1

Synthesis, Processing, and

Application of Nanostructures

1.1  Introduction to Nanotechnology

During the past years scientists have achieved significant successes in
nano science and technology. Nanotechnology is a branch of sciences that
deals with fine structures and materials with very small dimensions—less
than 100 nm. The measurement unit of “nano” has been extracted from
the nano- prefix, which is a Greek word meaning “extremely fine.” One
nano (10 –9 m) is the length equivalent to 5 silicon atoms or 10 hydrogen
atoms aligned side by side. To introduce a perspective note the following
examples: A hydrogen atom is about 0.1 nm; a virus is about 100 nm; the
diameter of a red blood cell is 7000 nm; and the diameter of a human hair
is 10000 nm.1–3
Nanotechnology is a field of applied sciences focused on design, produc-
tion, detection, and employing the nanosize materials, pieces, and equip-
ment. Advances in nanotechnology lead to improvement of tools and
equipment as well as their application in human life. Nanoscience is the
study of the phenomena emerged by atomic or molecular materials with
the size of several nanometers to less than 100 nm. In chemistry this size
involves a range of colloids, micelles, polymer molecules, and structures
such as very large molecules or dense accumulation of the molecules. In the
physics of electrical engineering, nanoscience is strongly related to quan-
tum behavior or electron behavior in structures with nano sizes. In biol-
ogy and biochemistry, also, interesting cellular components and molecular
structures such as DNA, RNA, and intercellular components are considered
as nanostructures.4–7
Nanotechnology is applying the sciences in control of the phenomena with
molecular dimensions. In this range, materials properties are significantly
different than those of its mass state. These differences are related to design,
properties’ detection analysis, structures application, as well as tools and

1
2 Two-Dimensional Nanostructures

systems for nano shape and size control. In other words, nanoscience and
technology is a study field including

1. Advances in the methods for producing the materials and surface

analysis equipment for producing the materials and structures
2. Understanding the changes in physical and chemical properties in
order to materials fining
3. Using these properties for the development of new highly used
materials in the equipment

Alive cells are the best examples of machines working at the nano level. The
study field of the nanotechnology major is interconnected to physics, chem-
istry, materials science, microbiology, biochemistry, and molecular biology.
Integration of nanotechnology, biotechnology, and medical engineering
is demonstrated in the use of nano-size structures for disease prognosis,
defining the gene sequence, and medicine transport.8,9
The main applications of nanotechnology are

• Medicine: drug delivery and tissue engineering

• Chemistry and environmental studies: catalysts, filtration
• Energy: decrease in energy uses, increasing of the efficiency of the
products yielding batteries recycling energy, use of environmentally
friendly energy systems
• Information and communications: new semiconductors, new electri-
cal pieces, display monitors with low energy use, quantum computers
• Consumer goods: food production, safety, and packaging, self-
cleaner system, fibers and textiles, optical equipment, sport facilities

1.2  History of Nanotechnology

Use of nanotechnology by humans, contrary to the dominant belief, has a
long history. There is evidence implying the nanostructured nature of the blue
color used by the Mayans. Since then, Romans used these materials for fab-
rication of cups with live colors; they applied gold for dying these cups. One
of these cups was the Lycurgus cup that was made in 4 BC. This cup involves
gold and silver particles and reveals various colors once exposed to light. This
method was also used in the Middle Ages for making church windows.10,11
Among various scientific fields, biology was the first that entered this
realm. The basic mechanism of biological machines was nanodimensional
reactions. Mosquitoes, ants, and flies can be named as examples of natu-
ral nanomachines. However, the scientific account of nanotechnology varies
Synthesis, Processing, and Application of Nanostructures 3

from that explained above. Early investigations on nanoparticles stem from

Faraday. In 1811 working on the red colloid of Ag, he found that the red
colloid color depends on metallic particles sizes, and the gold and silver
found 2000 years ago were actually nanoparticles.
The use of nanostructured catalysts began 70 years ago. In the early 1940s
the evaporated and deposited nanoparticles of silicon were fabricated and
used as an alternative for tiny particles of black carbon for rubber reinforce-
ment in the United States and Germany. These products have a wide range of
applications, from dry milk used with coffee to car tires and optical fibers. In
the 1960s and 1970s, metallic nanopowders were made for information stor-
ing on film. In 1976, nanocrystals were invented by some researchers using
the complete gas evaporation method.
The first breakthrough in the history of nanotechnology originates from
the speech of Richard Feynman in a conference in 1959. In this conference, he
discussed materials manipulation in nano dimensions in his paper entitled
“There Are Plenty of Rooms in the Bottom.” Today this paper is used as part of
a nanotechnology committee’s regulation. He extracted his notion from biolog-
ical mechanisms, which are very tiny on one hand, and very active on the other.
He stated that “There is nothing that I can see in the physical laws that says the
computer elements cannot be made enormously smaller than they are now.”*
The first impetus for materials and structures’ fining arose from the elec-
tronics industry. Their goal was to industrialize their equipment to produce
tinier electronic tools on silicon chips with sizes of 40 to 70 nm. Nowadays,
nanoengineering is rapidly developing and introduces mechanical, cata-
lyzer, electrical, magnetic, optical, and electronic potentials.12–17

1.3  What Is a Nanomaterial?

A nanomaterial belongs to a group of substances that have exterior dimensions
or constituent phases (at least in one dimension) less than 100 nm; however,
most of their unique properties occur in dimensions less than 50 nm. With
respect to this definition, nanomaterials are divided into the following groups:18

1. Atomic clusters or nanoparticles

2. Nanolayers
3. Nanotubes and nanorods
4. Nanocrystals
5. Nanocomposites

* “There's Plenty of Room at the Bottom, An Invitation to Enter a New Field of Physics,”
Richard P. Feynman, transcript of the classic talk that Richard Feynman gave on December
29th 1959 at the annual meeting of the American Physical Society.
4 Two-Dimensional Nanostructures

Dimensionality classification of nanostructures (L < 100 – 500 nm)

Designation: dimensionality of NS kDlmn.. Dimensionality of elementary units

k ≥ l, m, n {k, l, m, n} = {0, 1, 2, 3}
Elementary building units:
1. 0D Molecules, clusters, fullerenes, rings, 2. nanotubes, fibers, filaments, whiskers,
3. 2D
metcarbs, thoroids, domens, particles, 1D spirals, belts, springs, horns, columns,
powders, grains, schwartzons needles, pillars, helicoids, wires, ribbons layers

4. 0D0 5. 0D00 hetero-

0D-nanostructures: uniform geneous particles arrays,
particles arrays “core-shell” dendrimers,
onions
6. 1D0
1D-nanostructures: molecular chains,
polymers
7. 8. 1D1 9. 1D11 10.
1D10
1D00 beads,
heteropolymers bundles, ropes, heterochains, heterocables, saws, hair, pea-pods,
cables, corals heterobundles, junctions, combs, bows fullereno-fibers

11. 2D0 12. 2D1

2D-nanostructures:
nanostraw, PhC,
fullerene films fibers films
13. 2D2 14. 2D00 15. 2D10 16. 2D11 films of fibers
tiling, heterofilms and nanotubes,
mosaic, of heteroparticles, films of pods,
layered films fullereno-powders fullereno-fibers PhC-waveguides
17. 2D20 18. 2D21 19. 2D22 hetero-layers, 20. 2D210
fullereno- bridges, fullerene-fiber-
plate films fiber-layer films MOS-structures layer films

3D-nanostructures:
21. 3D0 22. 3D1 23. 3D2 24. 3D00
Fullerites, skeletons layer skeletons sols, colloids,
clathrates, of fibers, buildings, smogs,
powder skeletons, fog nanotubes honeycombs, foams heteroparticles composites
25. 3D10 26. 3D11 27. 3D20 28. 3D21
skeletons of skeletons of intercalates, Cross-bar-layers,
fibers-powders heterofibers skeletons of layer-fiber
nanotubes layers and powders skeletons
29. 3D22 30. 3D30 31. 3D31 32. 3D32 friction
opals, membranes, pairs, contacts,
heterolayers dispersions, PhC, fiber interfaces, cavities,
particles, pores, compositers,
waveguides grain boundaries
fullerenes in matrix
33. 3D210 34. 3D310 35. 3D320 36. 3D321
composites membranes powder-layers layers-fibers-
of layers, + impurities, composites composites in
fibers and powder-fiber matrix, VCSEL
particles in matrix composites
Notices:
1. Interfaces between building units not regarded as additional 2D-NSs
2. Inverse NSs with cavity building units not regarded as separate ones
3. The classification may be extended with account of fourfold combinations

FIGURE 1.1
Dimensionality classification of nanostructures. (Reprinted from Pokropivny, V. V., and
Skorokhod, V. V., Classification of nanostructures by dimensionality and concept of surface
forms engineering in nanomaterial science, Materials Science and Engineering C 27 (5-8 SPEC.
ISS.), 990–993, Copyright 2007, with permission from Elsevier.)
Synthesis, Processing, and Application of Nanostructures 5

Categorization of nanomaterials by their nanometric dimensions is

shown in Figure  1.1. Atomic clusters are known as nondimensional
nanomaterials, while bulk nanocrystals and nanocomposites are called
three-dimensional (3D) nanomaterials. Within the nanocrystals, the
grains (crystallites) are co-axis and their size is in the nano range. The
structure of nanocomposites is made of two or more phases, where one
of the phases is presented in zero, one-, two-, or three-dimensional states.
Nanocrystals and nanocomposites are generally known as nanostruc-
tured materials.
All nanomaterials share this feature that a significant portion of their
atoms is located in interfaces such as free surfaces, grains boundaries, and
interphase faces. Most nanomaterial properties come from this fact. There
are several physical, chemical, and mechanical methods invented for pro-
duction of nanomaterials. Nanomaterial is made of structural units that are
laid side by side. In some methods for production of nanomaterials, first
the structural units are made from atoms or molecules and then combining
these structural units the given nanostructure is achieved. These methods
are known as “bottom-up.” However, there are some other methods known
as “top-down,” in which the large structural units of a material are gradu-
ally divided into smaller parts until we reach nano dimensions.19–22
The first point in production of nanomaterials can be started from a gas,
liquid (or melted), and even solid phase. Table 1.1 shows some of the main
processes in each group. Figure 1.2 presents an example for a method that
has been used in order to fabricate reduced graphene oxide.
In each of these processes, it is possible to change the dimension, mor-
phology, and texture of nanostructured material by controlling the involved
parameters and achieving favorable characteristics. Nevertheless, it must be
noted that in processes that involve a change of phase (e.g., changing the
vapor phase into a solid or changing the liquid phase into a solid), creating
the structure requires an increase in nucleating rate and a decrease of growth
rate during the production process. Each of these processes involves advan-
tages as well as disadvantages. Choosing a production method depends
on multiple factors such as characteristics of the final structure (grain size,
phase morphology, etc.) and purity of the final product.
Processes for producing nanomaterials in solid phases involve low pro-
duction costs. The operation is performed in low temperatures (generally

TABLE 1.1
Classification of Nanomaterials Production Processes
Production from vapor phase Physical and chemical deposition of the vapor
Production from liquid (or melted) phase Sol-gel, electrochemical deposition, sudden freezing
Production from solid phase Mechanical alloying, severe plastic deformation,
mechanochemical process, crystallization of the
amorphous phase
6 Two-Dimensional Nanostructures

Graphite oxide Graphene oxide

Exfoliation

Reduction Reduction

Reduced graphite oxide Reduced graphene oxide

less reduction

FIGURE 1.2
Representative scheme of a degree of reduction of graphite/graphene oxides. (Reprinted from
Park, S., An, J., Potts, J. R., Velamakanni, A., Murali, S., and Ruoff, R. S., Hydrazine-reduction
of graphite- and graphene oxide, Carbon 49 (9), 3019–3023, Copyright 2011, with permission
from Elsevier.)

in room temperature). In addition, these processes can be applied for a vari-

ety of materials including pure metals, metallic alloys, intermetallic com-
ponents, ceramics, and polymers. Moreover, it is possible to easily control
production conditions to create ideal fine structures. This feature has caused
wide use of solid-state production processes for creating 3D nanomaterials,
particularly once the high rate of purity is not our objective. In the following
sections of this chapter, the techniques applied for production of nanostruc-
tured materials will be discussed briefly.24–27

1.4  Properties of Nanostructured Materials

In general, a material’s properties depend on atom arrangement and atom
alignment in its structure. For instance, steel’s properties differ from those
of copper, because their atoms are different. Furthermore, properties of face-
centered cubic (FCC) crystalline steel are different from body-centered cubic
(BCC) crystalline steel because their atom arrangement in the crystal struc-
ture is not the same.
One distinct property of nanomaterials is their different behavior in
macro- or microstructural states. All materials, irrespective of their compo-
sition, reveal new features (such as improvement of their optical features,
Synthesis, Processing, and Application of Nanostructures 7

decrease of melt point, increase of tensional strength, enhancement in cata-

lytic properties, increase of semiconductors’ band gap, increase of magnetic
properties, and decrease of electrical resistance) once their size drops lower
than 100 nm. As well as composition and structure of a substance, its dimen-
sion, once it goes below a specific limit, is another critical factor that has an
effect on its properties. The following items can be mentioned as reasons for
these behaviors of the materials:

1. Material size approaching molecular and atomic ranges

2. The high surface-to-volume ratio in nanomaterials; this means that
the atom’s distance from the surface is very short, so the interatomic
forces and chemical bounds are of great importance and have a
determining role
3. Increase in the volume of grains’ boundaries with decrease of grains’
sizes which, in turn, affects the material’s physical features

It must be noted that with an increase in the surface ratio, the free energy
of the material rises; this causes changes in the material’s features. This
can be explored in another way: According to the above-mentioned points,
materials’ characteristics also depend on their atoms arrangement, so as
the grains sections increase, the larger number of atoms would be pres-
ent in its exterior surface, implying that the material’s atoms are in an
environment different than that of atoms in conventional materials; hence,
atoms placed at the surface experience a different environment than that
of interior atoms.28–30
Materials properties considerably rely on their internal structures’ dimen-
sions. As the size of grains or constituent phases of a material decreases
up to the nano range, common mechanisms of the mechanical and physi-
cal properties cannot be considered, and the material’s properties dramati-
cally change. For instance, pure microcrystalline metals indicate a low yield
strength, which results from ease of dislocation movements and develop-
ment across their grains. However, once grain size of pure metal drops to
the nanometric range, the dislocations mechanism would not be active, and
yield strength of the material will be significantly enhanced.
Properties of nanostructured materials depend on three main factors:

• Size of constituent phases or grains of the material

• Structure or nature of the existing interfaces such as grain contacts
and interphase faces
• Chemical of the substance

In some cases it is possible that just one of the above-mentioned factors

plays a main role in defining properties of the nanostructured material.
8 Two-Dimensional Nanostructures

In different control methods, it may be possible to partially control these

three factors and achieve the objective properties through control of process
parameters. But the efficacy of controlling all these three factors is not equal
in all methods.
One of the most important characteristics of nanostructured materials is
their having an extensive interface surface with each other.31–36 So, a consider-
able ratio of their atoms is located in their interfaces. For example, once we have
a nanocrystalline material with spherical or cubic grains with a diameter of
d, the surface-to-volume ratio will be 6/d taking the grain boundary’s thick-
ness (δ) into account and regarding this fact that each grain boundary is shared
with two adjacent grains, the ratio of atoms located in grain boundaries (Xb) is
defined by the following equation:

Xb = 3δ/d × 100 (1.1)

Usually as the grain size drops, the number of atoms in grain boundar-
ies greatly increases (e.g., when the grain size is 5 nm the atom number in
the grain boundary of 0.5 nm will be 50%). If the grain boundary thickness
is 1 nm, 80% of the atoms will be located in grain boundaries. Thus, it is
predicted that in this condition the nanocrystalline material’s properties is
strongly influenced by grain boundaries’ properties. The relation between
the number of atoms per grain boundary (GB) interface and the calculated
grain boundary interface area is calculated in Figure 1.3.
Although several studies have been performed to identify grain bound-
aries in nanocrystalline materials, it is not clear that weather atoms
arrangement in grain boundaries of nanocrystalline and microcrystalline
materials is the same, and weather structure and nature of grain sizes in
nanocrystalline materials are influenced by their production technique. In
any event, the average distance between atoms in grain boundaries is the
maximum, and the number of closest neighbors for each atom is the mini-
mum. In addition, interatomic bonds in grain boundaries are the weakest.
In addition to an extensive interface surface, the presence of voids created by
production steps and crystalline defects such as atomic vacancies, or resid-
ual dislocations, has a significant effect on the properties of nanostructured
materials. Therefore, it is expected that nanostructured materials proper-
ties, even in grain size and chemical composition, be varied according to
their production method.38–43
As previously mentioned, there is an extensive interface surface in nano-
structured materials, where a considerable ratio of atoms can be accommo-
dated. Such a structure results in different and superior chemical, physical,
and mechanical properties of nanostructured materials compared with
traditional substances (microcrystals). There is also a possibility to change
different characteristics in a definite range by controlling the grain size
and phases. Some of these changes are shown in Figure 1.4.
Synthesis, Processing, and Application of Nanostructures 9

18000
Calculated GB Interface Area,

16000
14000
a, Angstrom2

12000
10000
8000
6000 <d>=12.17 nm
4000 a=1.8629 nf – 659.2112
2000
0
0 2000 4000 6000 8000 10000
Number of Atoms per GB Interface, nf
(a)

140
Calculated TJ Length,

120
100
I, Angstrom

80
60 <d> = 12.17 nm
40 I = 0.2733 ntj – 1.2979
20
0
0 100 200 300 400 500 600
Number of Atom per TJ, ntj
(b)

FIGURE 1.3
(a) The linear relation between the number of atoms per grain boundary (GB) interface, nf,
and the calculated GB interface area; (b) the linear relation between the number of atoms per
triple junction (TJ), ntj, and the calculated TJ length. The number of grains in the nanocrystal-
line Cu sample is 50, and the mean grain size is 12.17 nm. (Reprinted from Li, M., and Xu, T.,
Topological and atomic scale characterization of grain boundary networks in polycrystalline
and nanocrystalline materials, Progress in Materials Science 56 (6), 864–899, Copyright 2011, with
permission from Elsevier.)

1.4.1  Physical Properties

1.4.1.1  Diffusion Coefficient
For their wider atomic arrangement, grain boundaries and interphase faces are
considered as quicker diffusion paths in polycrystalline materials, as activation
energy of atoms’ diffusion through grains boundary is about half of their activa-
tion energy for diffusion across the grains. The difference between the diffusion
rate in a grain’s boundary and the diffusion rate across the grains themselves
is of a great importance in low temperatures.44–56 Diffusion coefficient and tem-
perature are correlated by the following exponential Arrhenius function:

−Q
D = D0 exp (1.2)
RT
10 Two-Dimensional Nanostructures

Diffusion coefficient
Strength
Toughness
Thermal expansion
coefficient
Hardness

Thermal conductivity
Density
Saturated magnetism
Electrical conductivity
Corrosion resistance
Curie temperature

FIGURE 1.4
Usual mechanical and physical trends of changes for nanostructured materials.

where D is the diffusion coefficient, D­0 is the constant coefficient, Q is the dif-
fusion activation energy, T is the temperature (K), and R is the universal gas
constant. Table 1.2 presents grain boundary and lattice diffusion coefficients
for self-diffusion of Au at two different temperatures.
In any case, in microcrystalline materials, the grain boundary share in
whole diffusion is negligible, but for nanocrystalline materials, where there
is an extensive grain boundary, it is predicted that the diffusion rate would be
considerably high, in comparison with microcrystalline materials. Table 1.3
shows diffusion coefficients of silver atoms in copper at three different tem-
peratures, which reveals that the diffusion coefficient for a nanocrystalline
sample is higher than that of grain boundaries.
An increase in diffusion of nanostructures is also observed in some other
metals. Here, it must be noted that the diffusion coefficient in a nanocrystal-
line sample (Dn) is even more than that of grain boundary (Db) diffusion,
suggesting that the structure of the grain boundary for nanocrystals might

TABLE 1.2
Diffusion Coefficient across the Grain Boundary (D b) and Lattice (DL) for
Self-Diffusion of Au
Temperature
Material (°C ± 0.2°C) α–5/3t–1/2 × 10–9 DL (cm2/sec) δDb (cm3/sec)
(A) Bulk 444.1 1.23 1.85 × 10–14 2.11 × 10–16
367.2 1.37 5.54 × 10–16 4.19 × 10–17
(B) Films (Au-Mo-SiO2) 177.0 0.58 5.41 × 10–22 1.78 × 10–20
117.0 0.33 4.17 × 10–25 2.81 × 10–22
Synthesis, Processing, and Application of Nanostructures 11

TABLE 1.3
Diffusion Coefficients of Silver Atoms in Nanocrystalline Copper,
in Copper Grain Boundaries, in the Lattice of Copper, and on
Copper Surfaces
Nanocrystalline Grain boundaries(a) Lattice Surface(b)
T (°K) Di (m2/s) Db (m2/s) DL (m2/s) Ds (m2/s)
373 1.2 × 10–17 22.5 × 10–20 8.1 × 10–33 9 × 10–14
353 3.1 × 10–18 6.9 × 10–21 1.4 × 10–34 5.3 × 10–14
303 0.3 × 10–18 1.3 × 10–22 2.6 × 10–38 1 × 10–14
a Assuming a grain boundary thickness of 1 nm.
b Silver diffusion on Cu (110) and (331) surfaces.
Source: Reprinted from Schumacher et al., Diffusion of silver in
nanocrystalline copper between 303 and 373k, Acta Metallurgica
37(9), 2485–2488, Copyright 1989, with permission from Elsevier.

be wider in microcrystalline materials though an increase of the diffusion

coefficient can originate from the presence of fine voids in nanocrystalline
samples. An effective diffusion coefficient in a polycrystalline material can
be obtained by the following equation:

Deff = (1 − F )DL + FDb (1.3)

where F is the grain boundary fraction. Once δ is the grain boundary thick-
ness and d is the grain size, one can say

2δ
F≈ (1.4)
d

Assuming that the thickness of the grain boundary is 7 nm, Equation (1.3)
shows that decreasing grain size from 100 to 50 nm caused the effective dif-
fusion coefficient to increase from 1 × 10 –18 (m2/sec) to 5.7 × 10 –15 (m2/sec).
Equation (1.3) also shows that supposing that diffusions are mainly per-
formed through grain boundaries, the following condition must be achieved:

FDb  (1 − F )D (1.5)

or

δ δ
Db  1 − DL (1.6)
d d

These conditions will be achieved once the grain size is very fine.
An increase of the diffusion rate in nanostructures is followed by accel-
eration of solid-state alloying and a considerable change in creep and
12 Two-Dimensional Nanostructures

superplastic behavior of the material. This also causes acceleration of the sin-
tering process during preparation of pieces from nanostructured powders.
This means that the sintering process of the powder metallurgy pieces can
be performed in much lower temperatures. For instance, it was reported that
the required temperature for sintering titanium dioxide powder (TiO2) with
grain sizes around 12 nm is about 400°C to 600°C lower than that of the same
powder with grain size of 1.3 µm.

1.4.1.2  Thermal Expansion Coefficient

Metallic nanoparticles and semiconductors are of lower melt or phase transi-
tion temperature in contrast to their mass state. The lower melting tempera-
ture of the particles emerges once the particle size is less than 100 nm, which
is due to a decrease of surface energy with grain size. A drop in phase transi-
tion temperature can be described with changes in surface energy to volume
energy as a function of grain size.
It is supposed that the optimum diffusion in the grain boundaries of the
nanomaterials is due to changes in their thermal features. In the metals, melt
point and thermal conductivity decrease through use of nanotechnology
(e.g., melt temperature of the nano-gold is 27°C less than that of conventional
gold). Besides, the thermal expansion coefficient has been decreased in the
nano-gold. Decrease in thermal conductivity of the nanostructured ceramics
can develop their application as a thermal shield. Another application of
these materials is in the coating blades of airplanes’ turbines, which multi-
plies their life up to six times more than the common ones.46,59–69
Contradictory results were reported about the effect of grain size drop on
the thermal coefficient of the materials. Basically, because a high frac-
tion of atoms are located in grain boundaries, it is expected that the thermal
expansion coefficient of nanostructures is a large figure. Some measure-
ments on several metals and nanocrystalline alloys prove this prediction.
For example, it was reported that the thermal expansion coefficient of
copper with a grain size of 8 nm in the range of 110°K to 293°K is twice
as much as that of a single crystal copper sample. On the other hand,
some other results imply no change in the thermal expansion coefficient
of nickel in the nanocrystalline state, in comparison with the micro-
crystalline state. In addition, some results have shown that the thermal
expansion coefficient of nanocrystalline samples, which are made by
consolidation of the initial powder, decreases with an increase of applied
pressure. Based on these findings, one can conclude that there is basi-
cally no significant difference between the thermal expansion coefficient
of common nanocrystalline and microcrystalline materials. An increase
of the thermal expansion coefficient of some nanocrystalline materials,
presented in some experiments, can be interpreted as a result of voids,
fractures, and other structural defects in the final structure of the pre-
pared samples. Figure 1.5 compares the thermal conductivity, the specific
Synthesis, Processing, and Application of Nanostructures 13

0.16

Thermal Conductivity (W/cm/K)

0.15 Polycrystalline
0.14
0.13
0.12
0.11
0.10
0.09
Nanocrystalline
0.08
0 100 200 300 400 500 600
Temperature (°C)
(a)
45
Specific Heat Capacity (J/K/mol)

40 Nanocrystalline

35

Polycrystalline
30

25
100 150 200 250 300 350 400 450
Temperature (°C)
(b)
Thermal Expansion Coefficient (10–4/K)

1.2
1.0
0.8 Nanocrystalline
0.6
0.4
0.2
0.0 Polycrystalline

–0.2
–0.4
150 200 250 300 350 400 450
Temperature (°C)
(c)

FIGURE 1.5
(a) The thermal conductivity, (b) the specific heat capacity, and (c) the thermal expansion coeffi-
cient of the prepared ultrafine nanocrystalline Gd bulk as a function of the temperature, together
with a comparison with those of the polycrystalline Gd bulk. (Reprinted from Lu, N., Song, X.,
and Zhang, J., Microstructure and fundamental properties of nanostructured gadolinium (Gd),
Materials Letters 63 (12), 1089–1092, Copyright 2009, with permission from Elsevier.)
14 Two-Dimensional Nanostructures

100

80
ρ, µΩ·cm

60

40

20

50 100 150 200 250

T, K

FIGURE 1.6
Dependence of electrical resistivity on temperature for nanocrystalline Fe-Cu-Si-B alloys with
grain sizes of (⚬) 30 nm, (◽) 40 nm, (⦁) 50 nm, and (◾) 90 nm. (Reprinted from Wang, Y. Z., Qiao,
G. W., Liu, X. D., Ding, B. Z., and Hu, Z. Q., Electrical resistivity of nanocrystalline Fe-Cu-Si-B
alloys obtained by crystallization of the amorphous alloy, Materials Letters 17 (3–4), 152–154,
Copyright 1993, with permission from Elsevier.)

heat capacity, and the thermal expansion coefficient of ultrafine nano-

crystalline Gd bulk as a function of the temperature with those of the
polycrystalline bulk Gd.

1.4.1.3  Electrical Resistance

Figure 1.6 indicates changes of specific electrical resistance with temperature
for some nanocrystalline alloys of Fe-Cu-Si-B with different grain sizes.
For nanocrystalline materials, like microcrystals, specific electrical resis-
tance increases with temperature. However, once the grain size rises, this
increase grows with higher rates. Also, at a constant temperature, specific
electrical resistance considerably intensifies with grain size increase.
Due to entropies in atoms’ arrangement in grains’ boundary, electrons are
scattered during passing from the boundaries; this, in turn leads to enlarge-
ment of specific electrical resistance of the material. It is obvious that as
grain size decreases, or in other words area of grain boundaries increases,
electron dispersion and consequently electrical resistance, increases. Then,
by controlling the grain size, it is possible to change the specific electrical
resistance.66,72–80
Synthesis, Processing, and Application of Nanostructures 15

1.4.1.4  Solubility of Alloy Elements

Solubility of elements in nanocrystalline materials is notably higher than
common polycrystalline materials. Due to the presence of an expanded
grain boundary in nanocrystalline materials and low concentration of
atoms in grain boundaries, a large amount of alloy elements can be dis-
solved in nanocrystalline materials. For instance, solubility of mercury in
polycrystalline copper is less than 1 atomic percent, while it is 17 atomic
percent for mercury dissolved in nanocrystalline copper. This phenomenon
even exists in alloy systems in which there is a solubility defect area (like
alloy systems such as Ag-Fe, Ti-Mg, and Cu-Fe). For example, the solubility
of Mg in Ti in the solid phase is less than 0.2 atomic percent, but decreasing
the titanium grain size up to the nanometric range brings the number up to
30 times.81–87 Thus, it is possible to produce new alloys with new properties
via increasing solubility of alloy elements. Figure  1.7 indicates that lower
temperatures are needed for nominal copper solubility in Al-Cu alloys with
lower nanometric grain sizes.

1.4.1.5  Magnetic Properties

Because the magnetic properties increase with the increase of the surface-
to-volume ratio, magnetic nanomaterials demonstrate unusual behaviors,
which is due to particle size and their charge transmission properties.
Magnetic properties in nanostructured materials vary with those in a mass

Eutectic temperature 821.2 K

800 a
b
750 c
700 d
Temperature (K)

650 e
600

550

500

450

0.01 0.02 0.03 0.04 0.05 0.06

Nominal Cu Concentration (wt)

FIGURE 1.7
The nominal copper solubility (solvus) in Al-Cu alloys with different grain sizes. Grain size (a)
d = ∞, (b) d = 100 nm, (c) d = 50 nm, (d) d = 25 nm, and (e) d = 10 nm. (Reprinted from Meng, Q. P.,
Rong, Y. H., and Hsu, T. Y., Distribution of solute atoms in nanocrystalline materials, Materials
Science and Engineering A 471 (1–2), 22–27, Copyright 2007, with permission from Elsevier.)
16 Two-Dimensional Nanostructures

state of the materials, because an increase of surface energy leads to devel-

opment of enough energy for spontaneous changes of the magnetic fields in
polar directions, which changes the material into a paramagnetic state. As
the behavior of these modified paramagnetic differs from that of prevalent
paramagnetic, it is called supermagnetic. In other words, due to high levels
of the energy paramagnetic properties of the mass, materials are removed
in nanodimensions and the material turns into a supermagnetic state.
Materials’ ferromagnetic properties are controlled by their interatomic
distances, grain size, and constituent phases. For this reason, saturated mag-
netic properties (Ms) and Curie temperature (TC) in nanocrystalline mate-
rials are considerably low compared with microcrystalline materials. For
instance, magnetism of microcrystalline Fe is 220 emu/g, while this declines
to 130 emu/g once Fe grains size goes down to 6 nm. Or it is reported that
Curie temperature of nanocrystalline Gadolinium (Gd) with grain size of
10 nm is about 10°C less than that of microcrystalline Gd. These changes
all come from decreasing the grain size to the nanometric range, as each
grain can act like an independent unit. In addition, a considerable fraction
of the atoms in nanocrystalline structures are located in the grain bound-
ary, where average atomic distances are more than those in grains.
Alloys of nanostructural Fe, such as Fe73.5Cu1Nb3Si13.5B9 (commercially
known as Finement) and Fe91Zr7B2 (commercially known as Nanoperm)
manifest an efficient complex of magnetic properties. These materials
involve a low inhibition of 5 to 10 A/cm, high permeability of 105, and a low
energy waste, as well as magnetic properties of about zero (less than 2 × 10 –6).
Furthermore, due to a high electrical resistance, nanostructured materials
display a low core waste of 200 KW/m3. These characteristics all together
have made nanocrystalline Fe alloys among the best magnetic materials and
an alternative for matrix amorphous alloys of cobalt. Figure 1.8 presents a
comparison of magnetic properties of nanocrystalline magnetic Fe alloy
(Nanoperm) and conventional soft magnetic materials.89–96
Creating nanostructures in permanent magnets such as Fe90Nd7B3 has
significantly improved their magnetic properties. The magnetic properties
of these alloys are induced from the Nd2Fe14B phase, which has hard mag-
netic properties. This phase with the Fe phase (ferrite), which involves soft
magnetic properties, is present in the structure of Fe-Nd-B alloy. Once this
biphasic structure is created in nanodimensions, the residual magnetism
(Mr) increases, and then Mr will be considerably larger than 1/2 Ms.
Development of nanostructures causes improvement of the high magnetic
resistance phenomenon. This feature is defined as dramatic reduction of
electrical resistance due to applying a magnetic field. This reduction is
about 1% to 2% for microcrystalline materials, while for nanocrystalline
materials this has been reported to be 50% or even more. The creation
of nanostructures in magnetic coolers improves their performance and
output.
Synthesis, Processing, and Application of Nanostructures 17

Co-based amorphous alloys

Nanocrystalline
Fe-M-B alloys
105
Fe-Al-Si “NANOPERM®”
Permeability, µe(1 kHz)

alloys

Ni-Fe alloys

104

Fe-based
amorphous alloys

MnZn-ferrite Silicon steels

103
0 0.5 1.0 1.5 2.0 2.5
Saturation Induction, Ba/T

FIGURE 1.8
A comparison between magnetic properties of Nanoperm and conventional soft magnetic
materials. (Reprinted from Makino, A., Inoue, A., and Masumoto, T., Nanocrystalline soft
magnetic Fe-M-B (M = Zr, Hf, Nb), Fe-M-O (M = Zr, Hf, rare earth) alloys and their appli-
cations, Nanostructured Materials 12 (5), 825–828, Copyright 1999, with permission from
Elsevier.)

1.4.1.6  Corrosion Resistance

A number of researchers have investigated corrosion resistance of nanocrys-
talline materials. A study on corrosion of Ni-P alloy shows that the corrosion
rate of nanocrystalline alloys is higher than that of common microcrystalline
alloys; however, corrosion is more general.
Higher rates of corrosion in nanocrystalline materials are due to their
extensive grain boundary, where atoms are in balance and then have higher
energy levels that make them able to participate in chemical corrosive reac-
tions. More regular corrosion of nanostructured materials is due to their
more homogenous structures. Experiments performed on nanocrystalline
304 stainless steel in HCl reveal that nanostructures have higher local resis-
tance against corrosion than traditional structures.98–103
Decreasing the average size of nanocrystallites usually can increase the
corrosion resistance, while some other factors such as the nature of the mate-
rial and its porosity can affect this trend. Figure 1.9 shows the close relation-
ship between corrosion resistance and average nanocrystallite size for a kind
of hard coating fabricated by plasma electrolysis.
18 Two-Dimensional Nanostructures

700

600
Polarization Resistance of Different
Treated Samples (kohms.cm–2)

500
PR = –10.825 ASN + 1029.2
R2 = 0.8085
400

300

200

100

0
35 40 45 50 55 60 65 70 75 80 85
Average Size of Nanocrystallites (nm)

FIGURE 1.9
Polarization resistances of different coatings versus the average size of their nanocrystallites.
(Reprinted from Aliofkhazraei, M., Sabour Rouhaghdam, A., and Heydarzadeh, A., Strong
relation between corrosion resistance and nanostructure of compound layer of treated 316 aus-
tenitic stainless steel, Materials Characterization 60 (2), 83–89, Copyright 2009, with permission
from Elsevier.)

1.4.1.7  Hydrogen Capacitance Properties

Hydrogen is among the best alternatives for fossil fuels such as oil and
gas. Hydrogen combustion produces no pollution and is available from
renewable energy resources. However, industrial use of hydrogen as a fuel
requires the development of safe and economic capacitance systems. One
of the best techniques to store the hydrogen is to use metallic hydrides.
Compounds such as LaNi5, ZrV2, Mg2Ni, and FeTi can store a considerable
amount of hydrogen (about 8 weight percent) by the development of metal-
lic hydrides and release it once there is a favorable condition of temperature
and pressure. In this regard, required rate, temperature, and pressure for
absorption or release of hydrogen by the material are of great importance
in industry. These characteristics can be surprisingly improved by creating
nanostructures.105–113

1.4.2  Mechanical Properties

Mechanical properties of the nanomaterials are improved as their size
decrease. Most studies conducted in this area are focused on mechanical
properties in one-dimensional structures such as nanowires. Enhanced
mechanical strength in nanowires or nanorods is attributed to the high rate
of internal defects in the nanowires. In general, defects, such as impurities,
Synthesis, Processing, and Application of Nanostructures 19

dislocations, and microtorsions, in crystals contain high energy content and

must be removed from the completely crystalline structures. As the section
area of the nanowires decreases, their defect rate drops because nanodimen-
sions allow for removal of such defects.
Also, as the grain size increases, the volumetric ratio of the grain’s size
would increase in a single cell, as for the grains with a size of 5 nm about 50%
of the volume would be empty space. One can explain the decrease of mate-
rial strength due to the decrease of grain size as follows: The grain sizes start
to slip because of high density of the defects in the stress field, so the atoms
and dislocations would be widely expanded in the stress field.
During recent years, various studies have been conducted on mechanical
properties of nanostructures. The results show that once the grain size is
fine enough (up to nanometric range), many mechanical properties of
materials—compared with common materials—dramatically change.
Mechanical properties of the nanostructured materials are mainly due to
their extensive interfaces and the presence of a considerable fraction of atoms
in these faces. Some factors including phase shape, distribution, size, impuri-
ties, and also density of crystalline defects influence mechanical behavior of
the nanostructured materials. It must be noticed that the presence of voids
or cracks in their structures, which mainly occur during the production
processes, can also change their many other characteristics. Some discrep-
ancy between results obtained by different researchers might be the result of
these factors. Unfortunately, there is no comprehensive study about the role
of voids, second-phase particles, alloy elements or impurities, and the nature
of interfaces on mechanical properties of nanostructured materials. Hence,
offering a complete summation is rather difficult.114–123
Table 1.4 shows mechanical properties of Ni in three different grain sizes.
Some of these properties such as yield strength, final strength, hardness,
and abrasive strength in the nanostructural state are several times higher
than those in the microcrystalline state. But on the other hand, some other
features such as Young elastic modulus (E) show no noticeable change and
some, like flexibility, even show a reduction.

1.4.2.1  Elastic Properties

Initial measurements to determine elastic constants of nanocrystalline mate-
rials were done on samples produced with the powder metallurgy method.
These research studies indicate that elastic properties such as E in nanocrys-
talline materials are greatly (up to 30%) more than traditional microcrystalline
materials. However, laboratory test results and the following models clearly
suggest that the presence of voids and cracks in samples can have a consider-
able effect on elastic modulus reduction of nanocrystalline materials, as it can
decrease up to 80% regarding size, percentage, and shape of the voids.36,121,125–
130 The presented results in Table 1.4 show that for a nanocrystalline sample

with insubstantial porosity, Young modulus basically does not change with
20 Two-Dimensional Nanostructures

TABLE 1.4
Mechanical Properties of Ni in Nanocrystalline and Microcrystalline States in
Ambient Temperature
Property Grain Size
10 µm 100 nm 10 nm
Yield strength (MPa, 25°C) 103 690 >900
Ultimate tensile strength (MPa, 25°C) 403 1100 >2000
Tensile elongation (%, 25°C) 50 >15 1
Elongation in bending (%, 25°C) — >40 ---
Modulus of elasticity (Gpa, 25°C) 207 214 204
Vickers hardness (kg/mm2) 140 300 650
Work hardening coefficient 0.4 0.15 0.0
Fatigue strength (MPa, 108) cycles/air/25°C) 241 275 —
Wear rate (dry air pin on disc, µm3/µm) 1330 — 7.9
Coefficient of friction (dry air pin on disc) 0.9 — 0.5
Source: Reprinted from Robertson, A., Erb, U., and Palumbo, G., Practical
applications for electrode-posited nanocrystalline materials, Nanostructured
Materials 12(5), 1035–1040, Copyright 1999, with permission from Elsevier.

grain size decrease. It is predicted that this trend is true up to a grain size of
5 nm. But, once grain size is smaller than 5 nm the number of atoms located
in the grain boundary will be significant131 and can dramatically change
the elastic properties of the material. Thus, most of the time nanocrystalline
materials with a grain size of 10 nm have the similar elastic constants with
common microcrystalline materials. The changes of different related properties
for an ultrananocrystalline diamond can be seen in Figure 1.10.

1.4.2.2  Plastic Properties

Yield strength and hardness of common polycrystalline materials depend on
their grain size. For polycrystalline materials the empirical Hall–Petch equa-
tion states the relationship between yield strength and grain size as follows:

σy= σ0 + kd–1/2 (1.7)

where σy is the yield stress, σ0 is the innate yield stress for starting a single
dislocation, d is the grain diameter, and k is a constant related to the grain
boundaries’ effect on dislocations. In the same way, Equation (1.8) shows the
effect of grain size on the hardness of polycrystalline materials:

H = H0 + k′d–1/2 (1.8)

where H and H0 are, respectively, hardness and innate hardness (hardness

of a single crystal).
Synthesis, Processing, and Application of Nanostructures 21

Ec B
B = 467 – 427/d + 204/d 2
Ec = –7.3 + 0.69/d – 0.19/d 2

–6.9 375

350
–7.0

B (GPa)
Ec (eV)

325
–7.1
300

–7.2 275

2.0 3.0 4.0 2.0 3.0 4.0

d (nm) d (nm)

E, H
E (exp.)
G
900 90

750 75
Modulus (GPa)

H (GPa)
600 60

450

300
2.0 3.0 4.0
d (nm)

FIGURE 1.10
Cohesive energy (left panel), bulk modulus (central panel), Young’s and shear moduli, and esti-
mated hardness (right) of ultrananocrystalline diamond (UNCD) versus the average grain size.
The solid lines in the left and central panels are fits to the data. The function used assumes dif-
ferent compressibilities for atoms in the bulk, grain boundaries, or edges. In the right panel, the
experimental value from Espinosa and colleagues is also shown. (Reprinted from Remediakis,
I. N., Kopidakis, G., and Kelires, P. C., Softening of ultra-nanocrystalline diamond at low grain
sizes, Acta Materialia 56 (18), 5340–5344, Copyright 2008, with permission from Elsevier; also
reprinted from Espinosa, H. D., Peng, B., Moldovan, N., Friedmann, T. A., Xiao, X., Mancini, D.
C., Auciello, O., Carlisle, J., Zorman, C. A., and Merhegany, M., Elasticity, strength, and tough-
ness of single crystal silicon carbide, ultrananocrystalline diamond, and hydrogen-free tetrahe-
dral amorphous carbon, Applied Physics Letters 89 (7), Copyright 2006, with permission from the
American Institute of Physics.)

Equations (1.7) and (1.8) show that drawing the σy (or H) in terms of d–1/2
leads us to a line with gradient of k (or k′). To describe these empirical equa-
tions, several models have been suggested that are mainly based on produc-
tion, movement, and concentration of dislocations behind the grains. If the
Hall–Petch equation is true for nanocrystalline materials without changing
the k (or k′) coefficient, these materials’ strength and hardness should increase
up to 10 times.134–136 For instance, if grain size reduces from 10 µm to 10 nm,
22 Two-Dimensional Nanostructures

300

Failed

200
Stress (MPa) σ = 249 MPa

100

σ = 52 MPa
0
0.0 0.5 1.0 1.5 2.0 2.5
Strain (%)

FIGURE 1.11
Stress–strain curve for nanocrystalline (grain size of 7 nm) and microcrystalline (grain size of
100 µm) Pd. (Reprinted from Nieman, G. W., Weertman, J. R., and Siegel, R. W., Tensile strength
and creep properties of nanocrystalline palladium, Scripta Metallurgica et Materiala 24 (1),
145–150, Copyright 1990, with permission from Elsevier.)

the strength must increase up to 30 times, though laboratory results do not

support this claim (Table 1.4).
Due to limitations in making laboratory samples with large scales, the
performed studies (particularly mechanical properties of nanostructured
materials) are limited for measuring fine hardness. However, some results
about tensional test will also be available. Figure 1.11 shows the result of the
tension test on Palladium (Pd) in both microcrystalline and nanocrystalline
states. This obviously reveals that in nanostructured Pd there would be a
dramatic rise in yield strength with a decrease of grain size.
In total, for nanocrystalline materials with a grain size of 10 nm, hardness
and yield strength are about two to seven times more than common materi-
als with grain sizes of more than 1 µm. As previously mentioned, the effect of
grain size on hardness and yield strength of a material is typically described
by the Hall–Petch equation. In Figures 1.12 and 1.13, some examples of this
equation for nanocrystalline materials are presented.
Evaluating these results implies that in all cases, disregarding the produc-
tion method, hardness and strength increase according to the Hall–Petch
equation, but once the grain size is lower than a critical range (15 to 25 nm)
it does not rise by the previous gradient. In other words, in grain sizes lower
than a critical size k′ (or k), the coefficient in the Hall–Petch equation will be
reduced. In grain sizes lower than the critical size, nanocrystalline materials
display three different behaviors.
In most of the cases, the Hall–Petch equation continues but its gradient
declines. In a few cases Hall–Petch curve’s gradient limits to zero. This occurs
Synthesis, Processing, and Application of Nanostructures 23

105 nm 100 nm 25 nm 11 nm 6 nm
800

700
Vickers Hardness (Kg/mm2)

600

500

400

300

200

100

0.1 0.2 0.3 0.4

d–1/2, nm–1/2

FIGURE 1.12
Hall–Petch diagram for nanocrystalline nickel (Ni). (Reprinted from El-Sherik, A. M., Erb, U.,
Palumbo, G., and Aust, K. T., Deviations from Hall–Petch behaviour in as-prepared nanocrys-
talline nickel, Scripta Metallurgica et Materiala 27 (9), 1185–1188, Copyright 1992, with permis-
sion from Elsevier.)

in a small group of materials in grain sizes lower than critical size where the
curve’s gradient is negative. This means that the smaller the grain size, the
lower is the hardness. In this situation, we are faced with an inverse Hall–Petch
equation, so instead of work hardening there will be work softening. Figure 1.13
shows these behaviors for Cu and Pd and alloys of γ-TiAl, respectively.
Why an inverse Hall–Petch curve behaves in this way is not yet fully
answered. However, it is mainly believed that common mechanisms, about
creation and movement of dislocations, offered for plastic deformation are
not at play in nano ranges. Principally, in grain sizes less than 50 nm disloca-
tions cannot be presented. The absence of dislocations in limited spaces such
as whiskers was proven a long time ago. The required stress for activation
of dislocations sources, such as the Frank–Read ones, are inversely corre-
lated with distance between two dislocations’ interlocking. Therefore, due
to close grain boundaries in nanocrystalline materials, the distance between
dislocations locking is negligible and the required stress for activation of
dislocation sources can amount to theoretical shear stress in a sample with
no dislocations. So, it is expected that in very small grain sizes some other
phenomena control the plastic behavior of the materials. For example, it is
suggested that processes such as grain boundary slips or grain disorienta-
tion (diffusive creep) are the main mechanism for plastic deformation of the
nanocrystalline materials with critical grain sizes.
24 Two-Dimensional Nanostructures

16.0 d (nm) 6.25

475

400 Pd
Cu
325
VPH

250

175

100
0.20 0.25 0.30 0.35 0.40
d –1/2 (nm–1/2)

FIGURE 1.13
Inverse Hall–Petch curve for hardness of nanocrystalline Cu and Pd. (Reprinted from Chokshi,
A. H., Rosen, A., Karch, J., and Gleiter, H., On the validity of the Hall–Petch relationship in
nanocrystalline materials, Scripta Metallurgica 23 (10), 1679–1683, Copyright 1989, with permis-
sion from Elsevier.)

Although the results above are mainly for pure metals, the reported results
for nanocrystalline intermetallic components or alloys bearing ceramic
nanoparticles (oxides, carbides, etc.) are qualitatively similar to the results
mentioned above. Observing inverse Hall–Petch behavior in ceramics and
composites promises production of these materials in lower temperatures.
Figure 1.14 schematically displays Hall–Petch behavior in two grain sizes for
ZrN coating.
Like hardness and strength, it is predicted that flexibility of a substance
would rise with the drop of grain sizes down to the nano range. This predic-
tion is based on empirical experimental results on common microcrystal-
line materials, suggesting that smaller grain sizes lead to higher flexibility
and fracture toughness. As a matter of fact, in these materials as the grain
size decreases fracture strength intensifies more than yield strength, and
the substance shows a soft behavior. Nevertheless, the empirical results do
not prove this. As previously mentioned, nanostructured materials have
lower flexibility (particularly in tension test) than the common materials.
Polycrystalline Ni with a grain size of 10 µm would have a linear strain of up
to 50%, while once the grain size is 100 nm this strain is 15% of its original
length. If the grain size is higher than 100 nm, Ni displays an insignificant
flexibility (about 1%). In this way, nanocrystalline Ni will basically behave
like a brittle substance.
Synthesis, Processing, and Application of Nanostructures 25

38
Nanocrystalline ZrN
36

34 Region 2

32
Hardness [GPa]

30
Region 1
28

26

24

22

20

18
0.12 0.14 0.16 0.18 0.20 0.22 0.24 0.26 0.28 0.30 0.32 0.34
Grain Size d–1/2 [nm]–1/2

FIGURE 1.14
Hall–Petch plot of hardness of nanocrystalline ZrN coatings against the inverse square-root of
grain size. (Reprinted from Qi, Z. B., Sun, P., Zhu, F. P., Wang, Z. C., Peng, D. L., and Wu, C. H.,
The inverse Hall–Petch effect in nanocrystalline ZrN coatings, Surface and Coatings Technology
205 (12), 3692–3697, Copyright 2011, with permission from Elsevier.)

It is worth mentioning that most of the tests for measuring mechanical

properties of the nanostructured materials were performed on samples pre-
pared by the powder metallurgy method. Under this condition, the sam-
ples will generally have a considerable amount of voids, and the measured
flexibility will be influenced by the presence of voids and lack of complete
consistency between particles of the powder. In addition, sample surface
quality intensely affects the results of flexibility tests. To examine the role
of these factors, samples with no porosity or cracks were prepared using
some other production methods such as precipitation from the vapor phase
or electrochemical deposition. Mechanical tests on these samples also prove
this limited flexibility in the nanocrystalline state. Figure 1.15 shows flex-
ibility of some metals and alloys in terms of grain size. Although the data
are highly distributed, they all show that once the grain size decreases the
flexibility also reduces, and if grain size is less than 25 nm the flexibility
will be negligible. However, all these materials demonstrate a significant
flexibility of 40% to 60% in the microcrystalline state. Figure 1.16 compares
true stress–true strain curves for electrodeposited nanocrystalline nickel
and coarse grained nickel.
The reported flexibility for nanostructured materials in a tensional test is less
than a compressive test. For example, nanocrystalline copper samples (with a
26 Two-Dimensional Nanostructures

20.0
Cu
Cu Different
Cu
Cu references
15.0 Cu
Elongation to Failure (%)

Cu/ZrC/O
Al/Al6.4Zr
Al-10Ti
Pd
Ag
10.0

5.0

0.0
1 10 100 1000
Grain Size (nm)

FIGURE 1.15
Flexibility (in tensional test) in terms of grain size for some alloys and metals. (Reprinted from
Malow, T. R., and Koch, C. C., Mechanical properties in tension of mechanically attrited nano-
crystalline iron by the use of the miniaturized disk bend test, Acta Materialia 46 (18), 6459–6473,
Copyright 1998, with permission from Elsevier.)

grain size of 20 nm) show 12% to 18% of flexibility in a compressive test, while
this sample’s flexibility in a tensional test is about 2%. This difference is par-
tially due to lack of sensitivity to the presence of voids and cracks of the sample
in the compressive test, but in the tensional test these defects lead to stress con-
centration and drop of flexibility. One factor limiting the use of intermetallic

2.5

2.0
Nanocrystalline - Ni
1.5
Stress [GPa]

1.0

0.5 Polycrystalline - Ni

0.0

0 1 2 3 4 5 6 7 8 9 10
Strain %

FIGURE 1.16
True stress–true strain curves for electrodeposited nanocrystalline nickel and coarse grained
nickel. The coarse grained nickel reached a total elongation of 20%. (Reprinted from Van
Swygenhoven, H., Footprints of plastic deformation in nanocrystalline metals, Materials Science
and Engineering A 483–484 (1–2 C), 33–39, Copyright 2008, with permission from Elsevier.)
Synthesis, Processing, and Application of Nanostructures 27

compounds and ceramics is their brittle behavior. It is expected that in the pro-
cess of creating nanostructures, intermetallic compounds and ceramics show
soft behavior in temperatures lower than half of their melting point (°K). This
prediction is based on the fact that in common materials a grain size decrease
leads to a quicker increase of fracture stress compared with yield stress, so
brittle fracture changes into a soft fracture occur in lower temperatures.
On the other hand, based on creep theories, we have

R ≈ Db/d3T (1.9)

where r is the creep rate, Db is the diffusion rate in grain boundary, d is the
grain size, and T is temperature (in Kelvin).
According to Equation (1.9), if the grain size decreases from 10 µm to 10 nm
(which is 1000 times) the creep rate will increase 109 times. In addition, the
higher diffusion rate in the grain boundary for nanocrystalline materials leads
to more growth in creep rate. It is expected that an increase in creep rate for
nanostructured materials makes it possible to perform plastic deformation
of ceramics and intermetallic compounds in lower temperatures. Although
plastic behavior of ceramics and intermetallic compounds was observed
in lower temperatures in some cases (including TiO2, CaF2, and NiAl), test
repeatability has not yet been proved. Hence, it is not possible to offer a con-
clusion at this point.
Fatigue strength is another important mechanical characteristic of materi-
als. To date, there have been few studies on fatigue behavior of nanostruc-
tured materials. The early results suggest that most nanocrystalline metals
have a longer fatigue life in high stress cycles and vice versa. These results
might originate from the fact that fatigue life in high stress cycles is closely
related to strength of the materials, whereas short fatigue life in low stress
cycles relates to flexibility of the material. Also, it was reported that surface
hardening treatments, such as shot peening, have no effect on improvement
of nanocrystalline materials’ fatigue properties.
Because nanostructured materials have higher strength and hardness
than common materials, it can be assumed that their abrasive strength is
considerably higher than the customary materials (e.g., hardness of cobalt-
tungsten carbide [WC-Co] nanocomposites is twice as much as their hard-
ness in the microcrystalline state). Figure  1.17 illustrates the wear rate of
WC-Co composites (summarized in Table 1.5) in both nanostructured and
traditional states. This increase in wear rate can enhance the life span of
cutting tools and piece exposed to abrasion up to five times. The variation of
wear coefficient with the carbide grain size can also be seen in Figure 1.18.

1.4.2.3  Superplasticity
Some polycrystalline substances at a given temperature and strain rate
demonstrate a high plastic deformation (100 to 1000 percent or even more)
28 Two-Dimensional Nanostructures

7 FC20

6
Wear Rate (10–7 mm3/Nm)

FC15
5
RTW10
FC6M

RTW6M
4
FC6
NA15
RTW6
3 NA13
NA7

2
800 1000 1200 1400 1600 1800 2000 2200 2400 2600
Hardness (Kg/mm2)

FIGURE 1.17
Comparison between hardness and wear rate in WC-Co composite in both nanostructured and
conventional states. (Reprinted from Jia, K., and Fischer, T. E., Sliding wear of conventional and
nanostructured cemented carbides, Wear 203–204, 310–318, Copyright 1997, with permission
from Elsevier.)

without any fracture or necking phenomenon. This phenomenon is known

as superplasticity that typically occurs in materials with fine grains (less
than 10 µm) and temperatures higher than Tm/2 (where Tm is the melting
point in Kelvin). As superplasticity behavior allows us to produce pieces
with very complicated shapes form materials such as metallic matrix com-
posites and intermetallic compounds (which cannot be machined), it is vital
and useful in industrial issues.
To the moment, industrial application of superplastic deformation is lim-
ited due to its requirement for a low rate of deformation (about 10 –3s–1), which
causes a longer deformation period (20 to 30 minutes). Still, the needed defor-
mation rate for the occurrence of the superplasticity behavior is inversely
related with square of grain sizes. Hence, one can claim that if grain size
decreases up to 10 times, the optimum rate of plastic deformation for achiev-
ing superplastic behavior increases up to 100 times. To simplify, a decrease
of grain size from 2 µm to 200 nm cut the superplasticity time from 20 to
30 minutes to 20 to 30 seconds. Moreover, with the decrease of grain size
the temperature range necessary for superplasticity will shrink. Then, it is
Synthesis, Processing, and Application of Nanostructures 29

TABLE 1.5
Nominal Composition and Structural Characteristics of WC-Co Composites in
Figure 1.17
Structural Characteristics Hardness and Toughness

Sample Vickers
WC Grain Size Cobalt Content Measured Mean Hardness K1C
( μm) (vol%) Free Path (μm) (GPa) (MPa.m1/2)
FC20 1.2 30.5 1.06 11 NA
FC15 1.0 23.6 0.61 13 NA
FC6 1.0 10.1 0.39 17 9
FC6M 0.7 10.1 0.25 18.6 8.2
RTW10 2.5 16.3 1.0 12.8 16.4
RTW6 1.2 10.1 0.43 16.8 10
RTW6M 0.8 10.1 0.14 18.4 8.4
NA15 0.07 23.6 0.068 19.4 8
NA13 0.07 20.8 0.068 20.5 8.3
NA7 0.07 11.7 0.039 23.0 8.4
Note: The number in the sample identification indicates the cobalt content in wt%. For
example, NA15 contains 15 wt% and 23.6 vol% Co. Hardness indicated in GPa.
1000 kg.mm–2 = 9.81 GPa.
Source: Reprinted from Jia, K. and Fischer, T. E., Sliding wear of conventional and nanocrystalline
cemented carbides, Wear 203–204, 310–318, Copyright 1997, with permission from Elsevier.

predicted that industrial applications of superplastic shaping with nano-

structures would have a huge development.144,145
Superplastic behaviors in low temperatures have been reported in some
nanostructured metals or even intermetallic compounds. For example, nano-
crystalline nickel in a temperature of 0.36 Tm shows a superplastic behavior.
10

8
k.106

5
0.0 0.5 1.0 1.5 2.0 2.5 3.0
WC Grain Size, µm

FIGURE 1.18
The variation of wear coefficient with the carbide grain size in WC-Co composites: Triangles,
nanocomposites; squares, cermets with 6% Co; circles, RTW10, FC15, and FC20 from Table 1.5.
(Reprinted from Jia, K., and Fischer, T. E., Sliding wear of conventional and nanostructured
cemented carbides, Wear 203–204, 310–318, Copyright 1997, with permission from Elsevier.)
30 Two-Dimensional Nanostructures

As Machined

725°C, 1×10–3 s–1

560% Elongation
1 mm

FIGURE 1.19
Nanocrystalline samples of Ni3Al before and after tension test in 725°C and strain rate of
1 × 10 –3 s–1. (Reprinted from Mishra, R. S., Valiev, R. Z., McFadden, S. X., and Mukherjee, A. K.,
Tensile superplasticity in a nanocrystalline nickel aluminide, Materials Science and Engineering
A 252 (2), 174–178, Copyright 1998, with permission from Elsevier.)

This temperature is about 450°C less than the superplastic temperature of

microcrystalline Ni. Pure nanocrystalline copper shows a linear strain of
5000% without any hardening, whereas microcrystalline copper samples
can have a linear strain of only 800%. A fascinating example on this issue
is superplastic behavior of an intermetallic compound of Ni3Al (Figure 1.19).
These materials (with grain size of 50 nm) manifest a superplastic behavior
in temperature more than 650°C, while the tensional sample of Ni3Al has a
linear strain of 560% in a temperature of 725°C. Figure 1.20 exhibits super-
plastic behavior in 7034 aluminum alloy under a tension test. It must be
mentioned that thermal stability of nanostructures and lack of grain growth
should be considered for use of their superplastic behavior. This thermal
stability will be discussed in the next section.
Mechanical properties of nanostructures can be summed as follows:

1. Elastic modulus of nanocrystalline materials almost equals that of

microcrystalline materials. However, in very fine grain size (less
than 50 nm) elastic properties have not fully been studied.
2. Once grain size decreases to 15 to 25 nm, hardness and yield
strength of nanostructured materials rise according to the Hall–
Petch equation. In some cases, in grain sizes less than 15 to 25 nm,
the curves gradient is zero, whereas in some others it is negative.
3. Creation of nanostructures in metals leads to a substantial rate of
flexibility. Also, it results in high flexibility for brittle materials (such
as ceramics and intermetallic compounds) in low temperatures.
4. Superplastic deformation of nanostructured materials takes place in
lower temperatures and with higher rates.
Synthesis, Processing, and Application of Nanostructures 31

Al-7034

Initial sample

T = 673 K

1.0×10–1 s–1 540%

3.3×10–2 s–1 790%

1.0×10–2 s–1 1090%

1.0×10–3 s–1 630%

2 cm

FIGURE 1.20
Appearance of the specimens after equal-channel angular pressing (ECAP) through six passes
at 473°K and then pulling to failure at different initial strain rates at 673°K: the upper specimen
is untested. (Reprinted from Xu, C., Furukawa, M., Horita, Z., and Langdon, T. G., Using ECAP
to achieve grain refinement, precipitate fragmentation and high strain rate superplasticity in a
spray-cast aluminum alloy, Acta Materialia 51 (20), 6139–6149, Copyright 2003, with permission
from Elsevier.)

1.5  Thermal Stability of Nanostructures

Due to having extensive interfaces, nanostructured materials have more
freedom than the common materials (microcrystals). As a result, nanostruc-
tured materials, disregarding their production method, are more stable in
terms of thermodynamic aspects. Nanostructured materials lose their free
energies by decreasing their interfaces, which result in growth of grains and
phase particles.
The study of thermal stability and growth of grains and phases of nano-
structures has two main aspects:

1. If the objective is production of a structure with the least grain size,

we must stop grain and phase growth during the production pro-
cesses (such as sintering), because enlarging the structure eliminates
so many desirable properties of the nanostructures.
2. Through grain size and phase change through the growth process, it is
feasible to obtain a wide range of mechanical and physical properties.
In this way, through the control of growth process, one can create a
fine structure in favorable dimension and size and given properties.
32 Two-Dimensional Nanostructures

According to the Gibbs–Thomson equation, the thermodynamic motive

force for grain growth in polycrystalline materials can be stated as follows:

2 γV
= (1.10)
d

where ∆µ is the chemical potential difference in both sides of the grain

boundary caused by their face curve, γ is the grain boundary energy in the
surface unit, V is the atomic volume, and d is the grain size.
Equation (1.10) shows that once the grain size is smaller, the thermody-
namic motive force (∆µ) for their growth would be higher. This means that
the growth rate of the grains is inversely correlated with their size. On the
other hand, grain growth is a diffusive process, so an increase in tempera-
ture leads to its increase. Then, one might say,

δd K
= (1.11)
δt d

where K is a quantity that depends on energy and structure of grain bound-

ary and varied with temperature according to the following equation:

K = K0exp(–Q/RT) (1.12)

where Q is the activation energy of the grain growth, T is the temperature

(in Kelvin), R is the gas constant, and K0 is a constant value.
If d is the grain size in the moment in which grains start to grow, integrat-
ing from Equation (1.11), we have

d2 – d02 = 2Kt (1.13)

If we consider that the d0 is small enough, then

d2 = 2Kt (1.14)

Equation (1.14) is a parabola that presents grain growth in ideal condi-

tions. This shows that passing the time, grain growth rate (curve’s gradient)
shrinks. However, due to the presence of alloy elements, impurities, second-
phase particles, voids, and so forth, on grain boundaries, Equation (1.14) does
not match data obtained in the laboratory, so the grain growth equation is
presented as

dn = Kt (1.15)

For standard polycrystalline materials, n is greater than two. Once the mate-
rials purity increases and temperature goes up, n approaches 2. The growth
Synthesis, Processing, and Application of Nanostructures 33

mechanism of the grains can be explained by two parameters of n and Q.

In common polycrystalline materials activation energy of grain growth is
rather equal to activation energy through grain boundary diffusion. This
implies that grain growth is performed by their movement and transition
through the grain boundary.
The presence of second-phase particles or impurities on the grain bound-
ary causes a decrease of the grain growth rate. The presence of second-
phase particles on the grain boundary leads to a decrease of its surface area.
Consequently, grain boundary movement and its separation from second-
phase particles requires a new grain boundary. To simplify, second-phase
particles inhibit grain boundary movements by inserting a force against
thermodynamic motive force. This is known as Zener force. When grain
boundary energy in the surface unit and radius of second-phase particles
are, respectively, γ and r, it can be inferred from Figure 1.21 that the magni-
tude of Zener force in a length unit of the grain boundary equals γsinθ. If we
multiply this by distance between intersection of the grain boundary with a
second-phase particle (2πcosθ), the total value of Zener force would be

F = 2πr γ sinθcosθ (1.16)

The maximum amount of this force (Fm) is when θ = 45°, so

Fm = πr γ (1.17)

Direction of grain
boundary movement
R
σgb
σgb

1
σp/m
y0 σgb

θ
r 2
σp/m

Fz

FIGURE 1.21
Effect of second-phase particles on movement of grain boundary. (Reprinted from Moelans,
N., Blanpain, B., and Wollants, P., A phase field model for the simulation of grain growth in
materials containing finely dispersed incoherent second-phase particles, Acta Materialia 53 (6),
1771–1781, Copyright 2005, with permission from Elsevier.)
34 Two-Dimensional Nanostructures

If f is the volume fraction of the second phase, the average number of par-
ticles in volumetric unit of second phase (N) is

f
N=
4 3 (1.18)
πr
3

Because it is only possible for particles with a distance of ±r to touch the

grain boundary, the number of particles in the second phase in the surface
unit of a grain boundary would be

3f
N = 2 rN = (1.19)
2 πr 2

Then, the total Zener force inserted on a surface unit of the grain boundary
can be obtained from the following equation:

3 fγ
P = Fm × N = (1.20)
2r

Because the grain size is small enough, the prohibiting force against grain
growth (P) is very unsubstantial in comparison with the thermodynamic
motive force for grain growth, so grain starts to be enlarged. But, once the
grain size goes up thermodynamic motive force decreases, and whenever it
is equal to the P grain growth would be stopped. Hence, the maximum grain
diameter (dm) achieved in the growth process in the presence of second-phase
particles is as follows:

2γ 3 f γ
= (1.21)
dm 2r

4r
dm = (1.22)
3f

The most important result obtained from Equation (1.21) is that the finer par-
ticle size of second phase and their higher volumetric fraction leads to their
greater influence on grain growth rate.
With respect to discussions above, it is expected that grain growth in
nanocrystalline materials can be done even in low temperatures, though
data and results of laboratory tests do not support this. In fact, many
nanocrystalline materials including metals, ceramics, and intermetallic
compounds produced in different methods are stable even in fairly high
temperatures. Thermal stability of nanomaterials has been reported even
Synthesis, Processing, and Application of Nanostructures 35

at 40% to 50% of their melting point, which is equal to that for common
polycrystalline materials.
The results show that activation energy for grain growth (Q) in nanocrys-
talline materials is in agreement with activation energy of grain boundary
diffusion (Q b), though different values have been reported for n (2 to 10).
Some other outcomes imply that for nanocrystalline materials, activation
energy of grain growth in high temperatures is in agreement with activation
energy of lattice diffusion; however, in low temperatures it is close to the
activation energy of grain boundary diffusion.
Thermal stability of nanocrystalline materials and lack of grain
growth can originate from several factors such as the presence of coaxial
grains with a flat surface, the presence of impurities and their separation
in the grain boundary, and the occurrence of voids in their structure. For
example, it was reported that grain size of nanocrystalline titanium oxide
(TiO2) with a porosity of 25%, after thermal operation in a temperature
of 700°C for 20 hours, shifts from 14 to 30 nm. However, once the poros-
ity drops to 10%, after performing the same thermal operation the grain
growth exceeds 500 nm. This high thermal stability of the nanocrystals
was assessed with several models. These models show that in grain sizes
lower than a critical value (dc), grain growth has a linear relationship with
time, but in grain sizes larger than dc, grain growth relationship with
the time, like common polycrystalline materials, is a parabolic equation.
Because d < dc grain growth is not controlled by thermodynamic motive
force caused by grain boundaries curve, it might be possible that some
other mechanisms, such as elimination of vacancies in grain boundaries,
are responsible for grain growth. Because grain growth leads to a decrease
of total area of grain boundary surface, then vacancies in grain bound-
aries must be located in other places or transferred to sample surfaces.
Computational models indicate that during the growth process, these
vacancies are mainly removed in areas close to grain boundaries and in
the form of atomic vacancies. As a result, this leads to creation of an unbal-
anced concentration in atomic vacancies of the sample and an increase of
free energy, which can compensate for the decrease of energy caused by
grain growth. Based on this model, once the grain growth is controlled by
redistribution of the vacancies, activation energy of the grain must be a
larger number (close to activation energy of lattice diffusion). The obtained
results from this model fairly match laboratory data. It is worth mention-
ing that the presence of second-phase particles, impurities, and voids cre-
ated by production operations is a source of contradictions between the
results of different researchers and laboratory data with mathematical
models. In the presence of the above-mentioned agents, grain growth can
mainly occur by atomic lattice diffusion.
Nanocomposites contribute to growth of reinforced phase particles, as
well as grain growth. Similarly, grain growth is due to thermodynamic
motive force of the second-phase particles and the extensive interface
36 Two-Dimensional Nanostructures

between second-phase particles and the matrix. Hence, the particles of

nanophases gradually start to grow, and their number in a volumetric
unit drops and the free energy of the system drops. This process leads
to removal of favorable features of a nanocomposite-like decrease of its
hardness and strength. Moreover, according to Equation (1.20), once the
particles of the second phase expand in size, their effect on stopping grain
growth will be less significant.
Like growth process of the grains, second-phase particles are controlled by
atomic diffusion and then they will grow with an increase in the tempera-
ture. Atomic diffusion can occur across the grains, from grain boundary, or
through the interface of second-phase particles and the matrix. Assuming
that the diffusion only occurs across the grains, growth rate of second-phase
particles (dr/dt) is offered as

dr/dt = K/r2 (1.23)

where r is the average size of second-phase particles in each moment, t is

time, and K is a value related to the diffusion coefficient (D) and interface
contact energy (γ).
If the particles’ initial size is z0, integrating from Equation (1.23) gives

r3 – r03 = 3Kt (1.24)

From Equation (1.23) it can be found that finer grains have a higher growth
rate. Because K increases with a increase of γ and D, then the growth rate
of the second-phase particles will be low in the cases of small γ and D.
Decrease of γ demands using a second phase that can create a shared inter-
face with the interface. In addition, if particles of the second phase have
elements with low solubility in the matrix, the diffusion coefficient (D)
will be extremely small which, in turn, leads to thermal stability of the
second phase.149–154

1.6  Nanotechnology and Future Perspectives

Nanotechnology mainly involves four key aspects including

1. Miniaturizing systems
2. Obtaining new materials with nanodimensions
3. Enhancing the efficiency and automation of the systems and equipment
4. Increasing informatics storage capability
Synthesis, Processing, and Application of Nanostructures 37

Nanotechnology is used in several aspects ranging from electronic,

visual communication, and biological systems to new intelligent materi-
als. The reasons for the wide use of nanostructures and nanomaterials are
listed below:

1. Unusual physical properties of the nanostructured materials, such

as Au nanoparticles as an inorganic color used for glass dyeing
2. Expanded surfaces, like Au nanoparticles that are placed on the
metallic oxides and used as low temperature catalyzers or nano­
particles for several types of the sensors
3. Extremely fine dimension, which is of great importance

Table 1.6 introduces some current and future applications of the produced

materials by the nanotechnology using the new technologies in this field.
In this text, some nanostructures and nanomaterials’ applications as well
as capabilities and potentials of the nanomaterials will be discussed in
detail.155–160

TABLE 1.6
Some Current and Future Applications of the Produced Materials by the
Nanotechnology
Technology Current Impacts Future Impacts
Heat-resistant coatings Optimum heat resistance coatings
Enhancing images’ quality Multiuse nanometric coatings
Distribution and
Antiabrasive coatings Fine-grain structures
coating
Information storing layers Information storing layers with
higher storage capacity
Molecular sifter Specific molecules sensor
Medicine carrier in the human body Stimulated spotter particles
High contact surface
Providing appropriate catalyzers Energy storage (fuel cells)
Absorptive and repellant materials Gas sensors
Soft magnetic materials Superplastic ceramics shaping
Ductile and hard cutting tools Ductile materials with high strength
Reinforced materials
Nanocomposite cements Composites filled with
nanostructured fillers
Biological-medical Activated nanoparticles Cellular marking
aspects Local heating
Reading heads made of giant Memories and microprocessors
magnetic resistance (GMR) with capacity of several thousands
Nanotools of Gigabites
Biological sensors
Nanotubes, highly bright monitors
38 Two-Dimensional Nanostructures

1.7  Some Applications of Nanostructures

Applying the nanomaterials, it is possible to achieve the following in the
nanomaterials and nanosystems:

1. Ability to control the systems’ size

2. Ability to determine the accurate needed composition (not approxi-
mate one) without any structural defects such as voids
3. Possibility to control frequency dimension
4. During the assemblage of the constituting pieces, control of the
mutual effect level between the pieces as well as materials designs

1.7.1  Nanoelectronic and Molecular Electronic

Many advances in the molecular electronic and nanoelectronic field have
been made. In the molecular electronic, single molecules are designed for
control of electron transfer. The control on the surface of common metals
and semiconductors is conducted by surface arrangement and solid mate-
rials molecules via designing an electrical circuit. Once the molecules are
biologically active the bioelectronics pieces would be obtained.
Many nanoelectronic pieces, such as adjustable connections, electronic
switches, carbon nanotube transistors, single-molecular transistors, and so
on, were fabricated until now. Au nanoparticles are widely used in nano-
electronics and molecular electronics, due to their surface characteristics and
unified sizes. For instance, Au nanoparticles can serve as carriers through
several types of applied organic molecules or biological components. Au
nanoparticles can be used as connectors in many practical connections in
the structure of the electronic nanoparticles for employing in the sensors
and detectors.161–165

1.7.2  Nanorobots
Future applications of nanotechnology in medical sciences, mainly in nano-
drugs, will be very broad. One interesting application of nanomedicine is
creating nanotools for promotion of curing and recognition level. These
types of nanoparticles are known as nanorobots. These nanorobots can be
used as transportation tools for carrying therapeutic factors and early detec-
tors of the diseases and maybe metabolic or genetic defect treatments.166–168

1.7.3  Biological Applications

Among the most important applications of the colloid biological nano-
crystals, one can name molecules detection. Some biomolecules are able to
Synthesis, Processing, and Application of Nanostructures 39

detect one another with high precision and selectivity and can connect one
to another. Antibodies as receptors have several applications in molecular
detection applications. For instance, if a virus enters a live creature’s body,
antibodies detect it as an invader and attach to it, so the other sections of the
immune system would be able to kill the virus.
Nanocrystals attached to a molecular receptor are directly connected to
the position of ligand molecules. In this way, molecular labeling would be
possible and completed by the receptor. For instance, in the very sensitive
chromatic analysis method of DNA, color change of the Au nanoparticles
from the rubious to the blue is used (because of its accumulation).
Other biological capabilities of the nanostructures and nanomaterials
include employing semiconductor nanocrystalline colloids as a fluores-
cence sensor in cellular and chemical detection and use of nanostructured
materials as artificial bone.169–172

1.7.4  Catalytic Applications

Each material with high catalytic absorption activity certainly includes a
high contact surface. Because a decrease in nanomaterials size leads to an
increase of the surface area, these materials are vastly used in catalysts. For
instance, in a nanocrystal with a diameter of 10 nm, 15% of the atoms are
placed on its surface, while in a nanocrystal with a diameter of 1 nm, 100%
of the atoms are placed on the surface. Thus, a tiny nanocrystal with a vast
surface would show further catalytic activities.
Metallic nanoparticles have fairly high catalytic potential and selective
reduction potential of the materials. For example, the smooth surface of
gold has no catalytic properties at the temperature of 473°K in the reaction
of H2 and O2, but gold nanoparticles (>10 nm) deposited on the oxide sur-
face show very high catalyst activity in the hydrogenation and oxidation
reaction of the carbon monoxide. This potential is up to an extent in which
oxidation reaction of the carbon monoxide is even possible at a temperature
of –70°C.173–177

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resonant nanostructures: Nano-antennas and resonators, Optics Express 15 (17),
10869–10877, 2007.
2. Luo, Y., and Gu, H., A general strategy for nano-encapsulation via inter-
facially confined living/controlled radical miniemulsion polymerization,
Macromolecular Rapid Communications 27 (1), 21–25, 2006.