molecules thus losing kinetic energy. As collisions
limit the mean free path, supersaturation can be achieved above the vapors source. At
high supersaturation, the vapors rapidly form no. of clusters that grow via coalescence
and agglomeration. These clusters get condensed on liquid nitrogencooled surfaces to form
nanoparticles. The size, morphology, and yield of the NPs should be controlled.
LASER ABLATION
Laser ablation pulsed laser deposition system. This method is applicable for high melting
point elements and transition metal

In this method, a solid metal rod is ablated using a Nd:YAG laser (high Power) in a chamber
containing Ar gas. In the plasma that results from the laser ablation, metal atoms are
evaporated and condensed on water cooled substrate. Later the substrate is heated to
remove the impurities. NPs of Iron, gold, palladium, and compounds of sulphide are
pepared by this method.
Advantage: capable of High deposition rate of 2-3 g/min
Disadvantage:High temperature method
low quality of material deposited
CHEMICAL VAPOR DEPOSITION
Chemical vapor Deposition: Bottom-Up approach Chemical vapour deposition (CVD) is a
chemical process used to produce high-purity, highperformance solid materials. The
process is often used in the semiconductor industry to produce thin films. In a typical
CVD process, the wafer (substrate) is exposed to one or more volatile precursors, which
react and/or decompose on the substrate surface to produce the desired deposit. Plasma
Enhanced CVD- • RF-plasma enhanced CVD • Microwave Plasma Enhanced CVD The
energy source (RF/ Microwave power) is intended to generate a plasma in which the gases
are broken down to form reaction species.
SPUTTERING
Sputter deposition are methods of depositing thin films by sputtering. They involve ejecting
material from a “target” that is a source onto a “substrate” such as a silicon wafer. Atoms
of Target (source) materials are ejected or sputtered by high energy ion bombardment of
high-energy noble gas atoms, commonly Argon, produced by ahigh voltage DC or RF glow
discharge. These ejected sputtered atoms (due to momentum transfer) form a thin film
coating after condensing on substrate kept as anodeplate. Sputtered atoms ejected from
the target have a wide energy distribution, typically up to tens of eV.
Advantages
Non-thermal process, no heating reqd.
low vacuum(10-3 torr) is needed.
Limitations-
controlling Deposition parameters is difficult
High cost

THIN FILM DEPOSITION BY SPUTTERING PROCESS


The sputtering process consists of the bombardment of the target material by fast
moving, heavy, inert gas ions from a plasma. The bombarding ions cause atoms to be
ejected from the target material by momentum transfer between the colliding ions and the
target atoms. The process is schematically shown in Figure, where a number of processes
are shown to occur when the ions collide with the target material. Some of the bombarding
ions are reflected back and are neutralized, but may still be sufficiently energetic to reach
the substrate were the film is being deposited. This can be a source of substrate
bombardment (back scattering) which can effect the resulting properties of the film. The
majority of the colliding ions tend to induce sputtering by ejecting atoms of the target
material by momentum transfer. This is a secondary collision process, as shown
schematically. The ejected atoms will have random directions but, as discussed, the
sputtering process can induce texture in the resulting films due to the sputtering
conditions. Secondary electrons which are emitted either join the oscillating plasma gas,
which cause the continuous ionization of the gas to sustain the incident ions needed for
sputtering, or they liberate their energy in the form of heat on colliding with the substrate
or other parts of the chamber. The sputtered target atoms which are deposited at the
substrate form the resulting thin film. The basic processes occurring at the surface of the
substrate are shown in Figure. The mobility of the incident atoms arriving at the substrate
is highly dependent upon the sputtering parameters (pressure and power), the
temperature of the substrate, the distance between target and substrate, and the surface.

PLASMA PROCESSING METHODS


In general, plasma processing involves chemical and physical reactions between particles
and solid surfaces in contact with the plasma. Some examples are plasma etching, thin
film deposition, protective coating, surface hardening, ion implantation etc.
In this electric arc discharge method, material is vaporized between two electrodes by arc
produced by applying very high voltage (50-100V) across the electrodes. This ionizes the
inert gas and plasma is generated (temperature 6000oC), due to which metal atoms are
evaporated and get condensed on water cooled substrate. Later the substrate is heated to
remove the impurities. Carbon nanotubes are prepared by graphite as cathode. Nanotubes
of dichalcogenides are prepared by such as MoS2, WS2 are prepared are prepared by
starting with MoO3 and WO3.
Arc discharges technique: plasma of inert gases is produced by DC (direct current) glow
or arc discharges,

MOLECULAR BEAM EPITAXY


Molecular beam epitaxy (MBE) is an experimental technique utilized for layer-by-
layer growth of thin films of various quantum materials. Out of the variety of thin film
growth techniques available, MBE is considered to be one of the cleanest, but also one of
the most technically challenging and demanding, as MBE growth takes place in ultra-high
vacuum (UHV) environment.
Typical MBE experimental setup consists of two or more Knudsen effusion cells
(K-cells), located at the bottom of a UHV chamber and aligned towards the center of the
chamber where a sample holder with a substrate is located. Each individual K-cell
contains a different element in ultra pure solid form (i.e. elemental 99.999% Selinum,
Bismuth, etc.) which can be used in the thin film synthesis. The process of MBE growth
starts by heating the K-cells to appropriate temperatures until the elements in each cell
reach a sublimation point. Then, the shutters are opened and physical vapor from each
K-cell diffuses though the chamber until it reaches the substrate where it gets deposited,
and the thin film gets formed. The final composition and stoichiometry of the film will
depend on the temperature and surface atomic structure of the substrate, as well as the
flux ratios of individual components reaching the substrate. For more uniform growth,
substrate can be continuously rotated at low rotation speeds (~1-2 rotations per minute)
by utilizing a stepper motor attached to the magnetic manipulator.
To characterize the samples in-situ during growth, we use reflection high-energy
electron diffraction (RHEED). Electrons emitted from the RHEED gun incident at a very
low angle with respect to the sample surface are diffracted, and the resulting diffraction
pattern is observed on the screen. This pattern can reveal: (1) quality of the film surface,
and (2) film thickness down to a single monolayer.

SOL-GEL METHOD
The sol-gel process may be described as: ”Formation of an oxide network through
polycondensation reactions of a molecular precursor in a liquid.” A sol is a stable
dispersion of colloidal particles or polymers in a solvent. The particles may be amorphous
or crystalline. An aerosol is particles in a gas phase, while a sol is particles in a liquid, A
gel consists of a three dimensional continuous network, which encloses a liquid phase, In
a colloidal gel, the network is built from agglomeration of colloidal particles. In a polymer
gel the particles have a polymeric sub-structure made by aggregates of sub-colloidal
particles. Generally, the sol particles may interact by van der Waals forces or hydrogen
bonds. A gel may also be formed from linking polymer chains. In most gel systems used
for materials synthesis, the interactions are of a covalent nature and the gel process is
irreversible. The gelation process may be reversible if other interactions are involved.
The idea behind sol-gel synthesis is to “dissolve” the compound in a liquid in order
to bring it back as a solid in a controlled manner. Multi component compounds may be
prepared with a controlled stoichiometry by mixing sols of different compounds. The sol-
gel method prevents the problems with co-precipitation, which may be inhomogeneous, be
a gelation reaction. Enables mixing at an atomic level. Results in small particles, which
are easily sinterable. The sol-gel method was developed in the 1960s mainly due to the
need of new synthesis methods in the nuclear industry. A method was needed where dust
was reduced (compared to the ceramic method) and which needed a lower sintering
temperature. In addition, it should be possible to do the synthesis by remote control. One
of the well known examples of a sol-gel system often cited is quick clay. Clay may form a
sol (quick clay) if it is washed sufficiently to remove the counter ions. Quick clay may be
gelled if enough counter ions are added, so that the colloidal particles aggregate.
(exfoliation/restacking may be involved) Sol-gel synthesis may be used to prepare
materials with a variety of shapes, such as porous structures, thin fibers, dense powders
and thin films. If the gel is dried by evaporation, then the capillary forces will result in
shrinkage, the gel network will collapse, and a xerogel is formed. If drying is performed
under supercritical conditions, the network structure may be retained and a gel with large
pores may be formed. This is called an aerogel, and the density will be very low. A record
is < 0.005 g/cm3.
SELF-ASSEMBLY
Nanoparticles are classified as having at least one of three dimensions be in the
range of 1-100 nm. The small size of nanoparticles allows them to have unique
characteristics which may not be possible on the macro-scale. Self-assembly is the
spontaneous organization of smaller subunits to form larger, well-organized patterns. For
nanoparticles, this spontaneous assembly is a consequence of interactions between the
particles aimed at achieving a thermodynamic equilibrium and reducing the system’s free
energy. The thermodynamics definition of self-assembly was introduced by Nicholas A.
Kotov. He describes self-assembly as a process where components of the system acquire
non-random spatial distribution with respect to each other and the boundaries of the
system. This definition allows one to account for mass and energy fluxes taking place in
the self-assembly processes.
This process occurs at all size scales, in the form of either static or dynamic self-
assembly. Static self-assembly utilizes interactions amongst the nano-particles to achieve
a free-energy minimum. In solutions, it is an outcome of random motion of molecules and
the affinity of their binding sites for one another. A dynamic system is forced to not reach
equilibrium by supplying the system with a continuous, external source of energy to
balance attractive and repulsive forces. Magnetic fields, electric fields, ultrasound fields,
light fields, etc. have all been used as external energy sources to program robot swarms at
small scales. Static self-assembly is significantly slower compared to dynamic self-
assembly as it depends on the random chemical interactions between particles.
HYDROTHERMAL GROWTH
Hydrothermal synthesis is one of the most commonly used methods for
preparation of nanomaterials. It is basically a solution reaction-based approach. In
hydrothermal synthesis, the formation of nanomaterials can happen in a wide temperature
range from room temperature to very high temperatures. To control the morphology of the
materials to be prepared, either low-pressure or high-pressure conditions can be used
depending on the vapor pressure of the main composition in the reaction. Many types of
nanomaterials have been successfully synthesized by the use of this approach. There are
significant advantages of hydrothermal synthesis method over others.
Hydrothermal synthesis can generate nanomaterials which are not stable at
elevated temperatures. Nanomaterials with high vapor pressures can be produced by the
hydrothermal method with minimum loss of materials. The compositions of nanomaterials
to be synthesized can be well controlled in hydrothermal synthesis through liquid phase
or multiphase chemical reactions. This special issue serves as a forum presenting the
recent research results of hydrothermal synthesis of nanomaterials. Several papers on
hydrothermal synthesis of nanoparticles, nanorods, nanotubes, hollow nanospheres, and
graphene nanosheets have been published in this special issue. New synthesis methods,
for example, microwave-assisted hydrothermal synthesis and template-free self-
assembling catalytic synthesis, etc.
THIN-FILM GROWTH OF NANO MATERIALS
A thin film is a layer of material ranging from fractions of a nanometer (monolayer)
to several micrometers in thickness. The controlled synthesis of materials as thin films (a
process referred to as deposition) is a fundamental step in many applications. A familiar
example is the household mirror, which typically has a thin metal coating on the back of
a sheet of glass to form a reflective interface. The process of silvering was once commonly
used to produce mirrors, while more recently the metal layer is deposited using techniques
such as sputtering. Advances in thin film deposition techniques during the 20th century
have enabled a wide range of technological breakthroughs in areas such as magnetic
recording media, electronic semiconductor devices, Integrated passive devices, LEDs,
optical coatings (such as antireflective coatings), hard coatings on cutting tools, and for
both energy generation (e.g. thin-film solar cells) and storage (thin-film batteries). It is also
being applied to pharmaceuticals, via thin-film drug delivery. A stack of thin films is called
a multilayer.
In addition to their applied interest, thin films play an important role in the
development and study of materials with new and unique properties. Examples include
multiferroic materials, \and superlattices that allow the study of quantum phenomena.
TOP-DOWN APPROACH OF NANO MATERIALS
Top-down approach Top-down approach involves the breaking down of the bulk
material into nanosized structures or particles. Top-down synthesis techniques are
extension of those that have been used for producing micron sized particles. Top-down
approaches are inherently simpler and depend either on removal or division of bulk
material or on miniaturization of bulk fabrication processes to produce the desired
structure with appropriate properties.
BALL MILLING
Ball milling is an economic and facile technique to produce nanosized materials.
It is a top-down approach of nanoparticle synthesis which includes mechanical breakdown
of large substances into smaller one. It is used in producing metallic as well as ceramic
nanomaterials. In this module, the readers will learn the working principle and
applications of Ball-mill technique in nanomaterials synthesis. The basic principle of a ball
mill is very ancient. However, the machine itself could be produced only after the industrial
revolution. Typically, ball mill is a grinder and is often employed blend materials by
grinding/crushing them, for potential applications in mineral dressing processes, paints,
pyrotechnics, ceramics as well as selective laser sintering.
The working of a ball mill is based on impact and attrition: the impact, caused by
the balls dropping from top of the shell, breaks down the particles, thereby resulting in
reduction in size. Ball mill includes a hollow cylindrical shell which is rotated about its
own axis. The axis of the shell is either horizontal or slightly inclined, thereby making a
small angle with the horizontal. The shell is partially filled with balls. The balls form the
grinding medium of the ball mill. These balls are usually made up of steel, ceramic, flint
pebbles, or hard rubber. The inner wall of the shell is generally contains a coating of
abrasion resistant material, e.g., manganese steel or rubber. Rubber lined (or coated) ball
mills cause less wear to the products. The mill is nearly equal in length and diameter.
In continuously operated mills, precursor material is fed from left side at an angle
of 60°, and the end product is removed from right side at 30°. When the shell is rotated,
the balls lift upwards on the rising side of the mill. After reaching near the top of the shell,
the balls fall down, causing an impact on the particles trapped between these balls and
the shell surface. This impact reduced the size of these particles.
a. It consists of stainless steel chamber and several small iron, silicon carbide, hardened
steel, or tungsten carbide balls to rotate inside the mill.
b. Powder of material is put in the steel chamber. The powder is reduced to nanosize using
ball mill. A magnet is positioned outside the chamber to apply pulling force on the material.
This force raises milling energy as the milling chamber or container rotates the metallic
balls.
c. The ball and material - mass ratio is generally kept at 2:1.
d. These metallic balls impart very high energy to the powder resulting in crushing of the
powder. The ball milling process generally takes 100 to 150 hrs to give uniformly crushed
fine powder.
e. It is mechanical processing technique; consequently the structural as well as chemical
changes are caused by the mechanical energy.

a. Initial Stage: Initially, compressive forces from collisions of balls flatten the powder
particles. Micro-forging causes variations in the shapes of individual particles, or cluster
of particles, owing to repeated impact of high energy (kinetic energy) milling balls. In spite
of this, such deformations of the powder cause do not effectively change the mass.
b. Intermediate stage: In this stage, considerable variations occur in contrast to the first
stage. Powders experience considerable cold welding. The fine blending of the constituents
of powder reduces the diffusion distance to few microns. The dominating processes at this
stage are fracturing and cold welding. Though dissolution may occur to a certain extent,
yet the alloyed powder does not have homogeneous chemical composition.
c. Final stage: This stage exhibits marked refinement and size reduction.
Microstructurally, particles appear more homogenous at this stage. This stage marks the
formation of true alloys.
d. Completion stage: The structure of the powder particles is tremendously deformed and
is metastable. The lamellae are not resolvable via optical microscope. Alloying beyond this
stage does not cause any improvement in the constituents’ distribution. True alloy is
formed which has same composition as the precursor.
MICROFABRICATION
Microfabrication is the process of fabricating miniature structures
of micrometre scales and smaller. Historically, the earliest microfabrication processes
were used for integrated circuit fabrication, also known as "semiconductor
manufacturing" or "semiconductor device fabrication". In the last two
decades microelectromechanical systems (MEMS), microsystems (European
usage), micromachines (Japanese terminology) and their subfields, microfluidics/lab-on-
a-chip, optical MEMS (also called MOEMS), RF MEMS, Power MEMS, BioMEMS and their
extension into nanoscale (for example NEMS, for nano electro mechanical systems) have
re-used, adapted or extended microfabrication methods.
Flat-panel displays and solar cells are also using similar techniques.
Miniaturization of various devices presents challenges in many areas of science and
engineering: physics, chemistry, materials science, computer science, ultra-precision
engineering, fabrication processes, and equipment design. It is also giving rise to various
kinds of interdisciplinary research.[1] The major concepts and principles of
microfabrication are microlithography, doping, thin films, etching, bonding,
and polishing.
icrofabrication is actually a collection of technologies which are utilized in making
microdevices. Some of them have very old origins, not connected to manufacturing,
like lithography or etching. Polishing was borrowed from optics manufacturing, and many
of the vacuum techniques come from 19th century physics research. Electroplating is also
a 19th-century technique adapted to produce micrometre scale structures, as are
various stamping and embossing techniques.
To fabricate a microdevice, many processes must be performed, one after the other,
many times repeatedly. These processes typically include depositing a film, patterning the
film with the desired micro features, and removing (or etching) portions of the film. Thin
film metrology is used typically during each of these individual process steps, to ensure
the film structure has the desired characteristics in terms of thickness (t), refractive index
(n) and extinction coefficient (k), for suitable device behavior. For example, in memory
chip fabrication there are some 30 lithography steps, 10 oxidation steps, 20 etching steps,
10 doping steps, and many others are performed. The complexity of microfabrication
processes can be described by their mask count. This is the number of
different pattern layers that constitute the final device. Modern microprocessors are made
with 30 masks while a few masks suffice for a microfluidic device or a laser diode.
Microfabrication resembles multiple exposure photography, with many patterns aligned to
each other to create the final structure.
NANOLITHOGRAPHY
Nanolithography is the branch of nanotechnology concerned with the study and
application of the nanofabrication of nanometer-scale structures, meaning nanopatterning
with at least one lateral dimension between the size of an individual atom and
approximately 100 nm. The term nanolithography is derived from the Greek words
“nanos”, meaning dwarf; “lithos”, meaning rock or stone; and “graphein” meaning to write.
Therefore the literal translation is "tiny writing on stone", however nowadays one
understands something different whenever this term is associated with nanotechnology.
Nanolithography is used e.g. during the nano‐ fabrication of leading-edge semiconductor
integrated circuits (nanocircuitry), for nanoelec‐ tromechanical systems (NEMS) or for
almost any other fundamental application across various scientific disciplines
Nanolithography is a powerful and versatile tool to fabricate nanoscale patterns.
Nanolithography can be used to construct well-defined 2D metal arrays on substrates with
fine controlled shape, size, and spacing through a multistep process. Electron beam
lithography (EBL) is a branch of nanolithography that is widely used to fabricate metal
nanostructures. The fabrication of metal nanostructures is carried out with scaling down
of a predeposited parent layer with a focused electron beam [67,68]. The gold nanohole
and/or nanodisk arrays with controlled spacing and size can be obtained with the use of
this technique.
The size-dependent surface-enhanced Raman spectroscopy (SERS) effect can be
studied by varying the diameter and the distance between the holes. In this, the nanohole
array plays a crucial role and acts as an excellent model to study the dimension-dependent
SERS effect. Nanosphere lithography (NSL) technique is another typical example of
nanolithography. This technique contains a multistep process developed by Van Duyne et
al. to produce surface-confined nanostructure arrays. In NSL the two-dimensional
nanostructures are deposited by using a monolayer self-assembly of polystyrene spheres
with controlled diameter as a mask. With this approach, ordered arrays of triangular Cu,
Ag, and Al nanocrystals have been prepared successfully. Another example of
nanolithography in addition to EBL and NSL are nanoimprint lithography and hole-mask
lithography, which are also beneficial tools for constructing two-dimensional metal
nanostructures.
This technology can be suitable to use in nanofabrication of various
semiconducting Integrated Circuits (ICs), NEMS and for various applications in research.
The modification in semicon‐ ductor chips at the nano-scale (in the range of 10-9 meter)
is also possible. This method is contrasting to various existing nanolithographic
techniques like Photolithography (Venugo‐ pal, 2011), Nanoimprint lithography (NIL),
Scanning Probe Lithography (SPL), Atomic Force Microscope (AFM) nanolithography,
Extreme Ultraviolet Lithography (EUVL) and X-ray Lithography.

CONSOLIDATION OF NANO POWDERS


The driving force of nano powder consolidation during sintering is the reduction of
the large surface area of nanoparticles. Additionally, the high sintering pressure also
assists the consolidation by inducing large shear stresses at the contact points between
particles that yield plastic deformation thereby contributing to the filling of pores. This
mechanism is especially important in the case of metallic powders having good
deformability. Although the high temperature during sintering facilitates the consolidation
by increasing the atomic mobility, it may also cause grain coarsening that is an unwanted
phenomenon in processing of nanomaterials.
To minimize grain growth, usually the time and temperature of sintering are
reduced together with a simultaneous increase of pressure for maintaining the low porosity
level in the final product. In this section, some nano powder consolidation procedures are
overviewed: shock wave consolidation, pressure less sintering, hot pressing, hot isostatic
pressing, and spark plasma sintering. The reason of selection of these methods for review
is that mainly they were used for the consolidation of the samples studied in the next
chapters. In shock wave consolidation, the high pressure and rapid loading rates applied
on the powder result in interparticle bonding due to localized melting at the interfaces
between the particles. In practice, the powder particles are enclosed in a steel block, which
is covered by a plate on the top that drives the shock wave caused by the explosion toward
the sample. The driver plate is usually made of a highly conductive, highly ductile material,
such as copper.
Explosives and the detonator are packed on the top of the driver plate. Of late, gas
guns are also widely used in performing shock wave consolidation. In the latter case,
hydrogen gas activates the projectile, which travels all the way through the barrel and hits
the powder sample. The duration and the pressure of the shock wave, which yields
consolidation of the powder, are ∼10−6 s and 20–600 GPa, respectively. Shock wave
consolidation technique is mainly used for metallic powders. As only the surfaces of the
particles are heated up, the grain growth is suppressed.
SHOCK WAVE CONSOLIDATION
Nanotechnology based thermoelectric materials are considered attractive for
developing highly efficient thermoelectric devices. Nano-structured thermoelectric
materials are predicted to offer higher ZT over bulk materials by reducing thermal
conductivity and increasing electrical conductivity. Consolidation of nano-structured
powders into dense materials without losing nanostructure is essential towards practical
device development. Using the gas atomization process, amorphous nano-structured
powders were produced. Shockwave consolidation is accomplished by surrounding the
nanopowder-containing tube with explosives and then detonated. The resulting shock
wave causes rapid fusing of the powders without the melt and subsequent grain growth.
We have been successful in generating consolidated nanostructured bismuth telluride
alloy powders by using shockwave technique. Using these consolidated materials, several
types of thermoelectric power generator devices have been developed. Shockwave
consolidation is anticipated to generate large quantities of nanostructred materials
expeditiously and cost effectively. In this paper, the technique of shockwave consolidation
will be presented followed by Seebeck Coefficient and thermal conductivity measurements
of consolidated materials. Preliminary results indicate a substantial increase in electrical
conductivity due to shockwave consolidation technique.

HOT ISOSTATIC PRESSING


Hot isostatic pressing (HIP) is a manufacturing process, used to reduce
the porosity of metals and increase the density of many ceramic materials. This improves
the material's mechanical properties and workability.
The process can be used to produce waste form classes. Calcined radioactive
waste (waste with additives) is packed into a thin walled metal canister.
The adsorbed gases are removed with high heat and the remaining material compressed
to full density using argon gas during the heat cycle. This process can shrink steel
canisters to minimize space in disposal containers and during transport. It was invented
in the 1950s by the Battelle Company and has been used to prepare nuclear
fuel for submarines since the 1960s. It is used to prepare inactive ceramics as well, and
the Idaho National Laboratory has validated it for the consolidation of radioactive ceramic
waste forms. ANTSO (Australia's Nuclear Science and Technology Organisation) is using
HIP as part of a process to immobilize waste radionuclides from molybdenum-
99 production.
The HIP process subjects a component to both elevated temperature
and isostatic gas pressure in a high pressure containment vessel. The pressurizing gas
most widely used is argon. An inert gas is used so that the material does not chemically
react. The choice of metal can minimize negative effects of chemical reactions. Nickel,
stainless or mild steel, or other metals can be chosen depending on the
desired redox conditions. The chamber is heated, causing the pressure inside the vessel
to increase. Many systems use associated gas pumping to achieve the necessary pressure
level. Pressure is applied to the material from all directions (hence the term "isostatic").

COLD ISOSTATIC PRESSING


One of the biggest challenges for making dye-sensitised solar cells (DSCs) on
plastic substrates is the difficulty in making good quality nanoporous TiO2 films with both
good mechanical stability and high electrical conductivity. Cold isostatic pressing (CIP) is
a powder compaction technique that applies an isostatic pressure to a powder sample in
all directions. It is particularly suitable for making thin films on plastic substrates,
including non-flat surfaces. Cold isostatically pressed nanocrystalline TiO2 electrodes with
excellent mechanical robustness were prepared on indium tin oxide (ITO)-coated
polyethylene naphthalate (PEN) substrates in the absence of organic binders and without
heat treatment. The morphology and the physical properties of the TiO2 films prepared by
the CIP method were found to be very compatible with requirements for flexible DSCs on
plastics. This room-temperature processing technique has led to an important technical
breakthrough in producing high efficiency flexible DSCs. Devices fabricated on ITO/PEN
films by this method using standard P-25 TiO2 films with a Ru-complex sensitiser yielded
a maximum incident photon-to-current conversion efficiency of 72% at the wavelength of
530 nm and showed high conversion efficiencies of 6.3% and 7.4% for incident light
intensities of 100 and 15 mW cm−2, respectively, which are the highest power conversion
efficiencies achieved so far for any DSC on a polymer substrate using the widely used,
commercially available P-25 TiO2 powder.
SPARK PLASMA SINTERING.
The main characteristic of SPS is that the pulsed or unpulsed DC or AC
current directly passes through the graphite die, as well as the powder compact, in case
of conductive samples. Joule heating has been found to play a dominant role in the
densification of powder compacts, which results in achieving near theoretical density at
lower sintering temperature compared to conventional sintering techniques. The heat
generation is internal, in contrast to the conventional hot pressing, where the heat is
provided by external heating elements. This facilitates a very high heating or cooling rate
(up to 1000 K/min), hence the sintering process generally is very fast (within a few
minutes).
The general speed of the process ensures it has the potential of densifying powders
with nanosize or nanostructure while avoiding coarsening which accompanies standard
densification routes. This has made SPS a good method for preparation of ceramics based
on nanoparticles with enhanced magnetic,[magnetoelectric, piezoelectric, thermoelectric
optical or biomedical properties. SPS is also used for sintering of Carbon Nanotubes for
development of field electron emission electrodes. Functioning of SPS systems is
schematically explained in a video link. While the term "spark plasma sintering" is
commonly used, the term is misleading since neither a spark nor a plasma is present in
the process It has been experimentally verified that densification is facilitated by the use
of a current.
The spark plasma sintering (SPS), a variant of field-assisted sintering (FAST) or
pulsed electric current sintering (PECS), is a novel pressure assisted pulsed electric
current sintering process, which utilizes ON-OFF DC pulse energizing. Due to the repeated
application of an ON-OFF DC pulse voltage and current flow between powder particles, the
spark discharges and the Joule heating (local high temperature state) are therefore
dispersed to the overall specimen. The SPS process is based on the electrical spark
discharge phenomenon and is a high efficient, energy saving technique with a high heating
rate and a short holding time. The problem of rapid grain growth of nanomaterials during
conventional sintering can be inhibited to a larger extent by using the SPS technique. The
SPS can be used for diverse novel bulk material applications, but it is particularly suitable
for the processing of nanomaterials. Despite such anticipated advantages, the optimization
of the process window (heating rate-temperature-time) in SPS process is a challenging task
UNIT– IV:
TOOLS TO CHARACTERIZE NANOMATERIALS: X-Ray Diffraction (XRD), Small Angle X-ray
scattering, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM),
Atomic Force Microscopy (AFM), Scanning Tunneling Microscope (STM), Field Ion Microscope
(FEM), Three-dimensional Atom Probe (3DAP),Nano indentation
***************************************************************************************************
CHARACTERIZATION TECHNIQUES
Nanoscience and nanotechnology are considered to be the key
technologies for the current century. Efforts are being made worldwide to create
smart and intelligent textiles by incorporating various nanoparticles or creating
nanostructured surfaces and nanofibres which lead to unprecedented level of
performance, such as stain resistant, self-cleaning, antistatic, UV protective, etc.
However, there are many challenges in the research and development of
nanotechnology based products. The precise control of nanoparticle size, size
distribution, dispersion at nanolevel and deposition needs sophisticated
characterization techniques
X-RAY DIFFRACTION (XRD) AND SCHERRER METHOD
X-ray diffraction (XRD) relies on the dual wave/particle nature of X-rays to
obtain information about the structure of crystalline materials. A primary use of
the technique is the identification and characterization of compounds based on
their diffraction pattern.
The dominant effect that occurs when an incident beam of monochromatic X-rays
interacts with a target material is scattering of those X-rays from atoms within the
target material. In materials with regular structure (i.e. crystalline), the scattered X-
rays undergo constructive and destructive interference. This is the process of
diffraction. The diffraction of X-rays by crystals is described by Bragg’s Law, n(lambda)
= 2d sin(theta). The directions of possible diffractions depend on the size and
shape of the unit cell of the material.
The intensities of the diffracted waves depend on the kind and arrangement
of atoms in the crystal structure. However, most materials are not single crystals,
but are composed of many tiny crystallites in all possible orientations called a
polycrystalline aggregate or powder. When a powder with randomly oriented
crystallites is placed in an X-ray beam, the beam will see all possible interatomic
planes. If the experimental angle is systematically changed, all possible diffraction
peaks from the powder will be detected. The parafocusing (or Bragg-Brentano)
diffractometer is the most common geometry for diffraction instruments.
This geometry offers the advantages of high resolution and high beam
intensity analysis at the cost of very precise alignment requirements and carefully
prepared samples. Additionally, this geometry requires that the source-to-sample
distance be constant and equal to the sample-to- detector distance. Alignment
errors often lead to difficulties in phase identification and improper quantification.
A mis-positioned sample can lead to unacceptable specimen displacement errors.
Sample flatness, roughness, and positioning constraints preclude in-line sample
measurement. Additionally, traditional XRD systems are often based on bulky
equipment with high power requirements as well as employing high powered X-
ray sources to increase X-ray flux on the sample, therefore increasing the
detected diffraction signals from the sample. These sources also have large
excitation areas, which are often disadvantageous for the diffraction analysis of
small samples or small sample features.
Polycapillary X-ray optics can be used to overcome many of these drawbacks
and constraints to enhance XRD applications. Polycapillary collimating optics
convert a highly divergent beam into a quasi-parallel beam with low divergence.
They can be used to form a Parallel Beam XRD instrument geometry which greatly
reduces and removes many sources of errors in peak position and intensity
inherent to the parafocusing geometry, such as sample position, shape,
roughness, flatness, and transparency. Polycapillary focusing optics collect X-rays
from a divergent X-ray source and direct them to a small focused beam at the
sample surface with diameters as small as tens of micrometers for micro X-ray
diffraction applications of small samples or small specimen features. Both types
of polycapillary optics direct very high X-ray intensities to the sample surface,
such that XRD systems employing optics can use low power X-ray sources,
reducing instrument size, cost, and power requirements.
X-ray diffraction using X-ray optics has been applied to many different types
of applications including thin film analysis, sample texture evaluation, monitoring
of crystalline phase and structure, and investigation of sample stress and strain.
Small Angle X-ray scattering (SAXS)
X-ray scattering is a nondestructive technique used to characterize the
morphology of materials. A collimated beam of X-rays is transmitted through a
specimen, and interactions with the matter within the sample cause some portion
of the X-rays to be scattered away from the transmitted primary beam. When 2
photons having wavelength λ are scattered by features separated by a distance, d,
the scattered photons are in phase only at a specific angle, 2θ. This relationship
is described by Bragg’s law.
Small-angle X-ray scattering (SAXS) is a small-angle scattering technique by
which nanoscale density differences in a sample can be quantified. This means
that it can determine nanoparticle size distributions, resolve the size and shape of
(monodisperse) macromolecules, determine pore sizes, characteristic distances of
partially ordered materials, and much more. This is achieved by analyzing the
elastic scattering behaviour of X-rays when travelling through the material,
recording their scattering at small angles (typically 0.1 – 10°, hence the "Small-
angle" in its name). It belongs to the family of small-angle scattering (SAS)
techniques along with small-angle neutron scattering, and is typically done using
hard X-rays with a wavelength of 0.07 –
0.2 nm.[clarification needed]. Depending on the angular range in which a clear
scattering signal can be recorded, SAXS is capable of delivering structural
information of dimensions between 1 and 100 nm, and of repeat distances in
partially ordered systems of up to 150 nm. USAXS (ultra-small angle X-ray
scattering) can resolve even larger dimensions, as the smaller the recorded angle,
the larger the object dimensions that are probed.
SAXS and USAXS belong to a family of X-ray scattering techniques that are
used in the characterization of materials. In the case of biological macromolecules
such as proteins, the advantage of SAXS over crystallography is that a crystalline
sample is not needed. Furthermore, the properties of SAXS allow investigation of
conformational diversity in these molecules.Nuclear magnetic resonance
spectroscopy methods encounter problems with macromolecules of higher
molecular mass (> 30–40 kDa). However, owing to the random orientation of
dissolved or partially ordered molecules, the spatial averaging leads to a loss of
information in SAXS compared to crystallography.
SCANNING ELECTRON MICROSCOPY
Scanning Electron Microscope functions exactly as their optical counterparts
except that they use a focused beam of electrons instead of light to “image” the
specimen and gain information as to its structure and composition. Given
sufficient light, the unaided human eye can distinguish two points 0.2 mm apart.
If the points are closer together, they will appear as a single point. This distance
is called the resolving power or resolution of the eye. Similarly, light microscopes
use visible light (400- 700nm) and transparent lenses to see objects as small as
about one micrometer (one millionth of a meter), such as a red blood cell (7 μm)
or a human hair (100 μm). Light microscope has a magnification of about 1000x
and enables the eye to resolve objects separated by 200 nm. Electron Microscopes
were developed due to the limitations of light microscopes, which are limited by
the physics of light. Electron Microscopes are capable of much higher
magnifications and have a greater resolving power than a light microscope,
allowing it to see much smaller objects at sub cellular, molecular and atomic level.
The smallest the wavelength of the illuminating sources is the best resolution of
the microscope
Working principles of SEM A beam of electrons is formed by the Electron
Source and accelerated toward the specimen using a positive electrical potential.
The electron beam is confined and focused using metal apertures and magnetic
lenses into a thin, focused, monochromatic beam. Electrons in the beam interact
with the atoms of the specimen, producing signals that contain information about
its surface topography, composition and other electrical properties. These
interactions and effects are detected and transformed into an image.
Components of SEM
Electron Column The electron column is where the electron beam is
generated under vacuum, focused to a small diameter, and scanned across the
surface of a specimen by electromagnetic deflection coils. The lower portion of the
column is called the specimen chamber.
Electron gun: An electron beam is thermionically emitted from an electron gun
fitted with a tungsten filament cathode. Tungsten has the highest melting point
and lowest vapour pressure of all metals, thereby allowing it to be heated for electron
emission, and because of its low cost. Other types of electron emitters include
lanthanum hexaboride (LaB6) cathodes, and field emission guns (FEG), which may
be of the cold-cathode type using tungsten single crystal emitters or the
thermally assisted Schottky type, using emitters of zirconium oxide.
Condenser Lenses: After the beam passes the anode it is influenced by two
condenser lenses that cause the beam to converge and pass through a focal point.
In conjunction with the selected accelerating voltage the condenser lenses are
primarily responsible for determining the intensity of the electron beam when it
strikes the specimen.
Apertures: The function of these apertures is to reduce and exclude extraneous
electrons in the lenses. The final lens aperture located below the scanning coils
determines the diameter or spot size of the beam at the specimen. The spot size on
the specimen will in part determine the resolution and depth of field. Decreasing
the spot size will allow for an increase in resolution and depth of field with a loss of
brightness.
Scanning System: Images are formed by rastering the electron beam across the
specimen using deflection coils inside the objective lens. The stigmator or
astigmatism corrector is located in the objective lens and uses a magnetic field in
order to reduce aberrations of the electron beam. The electron beam should have
a circular cross section when it strikes the specimen however it is usually elliptical
thus the stigmator acts to control this problem.
Specimen Chamber: The lower portion of the column is specimen stage and
controls are located. Specimens are mounted and secured onto the stage which is
controlled by a goniometer. The secondary electrons from the specimen are
attracted to the detector by a positive charge Manual stage controls are found on
the front side of the specimen chamber for x-y-z movement.
Electron Detectors: Detectors collect the signal generated from interaction of beam
with specimen. Electronic detectors convert the signal into digital images and most
often collected signal are Secondary electrons by secondary electron detector
(Everhart–Thornley) Backscattered electrons by backscattered electrons detector
(Solid-State detector) and X-rays signal by Energy dispersive spectrometer (EDS)
detector.
Vacuum System: Vacuum is produced by an oil diffusion pump backed by a
mechanical pump. In the diffusion pump a stream of hot oil vapor strikes and pushes
air molecules toward a mechanical pump that expels them from the system. A
mechanical pump and valve system are used to preevacuate the system because
a diffusion pump only operates after a vacuum is created. If the column is in a gas
filled environment, electrons will be scattered collide with air molecules which would
lead to reduction of the beam intensity and stability. Similarly, other gas molecules,
which could come from the sample or the microscope itself, could form compounds
and condense on the sample. This would lower the contrast and obscure detail in the
image. The chemical and thermal stability is necessary for a well-functioning filament
(gun pressure). The field emission gun, LaB6 and tungsten filament requires ~ 10-
10, ~ 10-6 and 10-4 Torr, respectively. Hence, gun column of electron microscope
require vacuum to facilitate the electrons signals from the sample to the detector
for better imaging
How Scanning Electron Microscope (SEM) works Ernst Ruska and Max Knoll
developed first electron microscope during 1931with resolution of 100nm and
later by addition of electromagnetic lenses, brought the resolution to 0.05nm. SEM
is similar to the optical stereo-binocular microscope to observe the morphology
and shape of the specimen. The electron gun produces an electron beam when
tungsten wire is heated by current and accelerated by the anode. The beam travels
in the vacuum column through electromagnetic fields and lenses, which focus the
beam down toward the sample. A mechanism of deflection coils enables to guide
the beam so that it scans the surface of the sample in a raster pattern.
When the incident beam touches the surface of the sample and produces
signals viz., Secondary electrons (SE) Auger electrons Back scattered electrons
(BSE) Characteristic X – Rays y Cathodoluminescence The emitted signals are
trapped by electrical detectors, convert into digital images and displayed on a
screen as digital image. Provides information sample’s elemental composition,
structural variation and morphology. In the SEM, use much lower accelerating
voltages to prevent beam penetration into the sample since the requirement is
generation of the secondary electrons from the true surface structure of a sample.
Therefore, it is common to use low KV, in the range 1-5kV for biological samples,
even though the SEMs are capable of up to 30 kV.
Interaction of Electron Beam with Specimen: When the primary electron
beam interacts with the sample, the electrons lose energy by repeated random
scattering and absorption within a teardrop-shaped volume of the specimen
known as the interaction volume, which extends from less than 100 nm to
approximately 10 µm into the surface. The size of the interaction volume depends
on the electron’s landing energy, the atomic number of the specimen and the
specimen’s density. The energy exchange between the electron beam and the
sample results in the reflection of high- energy back scattered electrons by elastic
scattering, emission of low energy secondary, auger electrons by inelastic
scattering and the emission of electromagnetic radiation (X-rays and
cathodoluminescence), each of which can be detected by respective detectors.
The beam current absorbed by the specimen can also be detected and used to
create images of the distribution of specimen current. Electronic amplifiers of
various types are used to amplify the signals, electronic detectors convert the
signals into digital images and displayed on a computer monitor Backscattered
electron: Those electrons, which are deflected, back in the direction of the beam.
The special detector in scanning and transmission electron microscope traps
these signals. These are used to discriminate areas of different atomic numbered
elements. Higher atomic numbered elements gives off more backscattered
electrons and appear brighter than lower numbered elements. It has the
resolution to the level of 1000 nm. These electrons have high energy.
Secondary Electrons: These electrons are also collected with a special type of
detector used in SEM and TEM. They are used primarily to reveal topographical
feature of a specimen. It has the resolving power <10 nm. These electrons have low
energy
Auger Electrons: These are special types of low energy electrons that carry
the information about the chemical nature (atomic composition) of the specimen.
These are generated from the upper layer of specimen. It is a powerful tool in the
material sciences for studying the distribution of the lighter numbered atomic
elements on the surface of the specimen. It has limited application in biological
sciences. It is specialized equipment known as scanning auger electron
spectrometer.
Applications of Scanning Electron Microscopy Topography: The surface
features of an object or “how it looks”, its texture; direct relation between these
features and materials properties (hardness, reflectivity... etc.) Morphology: The
shape and size of the particles making up the object; direct relation between these
structures and materials properties (ductility, strength, reactivity...etc.)
Composition: The elements and compounds that the object is composed of and the
relative amounts of them; direct relationship between composition and materials
properties (melting point, reactivity, hardness...etc.) Crystallographic Information:
How the atoms are arranged in the object; direct relation between these
arrangements and materials properties (conductivity, electrical properties,
strength.etc.)
Advantages of SEM It gives detailed 3D and topographical imaging and the
versatile information garnered from different detectors. This instrument works
very fast. Modern SEMs allow for the generation of data in digital form. Most SEM
samples require minimal preparation actions
Disadvantages of SEM SEMs are expensive and large. Special training is
required to operate an SEM. The preparation of samples can result in artifacts.
SEMs are limited to solid samples. SEMs carry a small risk of radiation exposure
associated with the electrons that scatter from beneath the sample surface.
SCANNING TUNNELING MICROSCOPE (STM)
Scanning tunneling microscopy (STM) has been proven to be an extremely
powerful tool for studying the electronic structures of solid-state systems. The
STM topographic images, assisted by other surface analysis techniques with
chemical specifity, lead to the structural determination of clean and adsorbate-
covered surfaces. For example, the first atomically resolved STM image in history
confirmed the Si(111) 7 × 7 surface reconstruction and identified Takayanagi’s
dimer- adatomstacking-fault model as the correct Si(111) 7 × 7 surface structure.
Combining scanning tunneling microscopy with spectroscopy, a number of
beautiful experiments were carried out, e.g., to visualize the standing wave pattern
of the two-dimensional surface state electrons in an artificial quantum corral, to
provide the first direct spectroscopic signature of the Kondo resonance of an
isolated magnetic impurity in a non-magnetic host , and to map out the electronic
density of states inside a single vortex core of the Abrikosov flux lattice for a
conventional type II superconductor .
Furthermore, spatially resolved tunneling spectroscopy gave invaluable
insights into open questions in the physics of strongly correlated electronic
systems, such as the correlation between charge ordering and the metal-insulator
transition in magnetic manganites and the various ordering phases in high-
temperature cuprate superconductors. In this chapter, we summarize the
operating principles of scanning tunneling microscopy/spectroscopy and then
present our development of a magnetic-field-compatible, cryogenic, variable-
temperature STM for the study of cuprate superconductors.
OPERATION PRINCIPLES OF THE STM The central part of the STM is a sharp
conductive tip which is moved in a very precise and controlled manner in three
dimensions across the surface of the sample. A small voltage is applied between
tip and sample (typically a few mV to a few V,
depending on the sample material) and when the tip is brought close enough
to the sample (5-10 Å) a tunneling current flows (10 pA-10 nA). This is purely
quantum mechanical phenomenon (classically there would be no current, since
the region between tip and sample is insulating) as, as will be shown below, the
current is exponentially dependent on the distance between tip and sample,
varying approximately one order of magnitude per Ångström. By keeping the
current constant, the distance to the sample is held constant and if the tip is
scanned over the surface and its movement perpendicular to the sample required
to keep the current constant is registered, the result is a topographical image of
the sample surface.
Alternatively, the tip is scanned across the sample surface at a constant
average height and the current variations are registered (this requires a surface
that does not contain large protrusion into which the tip would crash). As will be
discussed below, the constant-current image is actually not a true topographical
image but an image of the surface electron density that, for certain sample
materials like metals, agrees fairly well with the true topography. The vertical
resolution is limited by the mechanical stability of the instrument and the
capability of the electronics to keep the current constant, something that is
facilitated by the exponential dependence on the distance between tip and sample.
Vertical resolution in the 0.01 Å range are readily accomplished. Horizontally, the
resolution is limited by the sharpness of the tip, and 10 Å resolution is routinely
achieved. Under favourable conditions a lateral resolution as high as 1 Å may be
achieved, such that individual atoms can be resolved.

One of the advantages of STM is the possibility to use most kinds of sample
materials, the only criterion being that the sample has to be conductive. STM has
been used for determination of the surface structure of metals and
semiconductors as well as for studies of nucleation and growth of thin films in
vacuum. Other applications include studies of biological materials and in situ
studies of electrochemical reactions. There are applications of the STM other than
pure topographical measurements, e.g. tunneling spectroscopy where different
electronic states of the surface may be mapped with very high spatial resolution.
Also emission of secondary particles such as electrons and photons induced by
electrons from the tunneling tip have been studied with high spatial resolution
using STM. Since the invention of the STM new exciting scanning probe
techniques using different probe-sample interactions to control the separation
have appeared. The most notable is the atomic force microscope (AFM) where the
force between the tip and the sample is used in the same manner as the tunneling
current in the STM. The resolution of the AFM is almost in the range of the STM
and the sample materials do not have to be conductive.
Mechanical considerations Due to the extremely small distances involved,
the mechanical rigidity and vibration isolation are of utmost importance. From the
first comparably voluminous STMs which required several stages of vibration
isolation, the development has gone towards small and rigid microscopes with
little or no vibration isolation at all. It has even been possible to fabricate working
miniature STMs on silicon wafers.
Tip The performance of the STM is much dependent on the condition of the
tip as it determines the resolution of the instrument. The tip consists of a
mechanically or electro-chemically sharpened wire of e.g. tungsten, gold, or
platinum. Ideally it has a mono atomic point, but the apex continuously
rearranges and sample atoms adsorb during operation. Since the image actually
is a convolution of the tip and the sample, the symmetry of the tip is reflected in
the recorded image and several different tips must be used for a given sample
before conclusions can be drawn about the surface structure. Sometimes
tunneling current flows simultaneously from several parts of the tip and the
resulting image is a superposition of more than one image. The problem with a
blunt, double tip is illustrated, where it can be seen that scanning the single
protrusion on the sample with the double tip results in an image showing two
“bumps”. When scanning with the sharp tip, the only distortion of the image is a
slight broadening of the “bump”.
SCANNING PROBE MICROSCOPY or ATOMIC FORCE MICROSCOPY (AFM)

Scanning probe microscopes (SPMs) are a family of tools used to make


images of nanoscale surfaces and structures, including atoms. They use a
physical probe to scan back and forth over the surface of a sample. During this
scanning process, a computer gathers data that are used to generate an image of
the surface. In addition to visualizing nanoscale structures, some kinds of SPMs
can be used to manipulate individual atoms and move them to make specific
patterns. SPMs are different from optical microscopes because the user doesn’t
“see” the surface directly. Instead, the tool “feels” the surface and creates an image
to represent it.
SPMs are a very powerful family of microscopes, sometimes with a resolution of
less than a nanometer. (A nanometer is a billionth of a meter.) An SPM has a probe
tip mounted on the end of a cantilever. The tip can be as sharp as a single atom.
It can be moved precisely and accurately back and forth across the surface, even
atom by atom. When the tip is near the sample surface, the cantilever is deflected
by a force. SPMs can measure deflections caused by many kinds of forces, including
mechanical contact, electrostatic forces, magnetic forces, chemical bonding, van
der Waals forces, and capillary forces. The distance of the deflection is measured by
a laser that is reflected off the top of the cantilever and into an array of photodiodes
(similar to the devices used in digital cameras). SPMs can detect differences in height
that are a fraction of a nanometer, about the diameter of a single atom. Scanning
probe microscope The tip is moved across the sample many times. This is why
these are called “scanning” microscopes. A computer combines the data to create
an image. The images are inherently colorless because they are measuring properties
other than the reflection of light.
However, the images are often colorized, with different colors representing
different properties (for example, height) along the surface. Scientists use SPMs in
a number of different ways, depending on the information they’re trying to gather
from a sample. The two primary modes are contact mode and tapping mode. In
contact mode, the force between the tip and the surface is kept constant. This allows
a scientist to quickly image a surface. In tapping mode, the cantilever
oscillates, intermittently touching the surface. Tapping mode is especially useful
when a scientist is imaging a soft surface. There are several types of SPMs. Atomic
force microscopes (AFMs) measure the electrostatic forces between the cantilever tip
and the sample. Magnetic force microscopes (MFMs) measure magnetic forces.
And scanning tunneling microscopes (STMs) measure the electrical current flowing
between the cantilever tip and the sample.
TRANSMISSION ELECTRON MICROSCOPY

Transmission electron microscopy (TEM) is a microscopy technique whereby


a beam of electrons is transmitted through an ultra thin specimen, interacting
with the specimen as it passes through. An image is formed from the interaction
of the electrons transmitted through the specimen; the image is magnified and
focused onto an imaging device, such as a fluorescent screen, on a layer of
photographic film, or to be detected by a sensor such as a CCD camera. The first
TEM was built by Max Kroll and Ernst Ruska in 1931, with this group developing
the first TEM with resolution power greater than that of light in 1933 and the first
commercial TEM in 1939.
The spatial resolution of the SEM depends on the size of the electron spot,
which in turn depends on both the wavelength of the electrons and the electron-
optical system which produces the scanning beam. The resolution is also limited
by the size of the interaction volume, or the extent to which the material interacts
with the electron beam. The spot size and the interaction volume are both large
compared to the distances between atoms, so the resolution of the SEM is not
high enough to image individual atoms, as is possible in the shorter wavelength
(i.e. higher energy) (TEM). Depending on the instrument, the resolution can fall
somewhere between less than 1 nm and 20 nm. By 2009, The world's highest
SEM resolution at high beam energies (0.4 nm at 30 kV) is obtained with the
Hitachi S-5500. In a TEM, a monochromatic beam of electrons is accelerated through
a potential of 40 to 100 kilovolts (kV) and passed through a strong magnetic field
that acts as a lens.
The resolution of a modern TEM is about 0.2 nm. This is the typical
separation between two atoms in a solid. This resolution is 1,000 times greater
than a light microscope and about 500,000 times greater than that of a human
eye. More recently, advances in aberration corrector design have been able to
reduce spherical aberrations and to achieve resolution below 0.5 Ångströms at
magnifications above 50 million times. Improved resolution allows for the imaging
of lighter atoms that scatter electrons less efficiently, such as lithium atoms in
lithium battery materials. The ability to determine the position of atoms within
materials has made the HRTEM an indispensable tool for nanotechnology
research and development in many fields, including heterogeneous catalysis and
the development of semiconductor devices for electronics and photonics.
The working principle of the Transmission Electron Microscope (TEM) is
similar to the light microscope. The major difference is that light microscopes use
light rays to focus and produce an image while the TEM uses a beam of electrons
to focus on the specimen, to produce an image. Electrons have a shorter
wavelength in comparison to light which has a long wavelength. The mechanism
of a light microscope is that an increase in resolution power decreases the
wavelength of the light, but in the TEM, when the electron illuminates the
specimen, the resolution power increases increasing the wavelength of the electron
transmission.
The wavelength of the electrons is about 0.005nm which is 100,000X shorter
than that of light, hence TEM has better resolution than that of the light
microscope, of about 1000times.This can accurately be stated that the TEM can
be used to detail the internal structures of the smallest particles like a virion
particle. Their working mechanism is enabled by the high-resolution power they
produce which allows it to be used in a wide variety of fields. It has three working
parts which include:
Electron gun
Image producing system Image recording system Electron gun
This is the part of the Transmission Electron Microscope responsible for producing
electron beams. Electrons are produced by a cathode that is a tungsten filament
that is V-shaped and it is normally heated. The tungsten filament is covered by a
control grid known as a Wehnelt cylinder made up of a central hole which lies
columnar to the tube. The cathode lies on top of or below the cylindrical column
hole. The cathode and the control grid are negatively charged with an end of
the anode which is disk-shaped that also has an axial hole.
When electrons are transmitted from the cathode, they pass through the columnar
aperture (hole) to the anode at high voltage with constant energy, which is efficient
for focusing the specimen to produce an accurately defined image.
It also has the condenser lens system which works to focus the electron beam on
the specimen by controlling the energy intensity and the column hole of the
electron gun. The TEM uses two condenser lenses to converge the beam of
electrons to the specimen. The two condenser lens each function to produce an
image i.e the first lens which has strong magnification, produces a smaller image
of the specimen, to the second condenser lens, directing the image to the
objectives.
Image- Producing system
Its made up of the objective lens, a movable stage or holding the specimen,
intermediate and projector lenses. They function by focusing the passing electrons
through the specimen forming a highly magnified image. The objective has a short
focal length of about 1-5mm and it produces an intermediate image from the
condenser which are transmitted to the projector lenses for magnification. The
projector lenses are of two types, i.e the intermediate lens which allows great
magnification of the image and the projector lens which gives a generally greater
magnification over the intermediate lens. To produce efficient high standard
images, the objectives and the projector lenses need high power supplies with high
stability for the highest standard of resolution.
Image-Recording System
Its made up of the fluorescent screen used to view and to focus on the image.
They also have a digital camera that permanently records the images captured
after viewing. They have a vacuum system that prevents the bombardment or
collision of electrons with air molecules disrupting their movement and ability to
focus. A vacuumed system facilitates the straight movement of electrons to the
image. The vacuumed system is made up of a pump, gauge, valves and a power
supply. The image that is formed is called a monochromatic image, which is
greyish or black and white. The image must be visible to the human eye, and
therefore, the electrons are allowed to pass through a fluorescent screen fixed at
the base of the microscope. The image can also be captured digitally and displayed
on a computer and stored in a JPEG or TIFF format. During the storage, the image
can be manipulated from its monochromatic state to a colored image depending
on the recording apparatus eg use of pixel cameras can store the image in color.
The presence of colored images allows easy visualization, identification, and
characterization of the images.
How does a Transmission Electron Microscope (TEM) work?
From the instrumentation described, the working mechanism is a sequential
process of the parts of the TEM mentioned above. To mean: A heated tungsten
filament in the electron gun produces electrons that get focus on the specimen
by the condenser lenses. Magnetic lenses are used to focus the beam of electrons
of the specimen. By the assistance offered by the column tube of the condenser
lens into the vacuum creating a clear image, the vacuum allows electrons to
produce a clear image without collision with any air molecules which may deflect
them. On reaching the specimen, the specimen scatters the electrons focusing
them on the magnetic lenses forming a large clear image, and if it passes through
a fluorescent screen it forms a polychromatic image. The denser the specimen,
the more the electrons are scattered forming a darker image because fewer
electron reaches the screen for visualization while thinner, more transparent
specimens appear brighter.
Applications of Transmission Electron Microscope (TEM)
TEM is used in a wide variety of fields From Biology, Microbiology,
Nanotechnology, forensic studies, etc. Some of these applications include:
To visualize and study cell structures of bacteria, viruses, and fungi To view
bacteria flagella and plasmids
To view the shapes and sizes of microbial cell organelles To study and differentiate
between plant and animal cells.
Its also used in nanotechnology to study nanoparticles such as ZnO nanoparticles
It is used to detect and identify fractures, damaged microparticles which further
enable repair mechanisms of the particles.
Advantages of Transmission Electron Microscope (TEM)
It has a very powerful magnification of about 2 million times that of the Light
microscope.
It can be used for a variety of applications ranging from basic Biology to
Nanotechnology, to education and industrial uses.
It can be used to acquire vast information on compounds and their structures. It
produces very efficient, high-quality images with high clarity.
It can produce permanent images.
It is easy to train and use the Transmission Electron Microscope Limitations of
Transmission Electron Microscope (TEM) Generally, the TEMs are very expensive
to purchase
They are very big to handle.
The preparation of specimens to be viewed under the TEM is very tedious.
The use of chemical fixations, dehydrators, and embedments can cause the
dangers of artifacts. They are laborious to maintain.
It requires a constant inflow of voltage to operate.
They are extremely sensitive to vibrations and electro-magnetic movements hence
they are used in isolated areas, where they are not exposed.
It produces monochromatic images, unless they use a fluorescent screen at the
end of visualization.
FIELD ION MICROSCOPE (FIM)
The field ion microscope (FIM) can image the atomic structure of
sharp metal tips with nanometer-sized radii and is notable as being the
earliest technique to produce atomically resolved images of matter in real
space. Using FIM, one can atomically characterize, and even engineer, the
sharp tips used in scanning probe microscopy (SPM). In this chapter, we
address the technical aspects of implementing these tips in SPM experiments
and review their application to scanning tunneling microscopy (STM), atomic
force microscopy (AFM), and SPM-based nanoindentation experiments.
Field emission microscopy (FEM) is an analytical technique used in
materials science to investigate molecular surface structures and their
electronic properties.
FEM was one of the first surface analysis instruments that
approached near-atomic resolution. This instrument approached to view a
surface on a scale of atomic dimensions and yet simultaneously allowed one
to follow rapid changes at the surface.

In its simplest form, FEM consist of a sharp needle emitter and a


fluorescent screen as shown by applying negative field to the emitter,
electrons are emitted from the surface of the emitter to the direction of the
screen. The image contrast appears due to the difference in current densities
of electron, which originated from the difference in work functions and electric
field on the emitter surface.
Requires a very good vacuum (ultra high vacuum) Emission is not due to the
clean surface. No vibrations Tip materials can tolerate the high electrostatic
fields and have high melting points
Surface Science (Electronic and Structural aspects) Field emission
has been extensively used in the characterization of surface structures and
electronic properties. The field ion microscope is a type of microscope that
can be used to image the arrangement of atoms at the surface of a sharp
metal tip. It was the first technique by which individual atoms could be
spatially resolved.The imaging gas atoms (He, Ne) near the tip are polarized
by the field and since the field is nonuniform the polarized atoms are attracted
towards the tip surface. The imaging atoms then lose their kinetic energy
performing a series of hops and accommodate to the tip temperature.
Eventually, the imaging atoms are ionized by tunneling electrons into the
surface and the resulting positive ions are accelerated along the field lines to
the screen to form a highly magnified image of the sample tip. FIM like Field
Emission Microscopy (FEM) . Both have same working conditions. However,
there are some essential differences as follows: The tip potential is positive.
The chamber is filled with a imaging gas (typically, He or Ne at 10-5 to 10-3
Torr). The tip is cooled to low temperatures (~20-80K).
Applications FIM has been used to study dynamical behavior of
surfaces and the behavior of adatoms on surfaces. The problems studied
include: Surface diffusion of adatoms , Adatom-adatom interactions, Step
motion, Equilibrium crystal shape, etc.
THREE-DIMENSIONAL ATOM PROBE (3DAP)
The development of three-dimensional (3-D), characterization
techniques with high spatial and mass resolution is crucial for understanding
and developing advanced materials for many engineering applications as well
as for understanding natural materials. In recent decades, atom probe
tomography (APT), which combines a point projection microscope and time-
offlight mass spectrometer, has evolved to be an excellent characterization
technique capable of providing 3-D nanoscale characterization of materials
with sub-nanometer scale spatial resolution, with equal sensitivity for all
elements. This review discusses the current state, as of APT instrumentation,
new developments in sample preparation methods, experimental procedures
for
different material classes, reconstruction of APT results, the current status of
correlative microscopy, and application of APT for micro structural
characterization in established scientific areas like structural materials as
well as new applications in semiconducting nanowires, semiconductor
devices, battery materials, catalyst materials, geological materials, and
biological materials.
NANOINDENTATION
Nanoindentation is called as The depth sensing indentation The
instrumented indentation Nanoindentation method gained popularity with
the development of, Machines that can record small load and displacement
with high accuracy and precision Analytical models by which the load-
displacement data can be used to determine modulus, hardness and other
mechanical properties.
Microindentation A prescribed load applied to an indenter in
contact with a specimen and the load is then removed and the area of the
residual impression is measured. The load divided by the by the area is
called the hardness. Nanoindentation A prescribed load is applied to an
indenter in contact with a specimen. As the load is applied, the depth of
penetration is measured. The area of contact at full load is determined by the
depth of the impression and the known angle or radius of the indenter. The
hardness is found by dividing the load by the area of contact. Shape of the
unloading curve provides a measure of elastic modulus.
UNIT– V:
APPLICATIONS OF NANO MATERIALS: Nano-electronics, Micro- and Nano-
electromechanical systems (MEMS/NEMS),Nano sensors, Nano catalysts, Food and
Agricultural Industry, Cosmetic and Consumer Goods, Structure and Engineering,
Automotive Industry, Water- Treatment and the environment, Nano-medical applications,
Textiles, Paints, Energy, Defense and Space Applications, Concerns and challenges of
Nanotechnology.
*************************************************************************************************
Applications of Nano Materials: Nano-electronics
The term nanoelectronics refers to the use of nanotechnology in electronic
components. These components are often only a few nanometers in size. However, the
tinier electronic components become, the harder they are to manufacture.
Nanoelectronics covers a diverse set of devices and materials, with the common
characteristic that they are so small that physical effects alter the materials ‘properties on
a nanoscale – inter-atomic interactions and quantum mechanical properties play a
significant role in the workings of these devices. At the nanoscale, new phenomena take
precedence over those that hold sway in the macro-world. Quantum effects such as
tunnelling and atomistic disorder dominate the characteristics of these nanoscale devices
The first transistors built in 1947 were over 1 centimetre in size; the smallest
working transistor today is 7 nanometers long – over 1.4 million times smaller (1 cm equals
10 million nanometers). The result of these efforts are billion-transistor processors where,
once industry embraces 7nm manufacturing techniques, 20 billion transistor-based
circuits are integrated into a single chip.
Nanoelectronics Devices Spintronics
Besides transistors, nanoelectronics devices play a role in data storage (memory).
Here, spintronics – the study and exploitation in solid-state devices of electron spin and
its associated magnetic moment, along with electric charge – is already an established
technology. Read more: "Graphene spintronics - from science to technology".
Spintronics also plays a role in new technologies that exploit quantum behaviours
for computing (read more: "Quantum computing moves forward with spintronics progress"
and "The birth of topological spintronics").
Optoelectronics
Electronic devices that source, detect and control light – i.e. optoelectronic devices
– come in many shapes and forms. Highly energy-efficient (less heat generation and power
consumption) optical communications are increasingly important because they have the
potential to solve one of the biggest problems of our information age: energy consumption.
In the field of nanotechnology, materials like nanofibers (see for instance: "Light-
emitting nanofibers shine the way for optoelectronic textiles") and carbon nanotubes have
been used and especially graphene has shown exciting potential for optoelectronic devices.
Displays
Display technologies can be grouped into three broad technology areas; Organic
LEDs, electronic paper and other devices intended to show still images, and Field Emission
Displays. For more, read our special section on Nanotechnology in Displays.
Wearable, flexible electronics
The age of wearable electronics is upon us as witnessed by the fast growing array of
smart watches, fitness bands and other advanced, next-generation health monitoring
devices such as electronic stick-on tattoos.
If current research is an indicator, wearable electronics will go far beyond just very
small electronic devices or wearable, flexible computers. Not only will these devices be
embedded in textile substrates but an electronics device or system could ultimately
become the fabric itself. Electronic textiles (e-textiles) will allow the design and production
of a new generation of garments with distributed sensors and electronic functions. Such
e-textiles will have the revolutionary ability to sense, act, store, emit, and move – think
biomedical monitoring functions or new man-machine interfaces – while ideally leveraging
an existing low-cost textile manufacturing infrastructure (see for instance "wearing single-
walled carbon nanotube electronics on your skin", a "temporary tattoo to monitor glucose
levels" or "graphene Nanosensors tattoo on teeth monitors bacteria in your mouth").
Nanoelectronics in Energy
Solar cells and supercapacitors are examples of areas where nanoelectronics is
playing a major role in energy generation and storage. To learn more read our detailed
sections on Nanotechnology in Energy and Graphene Nanotechnology in Energy.
Molecular Electronics
Distinct from nanoelectronics, where devices are scaled down to nanoscale levels,
molecular electronics deals with electronic processes that occur in molecular structures
such as those found in nature, from photosynthesis to signal transduction.
Molecular electronics aims at the fundamental understanding of charge transport
through molecules and is motivated by the vision of molecular circuits to enable miniscule,
powerful and energy efficient computers (see for instance: "Adding an optoelectronic
component to molecular electronics").
Applications of Nano-electromechanical systems
Nanoelectromechanical systems (NEMS) have advanced the technologies in a wide
spectrum of fields, including nonlinear dynamics, sensors for force detection, mass
spectrometry, inertial imaging, calorimetry, and charge sensing. Due to their low power
consumption, fast response time, large dynamic range, high quality factor, and low mass,
NEMS have achieved unprecedented measurement sensitivity. For optimized system
functionalization and design, precise characterization of material properties at the
nanoscale is essential. In this thesis, we will discuss three applications of NEMS:
mechanical switches, using anharmonic nonlinearity to measure device and material
properties, and mass spectrometry and inertial imaging.
The first application of NEMS is NEMS switches, switches with physical moving
parts. Conventional electronics, based largely on silicon transistors, is reaching a physical
limit in both size and power consumption. Mechanical switches provide a promising
solution to surpass this limit by forcing a jump between the on and off states. Graphene,
which is a single sheet of carbon atoms arranged in a hexagonal structure, has high
mechanical strength and strong planar bonding, making it an ideal candidate for
nanoelectromechanical switches. In addition, graphene is conductive, which decreases
resistive heating at the contact area, therefore reducing bonding issues and subsequently
reducing degradation. We demonstrate using exfoliated graphene to fabricate suspended
graphene NEMS switches with successful switching.
The second application of NEMS is the use of mechanical nonlinearity to measure
device and material properties. While the nonlinear dynamics of NEMS have been used
previously to investigate the longitudinal speed of sound of materials at nano- and micro-
scales, we correct a previously attempted method that employs the anharmonicity of
NEMS arising from deflection-dependent stress to interrogate the transport of RF acoustic
phonons at nanometre scales. In contrast to existing approaches, this decouples intrinsic
material properties, such as longitudinal speed of sound, from properties associated with
linear dynamics, such as tension, of the structure. We demonstrate this approach through
measurements of the longitudinal speed of sound in several NEMS devices composed of
single crystal silicon along different crystal orientations. Good agreement with literature
values is reported.
The third application of NEMS is mass spectrometry and inertial imaging. Currently,
only doubly clamped beams and cantilevers have been experimentally demonstrated for
mass spectrometry. We extend the one-dimension model for mass spectrometry to a novel
method for inertial imaging. We further extend the theory of mass spectrometry and
inertial imaging to two dimensions by using a plate geometry. We show that the mode
shape is critical in performing NEMS mass spectrometry and inertial imaging, and that
the mode shapes in plates deviate from the ideal scenario with isotropic stress. We
experiment with various non-ideal conditions to match non-ideal mode shape observed.
Applications of micro-electromechanical systems:
Microelectromechanical system (MEMS) are used in a wide range of sensors,
actuators, generators, energy sources, biochemical and biomedical systems and
oscillators. Some examples of MEMS applications in engineering product design include:
MEMS microphone
Sensors such as MEMS accelerometers, MEMS gyroscopes, MEMS pressure
sensors, MEMS tilt sensors and other types of MEMS resonant sensors. Actuators such
as MEMS switches, micro-pumps, micro-levers and micro-grippers. Generators and
energy sources such as MEMS vibration energy harvesters, MEMS fuel cells and MEMS
radioisotope power generators. Biochemical and biomedical systems such as MEMS
biosensors, lab-on-chips, and MEMS air microfluidic and particulate sensors. MEMS
oscillators for accurate timekeeping and frequency control applications.
MEMS optical switch
At an even smaller nanometre scale, the fabrication technology morphs into a
nanoelectromechanical system (NEMS). Furthermore, where MEMS is integrated with
other technologies, various combinatory embodiments can take form, such as, biomes
where biochemical and biomedical systems are realised on microfabricated devices, micro-
opto-electro-mechanical system (MOEMS) or Opto MEMS where optical systems such as
micro-mirrors are integrated to manipulate or sense light at the microscopic scale, radio
frequency microelectromechanical system (RFMEMS) typically involves close integration
with semiconductor microelectronics to provide RF transduction and switching
capabilities.
Applications of Nano Sensors
Nanosensors can be chemical sensors or mechanical sensors. They are used:
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Always Have, Now They Just Call it Nanotech Scientists Review Impact of Nanosensors for
Cardiovascular Diseases Diagnosis Atomic Force Microscopes (AFM) What They Are, How
They Work and What They Are Used For To detect various chemicals in gases for pollution
monitoring For medical diagnostic purposes either as bloodborne sensors or in lab-on-a-
chip type devices
To monitor physical parameters such as temperature, displacement and flow As
accelerometers in MEMS devices like airbag sensors To monitor plant signalling and
metabolism to understand plant biology To study neurotransmitters in brain for
understanding neurophysiology Nanosensors aid in the progression of fields such as
medical technology; precision agriculture; urban farming; plant nanoionics; prognostics
and diagnostics; SERS-based sensors; and many industrial applications.
Nanosensors include:
Carbon Nanotube–Based Fluorescent Nanosensors, Quantum Dot–Based
Fluorescent Nanosensors, DNA-Based Fluorescent Nanosensors, Peptide-Based
Fluorescent Nanosensors, Plasmon Coupling–Based Nanosensors, Plasmonic Enhancing–
/Quenching–Based Nanosensors, magnetic Resonance Imaging-Based Nanosensors,
Photoacoustic-Based Nanosensors, Multimodal Nanosensors (synergistic Nanosensors
with multiple modalities to overcome individual challenges), How Nanosensors Work
An analyte, sensor, transducer, and detector are the components of a sensor system,
with feedback from the detector to the sensor. Sensitivity, specificity and ease of execution
are the main goals in designing a sensor. Nanosensors typically work by monitoring
electrical changes in the sensor materials. For example, carbon nanotube-based sensors
work in this way. When a molecule of nitrogen dioxide (NO2) is present, it will strip an
electron from the nanotube, which in turn causes the nanotube to be less conductive.
If ammonia (NO3) is present, it reacts with water vapor and donates an electron to
the carbon nanotube, making it more conductive. By treating the nanotubes with various
coating materials, they can be made sensitive to certain molecules and immune to others.
Like chemical Nanosensors, mechanical Nanosensors also tend to measure
electrical changes. The Nanosensors used in the MEMS systems that car airbags depend
upon are monitoring changes in capacitance. These systems have a miniscule, weighted
shaft attached to a capacitor. The shaft bends with changes in acceleration and this is
measured as changes in capacitance. Nanosensors have been developed to the point of
measurement at the single-molecule level.
Applications of Nano catalysts
Nano catalysis is a rapidly growing field which involves the use of nanomaterials as
catalysts for a variety of homogeneous and heterogeneous catalysis applications.
Heterogeneous catalysis represents one of the oldest commercial practices of nanoscience;
nanoparticles of metals, semiconductors, oxides, and other compounds have been widely
used for important chemical reactions.
Although surface science studies have contributed significantly to our fundamental
understanding of catalysis, most commercial catalysts, are still produced by "mixing,
shaking and baking" mixtures of multi-components; their nanoscale structures are not
well controlled and the synthesis-structure-performance relationships are poorly
understood. Due to their complex physico-chemical properties at the nanometre scale,
even characterization of the various active sites of most commercial catalysts proves to be
elusive.
A key objective of nano catalysis research is to produce catalysts with 100%
selectivity, extremely high activity, low energy consumption, and long lifetime. This can be
achieved only by precisely controlling the size, shape, spatial distribution, surface
composition and electronic structure, and thermal and chemical stability of the individual
nanocomponents. In this article, the exciting opportunities of nano catalysis in chemical
and refining processes, as well as the challenges in developing nanostructured catalysts
for industrial applications, are discussed.
The field of nano catalysis (the use of nanoparticles to catalyse reactions) has
undergone an explosive growth during the past decade, both in homogeneous and
heterogeneous catalysis. Since nanoparticles have a large surface-to-volume ratio
compared to bulk materials, they are attractive candidates for use as catalysts.
In homogeneous catalysis, transition metal nanoparticles in colloidal solutions are
used as catalysts. In this type of catalysis, the colloidal transition metal nanoparticles are
finely dispersed in an organic or aqueous solution, or a solvent mixture.
Common Synthesis Methods for Colloidal Nanoparticles
The colloidal nanoparticle solutions must be stabilized in order to prevent
aggregation of the nanoparticles and also to be good potential recyclable catalysts. Metal
colloids are very efficient catalysts because a large number of atoms are present on the
surface of the nanoparticles. The method that is used in synthesizing transition metal
nanoparticles in colloidal solutions is very important for catalytic applications. The
reduction method employed controls the size and the shape of the transition metal
nanoparticles that are formed, which are very important in catalytic applications.
Applications of Nanotechnology in food industry
Nanomaterials are well designed as colour or flavour additives, preservatives, or
carriers for food supplement (i.e. nanoencapsulation and nano emulsion), including
animal feed products. The unique properties of engineered nanomaterials offer great
advantages for food processing as ingredients or supplement. Additionally, inorganic oxide
chemicals such as SiO2 (E551), MgO (E530), and TiO2 (E171) are permitted by the U.S.
FDA as anti-caking agent, food flavour carrier, and food colour additives. For instance,
TiO2 is widely used as additive in foods such as gum, white sauces, cake icing, candy and
puddings [19]. Current authorizations on the chemicals for food processing are all based
on conventional particle size, except carbon black (authorized by EC 10/2011 but no
longer authorized by the U.S. FDA) and titanium nitride. However, it is common to detect
those chemicals used in foods in nanometre scale.
In addition to food products directly serving human beings, animal feeds play a
significant role in the global food industry, ensuring economic and safe production of
animal products throughout the world. Copper oxide, iron oxide, and zinc oxide now have
been categorized as “generally recognized as safe” (GRAS) by the U.S. FDA as nutritional
dietary supplement in animal feeds. The European Food Safety Authority (EFSA) Panel on
Additives and Products or Substances used in Animal Feed (FEEDAP Panel) also concludes
the use of decapper oxide (Cu2O or copper(I) oxide) as nutritional supply for all animal
species is of no concern for consumer safety .
Food packaging
Food contact materials are intended to directly contact food products during
manufacturing, transportation, and storage. Nanotechnology as novel solution now has
been widely studied and developed for food packaging in food industry . Nanomaterials
designed for food packaging possess many advantages when compared to conventional
packaging materials. Among many novel nanomaterials, nano clay is one of the most
widely used and studied for food packaging due to their mechanical, thermal, and barrier
properties, and low cost. For instance, 1 wt % bentonite clay/poly (vinyl alcohol) loaded
nanocomposite membrane significantly enhanced permeance with a water permeance of
6500 gpu and a selectivity value of 46.
Another study from showed 3% nano clay loaded woven carbon fibre
/compatibilized polypropylene nanocomposites significantly improved interlaminar
fracture toughness and elevated glass transition temperature increased by about 6 °C [24].
Additionally, significant enhancement of corrosion resistance was reported for epoxy/clay
nanocomposites Nano clays are developed into several subclasses including
montmorillonite, bentonite, kaolinite, hectorite, and halloysite, depending on the
physiochemical properties of the nanomaterials. Montmorillonite and bentonite are now
listed as GRAS and in Effective Food Contact Substance (FCS) notifications by the U.S.
FDA. FCS acts as the U.S. FDA effective premarket notifications for food contact
substances that have been demonstrated to be safe for their intended use. However, recent
reports indicate potential migration risks associated with nano clay packaging
Applications of Nanotechnology in food industry
In agriculture, nanotechnology is employed to increase food production, with
equivalent or even higher nutritional value, quality and safety. Efficient use of fertilizers,
pesticides, herbicides and plant growth factors/regulators are the most important ways to
improve crop production. Controlled release of pesticides, herbicides and plant growth
regulators can be achieved via the usage of nanocarriers. For instance, poly (epsilon-
caprolactone) Nano capsules have been recently developed as herbicide carrier for
atrazine.
The treatment of mustard plants (Brassica juncea) with atrazine loaded poly
(epsilon-caprolactone) Nano capsules enhanced the herbicidal activity compared to
commercial atrazine, showing a drastic decrease in net photosynthetic rates and stomatal
conductance, a significant increase of oxidative stresses, and ultimately weight loss and
growth reduction of tested plants . Similarly, other nanocarriers like silica NPs [52] and
polymeric NPs have also been developed as modified release system to deliver pesticides
in a controlled manner. Nanoscale carriers can be utilized to perfectly achieve the delivery
and slow release of these species. Such strategies are known as “precision farming” that
improves crop yields but not damage soil and water.
Most importantly, application of nanoencapsulation can lower dosage of the
herbicide, without any loss of efficiency, which benefits environment. In addition to
nanocarriers, nanoparticle-mediated gene or DNA transfer in plants was used to develop
insect-resistant varieties. More details can be found in previously published reviews ].
Moreover, certain nanomaterials per se can act as pesticides with enhanced toxicity and
sensitivity. Metal oxide nanomaterials like ZnO, TiO2, and CuO are widely studied to
protect plant from pathogen infections owing to their intrinsic toxicity. We take ZnO NPs
as an example. It has been demonstrated that ZnO NPs can effectively inhibit growth of
microbes such as Fusarium graminearum, Aspergillus flavus [58], Aspergillus niger [58],
Aspergillus fumigatus.
Applications of Nanotechnology in cosmetics
Nanotechnology incorporation in cosmetic formulation is considered as the hottest
and emerging technology available. Cosmetic manufacturers use nanoscale size
ingredients to provide better UV protection, deeper skin penetration, long-lasting effects,
increased color, finish quality, and many more. Micellar nanoparticles is one of the latest
field applied in cosmetic products that becoming trending and widely commercialized in
local and international markets. The ability of nano emulsion system to form small
micellar nanoparticles size with high surface area allowing to effectiveness of bioactive
component transport onto the skin. Oil in water nano emulsion is playing a major role as
effective formulation in cosmetics such as make-up remover, facial cleanser, anti-aging
lotion, sun-screens, and other water-based cosmetic formulations. The objective of this
review is to critically discuss the properties, advantageous, and mechanism of micellar
nanoparticles formation in nano emulsion system. Therefore, present article introduce and
discuss the specific benefits of nano emulsion system in forming micellar nanoparticles
for cosmetic formulation which become major factors for further development of micellar-
based cosmetic segments.
Applications of Nanotechnology in consumer goods
Nanoparticles are now being used in the manufacture of scratchproof eyeglasses,
crack- resistant paints, anti-graffiti coatings for walls, transparent sunscreens, stain-
repellent fabrics, self-cleaning windows and ceramic coatings for solar cells. Nanoparticles
can contribute to stronger, lighter, cleaner and “smarter” surfaces and systems. At the
nanoscale, the properties of particles may change in unpredictable ways. Nanoparticles of
titanium oxide used in sunscreens, for example, have the same chemical composition as
the larger white titanium oxide particles used in conventional products for decades, but
nanoscale titanium oxide is transparent. Antimony - tin oxide provides another example
since nanoparticles of this oxide are incorporated into a coating to provide scratch-
resistance and offer transparent protection from ultra-violet radiation, not seen with larger
size particles.
There are several safety concerns in the automotive sector relating to
nanotechnology. Nanoparticles as fillers in tyres can improve adhesion to the road,
reducing the stopping distance in wet conditions. The stiffness of the car body can be
improved by use of nanoparticle-strengthened steels. New sol-gel deposition methods
make it possible to apply, economically, nanometre thick antireflection layers of silicon
dioxide or other materials onto displays or panes. Ultra-thin transparent layers on a silver
base can be used for eatable, and therefore mist and ice-free, window panes. Transparent
and light materials could substitute car body parts that reduce all-round vision at the
moment.
Applications of Nanotechnology in Structure and Engineering
Nanotechnology has the potential to make construction faster, safer, cheaper and
more varied, resulting in smart construction. Automation of nanotechnology construction
can allow for the creation of structures from advanced homes to gigantic skyscrapers
much more quickly and at much lower cost and higher efficiency. In the near future,
Nanotechnology can be used to sense cracks in foundations of structures and can send
nanobots to repair them. It can also provide self-powered failure prediction and prevising
mechanisms for high capital structures.
This paper explores the vision in making of smart and innovative infrastructure and
leading a smart city with the help of application of nanotechnology in civil structures. The
study of nanoscience and various nanoparticles and their implementation in construction
field is illustrated in this paper. The article further emphasizes more on the futuristic
demand and application of nanotechnology in constructing smart structures. The paper
is managed to be written in simple language for easy grasping.
Development of structural engineering, daring structures with record spans or
heights, meets two serious obstacles—the limitations of traditionally used materials and
the need of continuous monitoring of new structures subjected to complex loads, including
those of dynamic nature. Considering the responsibility for the life of people and the
budget of new structures, the need of constant monitoring is inevitable. This is why
structural engineers seek for new solutions; among them, smart structures based on self-
monitoring materials seem to be one of the most attractive proposals.
It is still an unexplored area, but current research shows a high potential of the use
of composites reinforced by carbon-based nanomaterials as self-sensing structural
materials. Nanomaterials also influence other important features of structural materials,
such as microstructure, mechanical, and transport-related properties. In this chapter, we
present the state of art of the use of nanomaterials in structural engineering in various
areas including mechanical and electrical properties as well as issues referring to
durability.
Applications of Nanotechnology in Automotive Industry
Nanotechnology will play a major role in the car industry; but don't hold your breath
to see anything like the Volkswagen Nano Spyder futuristic concept car anytime soon.
This entrance to the 2006 Los Angeles Design challenge was supported by hydrogen fuel
cells, solar power, wheel-mounted electric motors and inflatable organic body panels
combine to form the unusual shape of the two-seater concept.
Nanotechnology – the creation and use of devices and machines on almost an atomic
level – is likely to be the driving force behind the next great revolution to benefit
humankind. The actual definition of nanotechnology can be quite broad, generally, in
scientific and engineering terms, nanotechnology is the manipulation of matter with at
least one dimension sized from 1 to 100 nanometers (0.000000001 m). That really does
put it on an atomic scale, though the products that can be constructed in this way may
be a little larger and can range from microscopic to anything under a millimetre.
While this kind of technology will have applications in many fields, there are likely
to be huge advantages in the field of cars and motoring and in the near future,
nanotechnology is likely to have a massive impact on the world of driving and vehicles.
It is a fact that nanotechnology can impact so many areas of motoring makes it one
of the most important up and coming technologies, and it has attracted the attention of a
great number of researchers. This has led to a growing number of breakthroughs in the
field, and even more possibilities for this exciting and highly flexible area of science to
push different fields of motoring forward. But where is nanotechnology having the greatest
influence in car manufacture
We ask a lot of our internal combustion engines in terms of both increased
performance and decreased size and weight. Those two elements together would usually
mean disaster for a high-performance engine, but nano-engineering has allowed us to do
both, and safely. Engine blocks, which house the fundamental moving parts of the
mechanism, were traditionally made of cast iron, because it was the only practical material
that could resist the high temperatures and pressures that were produced in the heart of
an engine. But engineers soon found that certain grades of aluminium – which weighs
around a third that of cast iron – were found to be suitable too.
But now, engineers have learned how to manipulate aluminium’s on an atomic level
– nanoengineering – to create materials that are both stronger while being more lightweight
than even the current batch of strong aluminium alloys. This makes them even more fuel
efficient while having an increased durability, even in the increasingly hostile conditions
found in modern engines. It is a fact that an internal combustion engine performs better
and is more efficient at higher temperatures, so this is always a goal for engine designers.
We are now also experiencing methods of placing ultra-thin layers of engineering ceramics
on metal substrates, creating a surface that is capable of withstanding higher
temperatures and wear situations.
Manipulation of either the fundamental structure of the engine block material, or
the surface architecture – or both, even – gives designers far greater scope in heat
dissertation, wear characteristics, and strength at elevated temperatures. We have also
seen advances in motor oils, particularly in respect to their ability to withstand the
punishing environments of modern engines. Nano-manipulation has created a new breed
of oils that are able to cling to internal surfaces for longer, meaning that it is in the right
place when the engine starts, so that it offers protection right from the start.
Nanotechnology oils are also able to put up with much greater use as the tolerances
between engine parts decreases and they operate closer together.
Applications of nanotechnology in water treatment
The industrial contamination, along with domestic effluents, agricultural and urban
runoff are contaminating rivers and making it difficult for conventional water treatment
to remove all the pollutants. This contamination can impact in the quality of rivers, in the
quality of life of aquatic animals and can impact in the human health through the
consumption of water. In order to improve the water quality, nanotechnology has been
studied as an alternative to better remove contaminants, such as, heavy metals, oily water
separation and antimicrobial activity. Besides, with the increase in industrialization along
with the contamination of rivers, seawater could be an interesting alternative for drinking
water source after adequate treatment. Nanomaterials are being studied as a possibility
to remove salt from seawater, making it possible to drink. However, there is a need to
elucidate the potential risks to the environment that these nanomaterials can cause.
Therefore, the aim of this review is to describe some applications of nanotechnology in
water treatment regarding metals, oil removal from water, antimicrobial activity and
desalination in order to improve water quality, as well, as discuss their potential risk to
the environment.
Applications of Nanotechnology in environment
Nanotechnology has enormous potential for providing innovative solutions to a wide
range of environmental issues. These include improved methods for reducing pollution,
water treatment, environmental sensing, remediation, and making alternative energy
sources more cost-effective. The unique properties of engineered nanomaterials enable
these novel technologies for meeting the environmental challenges in a sustainable way.
This review broadly focuses on the environmental applications of engineered
nanomaterials in a sustainable approach and also emphasizes the future opportunities
for their application in the natural environmental systems.
Generating less pollution during the manufacture of materials. One example of this
is how researchers have demonstrated that the use of silver nanoclusters as catalysts can
significantly reduce the polluting by-products generated in the process used to
manufacture propylene oxide. Propylene oxide is used to produce common materials such
as plastics, paint, detergents and brake fluid.
Producing solar cells that generate electricity at a competitive cost. Researcher have
demonstrated that an array of silicon nanowires embedded in a polymer results in low
cost but high efficiency solar cells. This, or other efforts using nanotechnology to improve
solar cells, may result in solar cells that generate electricity as cost effectively as coal or
oil. Increasing the electricity generated by windmills. Epoxy containing carbon nanotubes
is being used to make windmill blades. The resulting blades are stronger and lower weight
and therefore the amount of electricity generated by each windmill is greater.
Cleaning up organic chemicals polluting groundwater. Researchers have shown that
iron nanoparticles can be effective in cleaning up organic solvents that are polluting
groundwater. The iron nanoparticles disperse throughout the body of water and
decompose the organic solvent in place. This method can be more effective and cost
significantly less than treatment methods that require the water to be pumped out of the
ground.
Cleaning up oil spills. Using photocatalytic copper tungsten oxide nanoparticles to
break down oil into biodegradable compounds. The nanoparticles are in a grid that
provides high surface area for the reaction, is activated by sunlight and can work in water,
making them useful for cleaning up oil spills. Clearing volatile organic compounds (VOCs)
from air. Researchers have demonstrated a catalyst that breaks down VOCs at room
temperature. The catalyst is composed of porous manganese oxide in which gold
nanoparticles have been embedded.
Reducing the cost of fuel cells. Changing the spacing of platinum atoms used in a
fuel cell increases the catalytic ability of the platinum. This allows the fuel cell to function
with about 80% less platinum, significantly reducing the cost of the fuel cell. Storing
hydrogen for fuel cell powered cars. Using graphene layers to increase the binding energy
of hydrogen to the graphene surface in a fuel tank results in a higher amount of hydrogen
storage and a lighter weight fuel tank. This could help in the development of practical
hydrogen-fuelled cars.
Applications of Nanotechnology in nano medical
The use of nanotechnology in medicine offers some exciting possibilities. Some
techniques are only imagined, while others are at various stages of testing, or actually
being used today. Nanotechnology in medicine involves applications of nanoparticles
currently under development, as well as longer range research that involves the use of
manufactured nano-robots to make repairs at the cellular level (sometimes referred to as
nanomedicine).

Whatever you call it, the use of nanotechnology in the field of medicine could
revolutionize the way we detect and treat damage to the human body and disease in the
future, and many techniques only imagined a few years ago are making remarkable
progress towards becoming realities. Nanotechnology in Medicine Application: Drug
Delivery. One application of nanotechnology in medicine currently being developed
involves employing nanoparticles to deliver drugs, heat, light or other substances to
specific types of cells (such as cancer cells). Particles are engineered so that they are
attracted to diseased cells, which allows direct treatment of those cells. This technique
reduces damage to healthy cells in the body and allows for earlier detection of disease.
For example researchers at North Carolina State University are developing a method
to deliver cardiac stem cells to damaged heart tissue. They attach nanovesicles that are
attracted to an injury to the stem cells to increase the amount of stem cells delivered to
an injured tissue. Read more about nanomedicine in drug delivery. Nanotechnology in
Medicine Application: Diagnostic Techniques Researchers John Hopkins University are
using nanoimprint lithography to manufacture a sensor that can detect covid-19 and other
viruses that can be used with hand held testing device for quick results.
Researchers at Worcester Polytechnic Institute are using antibodies attached to
carbon nanotubes in chips to detect cancer cells in the blood stream. The researchers
believe this method could be used in simple lab tests that could provide early detection of
cancer cells in the bloodstream. A test for early detection of kidney damage is being
developed. The method uses gold nanorods functionalized to attach to the type of protein
generated by damaged kidneys. When protein accumulates on the nanorod the colour of
the nanorod shifts. The test is designed to be done quickly and inexpensively for early
detection of a problem.
Nanotechnology in Medicine Application: Antibacterial Treatments Researchers at
the University of Houston are developing a technique to kill bacteria using gold
nanoparticles and infrared light. This method may lead to improved cleaning of
instruments in hospital settings. Researchers at the University of Colorado Boulder are
investigating the use of quantum dots to treat antibiotic resistant infections.
Nanotechnology in Medicine Application: Wound Treatment Researchers at the University
of Wisconsin have demonstrated a bandage that applies electrical pulses to a wound using
electricity produced by nanogenerators worn by the patient.
For trauma patients with internal bleeding another way to reduce the blood loss is
needed. Researchers at Chase Western Reserve University are developing polymer
nanoparticles that act as synthetic platelets. Lab tests have shown that injection of these
synthetic platelets significantly reduces blood loss. Read more about nanomedicine wound
treatments. Nanotechnology in Medicine Application: Cell Repair Nanorobots could
actually be programmed to repair specific diseased cells, functioning in a similar way to
antibodies in our natural healing processes. Read about design analysis for one such cell
repair nanorobot in this article: The Ideal Gene Delivery Vector: Chromalloy, Cell Repair
Nanorobots for Chromosome Repair Therapy
Applications of nanotechnology in textile industry
Nanotechnology is a growing interdisciplinary technology often seen as a new
industrial revolution. Nanotechnology (NT) deals with materials 1 to 100 nm in length. The
fundamentals of nanotechnology lie in the fact that the properties of materials drastically
change when their dimensions are reduced to nanometre scale. Nowadays also the textile
industry has discovered the possibilities of nanotechnology. So, we can define
nanotechnology in textile as the understanding, manipulation, and control of matter at
the above-stated length, such that the physical, chemical, and biological properties of the
materials (individual atoms, molecules, and bulk matter) can be engineered, synthesized,
and altered to develop the next generation of improved materials, devices, structures, and
systems. It is used to develop desired textile characteristics, such as high tensile strength,
unique surface structure, soft hand, durability, water repellence, fire retardancy,
antimicrobial properties, and the like.
Modern Application of Nanotechnology in Textile Industry:
Nanotechnology is increasingly attracting worldwide attention because it is widely
perceived as offering huge potential in a wide range of end uses. The unique and new
properties of nano materials have attracted not only scientists and researchers but also
businesses, due to their huge economical potential.
Nanotechnology also has real commercial potential for the textile industry. This is
mainly due to the fact that conventional methods used to impart different properties to
fabrics often do not lead to permanent effects, and will lose their functions after laundering
or wearing. Nanotechnology can provide high durability for fabrics, because nano-particles
have a large surface area-to-volume ratio and high surface energy, thus presenting better
affinity for fabrics and leading to an increase in durability of the function. In addition, a
coating of nano-particles on fabrics will not affect their breath ability or hand feel.
Applications of nanotechnology in paints industry
Nanomaterials are thought to improve these functionalities, i.e. water/dirt repellent
“easy to clean”, UV-protection, antimicrobial resistance, scratch resistance or extending
the paints’ lifespan. Nanomaterials in paints Nanomaterials are expected to improve the
existing properties of paints due to their specific structural characteristics such as size,
shape and greater surface area.
Currently, the most relevant nanomaterials for the paint industry are nanoscale
titanium dioxide and silicon dioxide; but silver, zinc oxide, aluminium oxide, cerium
dioxide, copper oxide, and magnesium oxide are also under investigation. The table
provides an overview of potential functional benefits by integrating nanomaterials into the
paints. Depending on the type of paint and the desired functionality, nanomaterials can
be integrated as free powders, as stabilised particles in a suspension/dispersion or
incorporated into master batches or granulate resulting in the nanomaterial being firmly
embedded in the paint matrix.
There also exist paints or products that have a nanostructured surface, contain
nano porous materials or temporarily contain nanostructured particles (e.g. produced
from water glass during the drying of the paint). As these end products do not contain any
nanomaterial, they are considered to pose no nano-specific risk to humans or the
environment. Effects of nanomaterials in paints Nano titanium dioxide is used in paint to
exploit two of its excellent properties: (i) photocatalytic activity and (ii) UV-protection. The
combination of the photocatalytic effect, along with hydrophilic properties results in a
paints’ self-cleaning effect. The surface will no longer need regular cleaning as the water
and dirt will no longer stick on it. However, studies have shown that the use of
photocatalytic nano titanium dioxide in organic paints leads to the degradation of the
binder by UV irradiation. For this reason, the rutile type is preferred in organic facade
coatings for UV-protection.
The addition of nano silicon dioxide to paints can improve the macro- and micro-
hardness, abrasion, scratch and weather resistance. Adding nano silicon dioxide to
polymeric resins creates paints with excellent abrasion properties. However, it decreases
the elasticity of the paints, which is needed to resist the swelling and shrinking associated
with temperature and humidity changes. Surfaces coated with nano silver containing
paint provide excellent antimicrobial properties against bacteria and human pathogens.
However, in contrast to indoor paint, the bactericidal efficiency of nano silver in paints for
outdoor application seems to be insufficient due to the exposure to external conditions.
Studies have shown that nano silver as well as nano titanium dioxide, are not able to fully
prevent microbial and algal growth on test substrates in addition to being a poor deterrent
from possible fungal colonisation.
Applications of nanotechnology in energy industry
Energy is of great importance in human life because of its benefits as the main
resource for human activity. According to International Energy Agency (IEA), energy
demands are expected to continue increasing until 2030. Because energy demand will
never decrease, it is necessary to develop modern technology, such as nano based
technology, in order to obtain a more effective and efficient process to produce more
energy. The application of nano technology or nano material in the field of energy, which
involves lithium-ion battery, fuel cell, light emitting diode (LED), ultra-capacitor, and solar
cell (including Grätzel cell), is a hot topic in many scientific researches. Unfortunately, its
current development is hampered by the expensive cost of production compared to
conventional technologies. Therefore, priority should be given to nano technology in the
energy sector order to obtain higher efficiency, lower production cost, and easier in its
application.
Applications of nanotechnology in defence
Currently, most militaries of the advanced countries are utilizing nanotechnology in
research, projects, and applications. Nanotechnology can provide the army with stronger
and lighter ware, supports nanomedicines and bandages for wound healing, and stops
bleeding, silver-packed foods as antibacterial and antiviral, gas and biological sensing.
Despite this progress and improvement in nanotechnology, this technology has certain
risks when manufactured or even when applied and disposed of. In this chapter, a
comprehensive view of potential military applications of nanotechnology has been
addressed. It also highlighted the potential applications of the cutting-edge developments
of nanotechnology in defence. Protection armours, invisibility ware, fuel economy, lighter
and stronger craft/ships/vehicles manufacturing, and radar undetected planes and
submarines by electromagnetic camouflage are the most focused applications in
nanotechnology to developed Marin, Air force, and even battlefield army.
Applications of nanotechnology in space
Nanotechnology may hold the key to making space flight more practical.
Advancements in nanomaterials make lightweight solar sails and a cable for the space
elevator possible. By significantly reducing the amount of rocket fuel required, these
advances could lower the cost of reaching orbit and traveling in space. In addition, new
materials combined with Nanosensors and nanorobots could improve the performance of
spaceships, spacesuits, and the equipment used to explore planets and moons, making
nanotechnology an important part of the ‘final frontier.’ High-strength low-weight
composites, advanced electronics, and screens with low power consumption, a range of
physical sensors, multipurpose materials with embedded sensors, large surface materials,
and modern air purification filters and membranes are among the aerospace applications
for nanotechnology.
Concerns of Nanotechnology
Although most of the press coverage has been on the dangers of 'nano-goo' such as
self-replicating particles that get out of control, or 'nano-robots', the real risks are much
more simple, and real. The miniature size of nanomaterials and the way their surfaces are
modified to increase the ease with which they can interact with biological systems - the
very characteristics that make them attractive for applications in medicine and industry -
makes nanomaterials potentially damaging for humans and the environment.
Nanoparticles are likely to be dangerous for three main reasons:
Nanoparticles may damage the lungs. We know that 'ultra fine' particles from diesel
machines, power plants and incinerators can cause considerable damage to human lungs.
This is both because of their size (as they can get deep into the lungs) and also because
they carry other chemicals including metals and hydrocarbons in with them.
Nanoparticles can get into the body through the skin, lungs and digestive system. This
may help create 'free radicals' which can cause cell damage and damage to the DNA. There
is also concern that once nanoparticles are in the bloodstream they will be able to cross
the blood-brain barrier.
The human body has developed a tolerance to most naturally occurring elements
and molecules that it has contact with. It has no natural immunity to new substances and
is more likely to find them toxic. The danger of contact with nanoparticles is not just
speculation. As more research is undertaken, concerns increase. Here are some of the
recent findings: some nanoparticles cause lung damage in rats. Several studies have
shown that carbon nanotubes, which are similar in shape to asbestos fibres, cause
mesothelioma in the lungs of rats other nanoparticles have been shown to lead to brain
damage in fish and dogs German study found clear evidence that if discrete nanometre
diameter particles were deposited in the nasal region (in rodents in this case), they
completely circumvented the blood/brain barrier, and travelled up the olfactory nerves
straight into the brain inhaled carbon nanotubes can suppress the immune system by
affecting the function of T cells, a type of white blood cell that organises the immune
system to fight infections.
Challenges of Nanotechnology.
The most tremendous challenges in Nanotechnology are materials and properties
about Nanoscale. At present, nanotechnology has been widely applied to the area of drug
development. Some Nanoparticles could be toxic. The Nanoparticles are small, which will
cross the blood-brain barrier, a membrane that protects the brain from poisonous
chemicals in the bloodstream. It has 3D structures requires to design and manufacturing
process to achieve a consistent product. Nanosized products like transistors and
nanowires. Rapid DNA sequencing, Single-stranded genomic DNA or RNA, Organic and
Inorganic Nano composites, Safety and Risk Assessment of Nanotechnology

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