Nano Technology (OE) - Unit 2

NANO TECHNOLOGY (OE) - Unit II
(E4-I Sem)
Unique Properties of Nanomaterials
DEPARTMENT OF CHEMICAL ENGINEERING

RGUKT-AP
RK VALLEY 1
MICROSTRUCTURE AND DEFECTS IN NANOCRYSTALLINE MATERIALS:
The microstructural features of importance in nanomaterials include:

 Grain size, distribution and morphology
 The nature of grain boundaries and interphase interfaces
 Nature of intragrain 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.
 In nanocrystalline materials, a substantial fraction of atoms lies at the grain
boundaries and interfaces.
 The behaviour of nanocrystalline materials is decided to a large extent by these
defects, and as such, nanomaterials exhibit vastly different properties
compared to bulk materials.
2
DEFECTS IN CRYSTALLINE 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’
3
CLASSIFICATION OF DEFECTS :
0D 1D 2D 3D
Point Line Surface Volume
defects Defects Defects Defects
vacancies Grain
Inclusions
Boundaries
Edge
substituti Dislocation
onal
Twin
Boundaries Voids
interstitial
Screw
Schottky Dislocation
Stacking Micro
faults cracks
Frenkel 4
DISLOCATIONS:
 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 driving force for dislocations to be annihilated 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 exerted
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 annihilation of
dislocations.
 Hence, for a small distance from the surface and grain boundaries,
one would not expect to find any dislocations.
DISLOCATIONS:
• When the magnitude of the critical distance becomes comparable with
that of the grain size, as in nanomaterials, the stability of
dislocations is altered significantly.
• Hence, with decreasing grain size of nanograined materials,
dislocation stability is reduced, due to the large grain boundary
area.
• Dislocation mobility and interactions play a large role in determining
the deformation and plastic flow behaviour of conventional
crystalline materials.
• The deformation behaviour of nanocrystalline materials is
significantly different from that of conventional microcrystalline
materials.
• Dislocation density in annealed crystalline materials is 1010/cm.
• As the grain size is reduced to about 10 nm, the dislocation density
can reduce by 2–3 orders or more
DISLOCATIONS - IMAGE FORCE:
 The force exerted by this virtual imaginary image dislocation on the
dislocation defect in bulk is referred to as image force (F image).
 The condition for dislocation stability can be given by, F image ≤ b σP
where b is Burger’s vector and σP is Peierl’s stress
 The critical size (dc) below which the image forces make the
dislocations unstable is given by dc = Gb/σP
where G is the shear modulus.
Dislocation stability in typical FCC and BCC metals

TWINS, STACKING FAULTS AND VOIDS:
• Twins are generally observed in crystals subjected to deformation under high
strain rate or at low temperatures.
• Thermodynamically metastable, planar defects are often observed, even after
annealing, in many faceted nanomaterials, including nanorods 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 FCC structure, but nanocrystals and
nanorods of the same material often exhibit various structural modifications.
• Single or multiple symmetric twinning, as well as five-fold cyclic twinning,
resulting in decahedral and truncated decahedral nanostructures below
critical siges
• 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
anticipate the formation of twins in the nucleating crystals.
• Thus, the origin of such twins during the growth of nanoparticles from liquid is
Twins in nanocrystalline Cu particles

embedded in amorphous Fe-Zr-B
alloy. The twins formation is possibly
due to strains developed at the
amorphous Cu interface during
solidification.
• Voids in nanocrystallites may be situated at either triple

junctions or as large porosities due to insufficient compaction and
sintering of nanocrystallites synthesized from the powder route.
• Both types of voids influence the behaviour of the

nanocrystallites, the former 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 :
Two types of atoms can be distinguished in crystals:
crystal atoms with nearest-neighbour configurations corresponding to
the lattice (black circles) and
boundary atoms with a variety of interatomic spacings (white circles).
Nanocrystalline materials typically contain a high number of interfaces with

random orientation relationships, and consequently, 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 ic refer to the crystalline and intercrystalline components

of nanocrystalline materials, and X and V denote the property and volume
fraction of the respective components.
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 subscripts 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.
 Triple junctions can be described based on the disclination defect model.
 Disclinations are line defects characterised by a rotation vector ω in contrast
to the translational vector b for dislocations.
 Consider a solid rubber ball. If you cut a slit in it of width only as thick as a
blade and then try to forcefully bring together the ends of the cut portion,
the resultant defect is a dislocation.
 Instead, if you cut a wedge in the ball and now try to bring the cut ends
together, the resultant defect is a disclination.
 Unlike dislocations, the elastic stress fields of disclinations diverge with
distance.
 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.
 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.
MULTIPLY TWINNED NANOPARTICLES:
 Multiply twinned particles (MTP) with a pseudo five-fold symmetry are
observed in nanocrystalline particles and thin films of cubic face-centred
metals, diamond-type semiconductors (C, Si, Ge) and alloys.
 MTP are formed by sequential cyclic five-fold twinning, with each twin
sharing a common twin plane boundary with the adjacent twin.
 For example, that twinning in FCC occurs along the {111} plane. The angle
between two {111} planes is 70.53 degrees.
 Thus, repeated twinning five times will still not result in 360 degrees, but will
result in an annular gap of about 7.35 degrees.
 The fivefold symmetry formed from an FCC structure should have a distortion
due to the geometrical arrangements along the five-fold axis.
 This results in a typical rotational defect, similar to disclination defects in such
multiply twinned particles.
 The maximum size of these particles without distortion has been reported to
be ~40 nm because the internal stresses of the crystals increase as they grow.
 In 1957, Segall observed pentagonal grains of pyramidal shape in cold rolled

Cu upon thermal etching.
 In 1959, Melmed and Hayward observation of pentagonal whiskers (i.e.,
rod-like shapes) of Ni, Fe and Pt grown from the vapour phase on W
substrates.
 Pseudo five-fold symmetry particles have been seen in microcrystalline
chemical vapour deposited (CVD) diamond films and in various other
nanoparticles of FCC, diamond cubic or BCC structure.
 Nanocrystalline MTPs of c-BN, TiN, Si, SiC, etc., have been synthesized by CVD.
 Physical and chemical properties of materials assembled from five-fold
twinned nanoparticles may differ from materials consisting of untwinned
nanoparticles in a variety of aspects, according to their respective structural
characteristics.
 These differences concern properties sensitive to the surface energy, lattice
symmetry, internal structure and surface structure, and they may cause
EFFECT OF NANO-DIMENSIONS ON MATERIALS
BEHAVIOUR :
Elastic Property:
 The elastic modulus of a material is proportional to the bond strength between atoms
or molecules.
 The higher the bond strength, the higher will be the melting point and elastic
modulus.
 The second differential of the interatomic force–distance curve at the position of
equilibrium separation distance is known to be proportional to the elastic modulus.
 The elastic properties of crystalline materials are usually considered to be structure
(microstructure) independent.
 If the temperature is increased, the mean separation between atoms increases and
the elastic modulus decreases.
 A large increase in vacancy and other defect concentrations can be treated as
equivalent to higher apparent temperature.
 Increasing the defect concentration is thus expected to decrease the elastic modulus.
 However, the effect of defects on the elastic modulus is manifested only at significantly
higher concentration of vacancies.
 Nanomaterials,by virtue of their very high defect concentration, may have considerably
BEHAVIOUR :
Elastic Property:
The first measurements of the elastic constants and, Young’s modulus, E, of
nanocrystalline materials were performed with samples prepared by the inert
gas condensation method.
The elastic modulus of nanocrystalline compacts was found to be 30%–50%
lower than bulk values .
One of the first explanations proposed was that the elastic moduli of the grain
boundary regions are much smaller than the corresponding moduli of the
grain bulk region, due to weaker bonds and lower density of atoms.
In terms of the linear theory of elasticity for polycrystalline
materials, the elastic constants are expected to be reduced
by a fraction determined by the volume fraction of the
grain Boundaries,
where Co is the grain bulk modulus, Cgr is the grain boundary modulus; α ≈ 3Δd/d
is its relative volume fraction, where d is the grain size and Δd is the grain
BEHAVIOUR :
Elastic Property:
 Above eqn lead to significant changes only for sizes about or below 10 nm.
 However, an anomalous elastic modulus reduction was observed also for
greater sizes, up to d = 200 nm.
 However, it was soon realised that the porosities in the compact due to
inadequate sintering can also influence the measured elastic properties.
 It is well known that elastic properties depend on the porosity content (Δρm)
according to the formula:
where β is a constant, while E and Eo correspond to the measured and

reference elastic modulus of the material, respectively.
 The effect of porosities on the elastic modulus is particularly predominant in
materials with grain size below ~ 20 nm.
 The presence of porosities can result in a decrease in modulus of up to 20%-
25%.
BEHAVIOUR :
MELTING POINT:
The decrease in bonding energy due to enhanced surface and grain boundary
area in nanocrystalline materials can reduce the enthalpy of fusion and the
melting temperature.
At the melting point of a material, the solid and liquid phases are in
equilibrium.
For this to be thermodynamically possible, it is necessary that the chemical
potential of a component (μi) is the same in both solid and liquid phases (μil=
μis).
However, due to inherent internal stresses, the pressure of the solid is greater
than that of the liquid.
where γ is the surface energy and r is the radius of the solid sphere.
The chemical potential is related to pressure by the following equation:

BEHAVIOUR :
MELTING POINT:
By substituting the pressure relationship into the above equation and recalling
that at equilibrium the chemical potential of the liquid is equal to that of the
solid, assuming the overall pressure change in the liquid is negligible, and
noting that Sl – Ss = ΔSm, the following equation is derived:
It should be recognised that the bulk melting temperature is related by:
Combining the above relations yields a relationship that describes the decrease in
the melting point of a substance as the radius decreases.
It can be seen that the change in melting temperature is inversely proportional

to the radius of the sphere. In other words, as the grain size is reduced, the
melting point is lowered.
BEHAVIOUR :
MELTING POINT:
 It has been observed that nano-CdS of diameter ~ 2.5 nm melts at 600 K, much lower
than the bulk melting point (1675 K).
 The SW carbon nanotube melts at ~ 1600 K, 0.42 times its bulk melting point (3800 K).
 It is known that atoms in a solid vibrate about their mean position.
 The amplitude of the vibrations increases with increasing temperature.
 When the vibration amplitude exceeds a certain percentage of the bond length,
melting begins at the surface and propagates through the solid.
 Atoms at the surface and grain boundary are less constrained to vibrate compared to
atoms inside the crystal lattice.
 As the grain size decreases, the percentage of atoms residing at surfaces and grain
boundaries increases significantly. Hence, freestanding nanoparticles may show a lower
melting point compared to bulk.
 A similar effect has been reported on zinc nanowires embedded in holes in an anodic
alumina membrane.
 The melting point of zinc nanowires was found to decrease with decreasing diameter
of the nanowire.
BEHAVIOUR :
MELTING POINT:
In contrast to nanoclusters and nano-agglomerates, nanoparticles within a
matrix may experience an enhancement in the melting temperature.
The matrix exerts a pressure, p, which can affect the melting temperature of the
particles. This is described by:
where μ is the shear modulus of the matrix, κ is a dimensionless factor that

takes into account the presence of other particles, ΔV is the change in particle
volume due to thermal expansion, and Vo is the initial particle volume.
From the Clausius–Clapeyron equation (dT/dP = ΔV/ΔS), it is understood that
the transition temperature will increase with increase in pressure, if change
in volume on melting is positive.
the melting point of nanoparticles embedded in a
bulk matrix increases with decreasing size of
particulate as the pressure increases with decrease
in particle size
BEHAVIOUR :
MELTING POINT:
 It is fascinating to observe that the melting temperature does not

continuously decrease with decreasing grain size in nano-dimensions.
 It has been found that a solid containing about 10 atoms of Ga or IV A
elements (C, Si, Ge, Sn and Pb) melts at temperatures that are higher than
the melting point of the corresponding bulk solid (Tm,b).
 This is in contrast to the behaviour of nanograined solids with grain size in

the range of 1–100 nm, where a universal decrease in melting point is
observed with the grain size.
 Compared to the melting point of bulk Ga, which is about 303 K, clusters of
Ga39–40 melt at 550 K, while smaller clusters of Ga17 do not melt up to 700 K.
BEHAVIOUR :
DIFFUSIVITY:
 Diffusion kinetics increases with increasing defect content of the material,
like vacancy concentration.
 Grain boundaries and dislocation cores provide easy diffusion paths
compared to bulk lattice, because the structure is more open/defective.
 Thus, fewer atomic bonds have to be disrupted for diffusion along defect
cores, resulting in lower activation energy paths.
 The numerous interfaces in nanocrystalline materials provide a high density of
short circuit diffusion paths.
 Thus, nanocrystalline materials are expected to exhibit enhanced
selfdiffusivity in comparison to single crystals or conventional polycrystals
with the same chemical composition.
 This idea was confirmed by self-diffusion measurements in nanocrystalline Cu.
 The measured diffusivities in nanocrystalline Cu are about 14–20 orders of
magnitude higher than lattice diffusion.
BEHAVIOUR :
DIFFUSIVITY:
It is known that the diffusion coefficient obeys an Arrhenius-type relation with

temperature:
where Q is the activation energy for diffusion.

The activation energy for lattice diffusion (Ql) is higher than that along short
circuit paths like dislocation cores (Qd),
grain boundaries (Qgb) and surfaces (Qs).
If log (D) is plotted as a function of (1/T),

the slope will be proportional to the activation energy.
BEHAVIOUR :
DIFFUSIVITY:
For the same reason, the difference in the diffusion coefficients between the
grain boundary and lattice are much higher at lower temperatures.
It can be inferred from the figure that grain boundary diffusion will have a
greater effect at lower temperatures.
At higher temperatures, the diffusion coefficients of lattice and grain boundary
diffusion are nearly the same.
Considering the much lower volume fraction of grain boundaries in conventional
materials, the effective diffusion coefficient would be largely determined by
the lattice diffusion coefficient.
Since the effective diffusion coefficient (Deff) is an average of diffusion along
different paths, it can be inferred that,
where Vd and Vs are volume fractions of dislocation cores and surfaces in the
material, respectively, d is the grain size, and Dl, Dp, Dgb and Ds are lattice,
dislocation pipe, grain boundary and surface diffusion coefficients,respectively.
BEHAVIOUR :
DIFFUSIVITY:
For a grain of about 1 μm in diameter, it is obvious that the second term in the
above equation will be significantly less than Dl, meaning that the lattice
diffusion coefficient will be nearly equal to the effective diffusion coefficient.
As the grain sizes reduce to nano-dimensions, the second term has a

dominating effect.
Since grain boundary diffusion coefficients are a few orders higher than lattice
diffusion, the effective diffusion coefficients of nanocrystalline materials are
higher than that observed in coarse-grained materials.
Diffusivities in nanomaterials (in m2/s at 300 K)

BEHAVIOUR :
Grain growth characteristics:
For sphere of radius r. Its surface area is proportional to the square of its radius,
while the volume is proportional to the cube of the radius.
The ratio of the surface area to the volume of a sphere, for example, can be seen
to be inversely proportional to the radius.
The smaller the crystallite size, the larger is the surface area per unit volume.
Nanocrystalline materials have a significantly larger surface area per unit
volume fraction of grain boundaries compared to microcrystalline solids.
Grain boundaries are higher energy regions in materials.
There is always a driving force for reduction in the grain boundary surface area
per unit volume.
This can happen only by coarsening of smaller grains involving migration of grain
boundaries.
Such a reduction in grain boundary surface area per unit volume is the major
driving force for grain coarsening in nanocrystalline materials, in order to
reduce the net energy of the system.
BEHAVIOUR :
 However, grain boundary mobility is predominantly a diffusion limited process and hence
depends to a large extent on composition and temperature, amongst other
considerations.
 Grain growth has an exponential dependence on the temperature as shown in
the equation below:
where r is the radius of the crystal, r0 a material constant, Qgb is the activation
energy for grain boundary migration, and n is an exponent factor and is
typically 2 for microcrystalline grains.
 the above expression derived for microcrystalline solids, it has also applicable
to nanocrystalline materials.
 Activation energy for grain growth in nanocrystalline solids is expected to be
lower.
 In addition, in nanocrystallline solids, owing to the higher driving force for
grain growth the exponent factor, n, is normally much higher than 2.
BEHAVIOUR :
It can be seen that nanocrystalline solids cannot be stable at high normalized
temperatures (T/Tm) for any given material.
If the nanocrystalline grains grow larger at high temperatures, all the
advantageous properties of nanomaterials envisaged cannot be utilized in
service.
Nanocrystalline solids are not suitable for high temperature applications.
However, there is progress in grain boundary engineering to reduce grain
coarsening kinetics of nanocrystalline materials.
Grain boundary migration can be reduced by pinning the grain boundaries
either with secondary particles (Zener pinning) or by vacancy clusters.
Grain boundaries being higher energy sites, there is a driving force for several
secondary phases to be located there.
Grain boundary migration would thus incur an additional energy to break the
bonding with such particles, acting as a source of inhibition for grain growth.
The effective pinning ability of secondary phases is obviously dependent on both
BEHAVIOUR :
It is clear that for effective Zener pinning, the particles should be stable at high
temperatures and should not undergo coarsening themselves.
This can also be achieved by having dispersoids of secondary phases like
ceramics decorating the grain boundaries of nanocrystalline materials.
An effective means of synthesizing such a solid is by powder metallurgy processes
involving ball milling and consolidation techniques.
Thus, such a technique can be an effective route for achieving grain boundary
pinning to enhance the service temperature applicability of nanomaterials.
Copper nanograins do not significantly grow in the presence of tungsten
nanoparticles, in spite of heating it to 0.6 of its melting point.
Figure (Next slide) demonstrates the Zener pinning effect of W on grain growth in
Cu–W nanocomposites.
BEHAVIOUR :
Grain growth restriction in Cu–W nanocomposites heated to 500°C in (a) Cu–10%W

and
(b) Cu–20%W. The as-prepared composite (by high-energy ball milling) shows a grain
size of about 20 nm, which is very similar to that observed after heating to 500°C. In
comparison, nanocrystalline pure Cu usually shows abnormal grain growth even at
200°C. This clearly brings out the Zener pinning effect in the nanocomposites.
BEHAVIOUR :
There is another way of grain boundary engineering to restrict grain growth.
This involves enabling a grain boundary with a composition different from
that of bulk.
Grain boundary migration will also have to simultaneously involve diffusion of all
involved chemical species to ensure the same composition of grain boundary.
Such a solute drag effect can act as a rate limiting step for grain boundary
migration.
A heterogeneous composition can be obtained, for example, by grain boundary
segregation effects.
The solute drag effect of Cu in Ag in controlling the grain coarsening tendency of
nano-silver is demonstrated in Fig (Next Slide).
In this case, nanoparticles of pure Ag obtained by inert gas condensation of Ag
clusters on a substrate grow significantly when heated to 600°C.
In contrast, when Cu (having a higher melting point than Ag) is alloyed with Ag,
the grain growth is significantly reduced at the same temperature due to
BEHAVIOUR :
Grain growth restriction in Ag–Cu nanoparticles:

(a) Ag nanoparticles heated to 600oC and (b) Ag–Cu nanoparticles heated to 600oC.
The figure clearly shows that alloying Ag with the higher melting Cu reduces the
diffusivity, which leads to grain growth inhibition due to solute drag effect in single-
phase alloys. This is different from the Zener pinning effects observed in two-phase
BEHAVIOUR :
Enhanced solid solubility:
The solubility of a solute A in a solvent B is controlled by the chemical potential,
μA, of A in B.
The chemical potential and the solubility may be enhanced (or reduced) in
nanocrystalline materials in comparison to single crystals or glasses with the
same chemical composition.
The solubility of H in nanocrystalline Pd (at concentrations <10–3) is increased
by a factor of 10 to 100 relative to a Pd single crystal.
Similar effects have been observed in Mg and with the Mg-based alloys that
have become popular for hydrogen storage applications.
Figure shows a schematic of how the hydrogen

adsorption increases with a decrease in particle
size. This result has significant technological
importance.
BEHAVIOUR :
A similar effect was observed for Bi in Cu. The solubility of Bi in crystalline Cu is less
than 10–4 at 100°C.
In contrast, the solubility of Bi in nanocrystalline Cu is about 4%, corresponding
to a solubility enhancement by about 10,000 times relative to crystalline Cu.
The solubility being greatly promoted with decreasing grain size when the size of
the matrix nanoparticles is less than 20 nm.
Figure (Next slide) demonstrates this phenomenon in the Fe–Si system.

It can be clearly seen that the solubility of Si in Fe is almost negligible up to a
crystallite size of Fe of about 20 nm, below which there is a sudden dissolution
of Si.
The figure also shows that this solubility can be correlated to the grain boundary
volume in nanocrystalline materials, which follows a similar trend.
It has also been possible to alloy conventionally immiscible systems by optimising
the process conditions to achieve nanocrystalline grains.
BEHAVIOUR :
Solubility of Si in Fe as a function of crystallite size of Fe. The figure demonstrates

significantly higher solubility of Si in nanocrystalline Fe below 20 nm.
Magnetic properties:
Magnetic nanoparticles applications:

 Ultrahigh density magnetic storage devices,
 Magnetic random access memory (MRAM),
 Ferrofluids,
 Spintronics,
 Magnetic semiconductors,
 Nanogranular magnetic materials, etc.
The strength of a magnet is decided by its coercivity and saturation

magnetization values.
They increase when the grain size decreases and the specific surface area per
unit volume of the grains increases.
 Soft magnetic nanocrystalline alloys:
 Coercivity, also called the magnetic coercivity, coercive field or coercive force, is
a measure of the ability of a ferromagnatic material to withstand an
external magneticfield without becoming demagnetized.
 In conventional soft magnetic alloys, low coercivity achieved using coarse-
grained materials so that magnetic flux pinning at the grain boundaries is
avoided.
 In nanocrystalline materials, when the grain sizes are much smaller than the
domain wall width, the magnetic anisotropy is averaged over many grains and
orientations and hence the coercivity is significantly reduced and permeability
is enhanced.
 Fe–Si–B–Nb–Cu amorphous alloys are found to transform to a BCC Fe–Si solid
solution with grain sizes of about 10 nm during annealing at temperatures above
the crystallization temperature.
 The presence of small amounts of Cu helps to increase the nucleation rate of
the BCC phase, while Nb retards grain growth.
Soft magnetic nanocrystalline alloys:
 These ‘Finemet’ alloys provide low core losses (even lower than amorphous soft
magnetic alloys such as Co–Fe–Si-B), exhibit saturation induction of about 1.2 T,
and exhibit very good properties at high frequencies.
 The Finemet-type nanocrystalline alloys are superior in their magnetic
properties, they exhibit lower saturation induction than Femetalloid
amorphous alloys, mainly because of the lower Fe content to attain amorphization
and because of the addition of Nb and Cu (or other elements to control the
nucleation and growth kinetics).
 To avoid this problem, ‘Nanoperm’ alloys based on the Fe–Zr–B system have
been developed.
 These contain larger concentrations of Fe (83%–89%) and have higher
saturation induction (∼1.6–1.7 T) compared to the Finemet alloys.
 The Nanoperm nanocrystalline alloys have very low energy loss at power
frequencies of 60 Hz, making them potentially interesting for electrical power
distribution transformers.
The small single-domain nanocrystalline Fe particles in the amorphous matrix
give these alloys their unique magnetic behaviour, the most dramatic being the
lowest energy losses (narrowest B/H hysteresis loop) of any high permeability.
These alloys exhibit nearly zero magnetostriction. These materials are made by
crystallization of rapidly solidified amorphous ribbons.
Figure shows amorphous melt spun ribbons of Fe-Si-B-Nb-Cu alloy.
Figure shows the transmission electron microscopic images of melt spun and annealed
alloys showing the amorphous and nanocrystalline structure, respectively.
(a) as melt spun and (b) annealed (525°C for 1 h) ribbons of Fe–Si–B–Nb–Cu alloy
The decrease in hysteresis loop size due to nanocrystalline phase formation on
annealing is shown in Fig.
 Permanent magnetic nanocrystalline materials:
 The nanoscale two-phase mixtures of a hard magnetic phase and a soft
magnetic phase can exhibit values of remanent magnetization, Mr, significantly
greater than the isotropic value of 0.5Ms.
 Enhancement of remanence in such a composite can be obtained when the
 nanocrystalline grain size and the degree of coherence across interphase
boundaries are such that exchange coupling occurs between the two phases.
 Exchange coupling allows crystallographically isotropic materials to exhibit

remanence values approaching those achieved after full alignment Fig.
 The Fe-rich compositions (e.g., Fe90Nd7B3)

 result in a mixture of the hard Fe14Nd2B-
 phase and a soft Fe-phase, which
 increases the magnetic induction.
Permanent magnetic nanocrystalline materials:
These two-phase nanoscale ferromagnetic alloys have been prepared by
nonequilibrium methods such as melt spinning, mechanical alloying and sputter
deposition.
Magnets made of nanocrystalline Y–Sm–Co grains possess unusual magnetic

properties due to their extremely large surface area.
The magnetic properties of the Sm2Co17 hard magnet can be significantly

improved by developing nanocomposites with either Fe or FeCo alloy soft magnet,
which is clearly demonstrated in Fig. (Next slide)
Typical applications for these highpower rare earth magnets:

quieter submarines, automobile alternators,
land-based power generators, motors for ships,
ultrasensitive analytical instruments and magnetic resonance imaging (MRI) in
medical diagnostics.
Permanent magnetic nanocrystalline materials:
Improvement in magnetic properties in Sm2Co17–FeCo nanocomposites in

relation to bulk microcrystalline composites. The improved magnetic
properties can be attributed to exchange coupling between the soft and hard
magnetic phases in the nanocomposites.
Giant magnetoresistance (GMR) :
 The phenomenon of significant decrease in electrical resistance when materials
are exposed to a magnetic field is known as giant magnetoresistance (GMR)
effect.
 This phenomenon is usually observed in bulk composites consisting of

ferromagnetic & non-magnetic phases or in thin film multilayers of these
materials, as shown in Fig (Next Slide)
 A significant decrease in resistance from the zero-field state is evident in these

materials when the external magnetic field leads to adjacent ferromagnetic
layers, aligning in an antiparallel fashion due to weak anti-ferromagnetic
coupling between layers.
 It was observed in both nanocrystalline thin films and equiaxed granular

nanocrystalline materials.
Schematic diagram showing GMR effect in magnetic ultrathin films.

 In case of granular materials, GMR is observed when small ferromagnetic single-
domain particles with randomly oriented magnetic axes are embedded in a non-
magnetic matrix.
 The explanation for the GMR is spin-dependent scattering of the conduction
electrons at the ferromagnetic/non-magnetic interfaces and, to a lesser extent,
within the magnetic grains.
 The GMR is inversely proportional to the average particle diameter.
 The effect can be up to 100% in multiple stacks of ultrathin films.

 This effect was first observed in Fe/Cr multilayer ultrathin films and is also
commonly observed in Cu/Co nanocomposites.
 This effect has wide application in magnetic reading heads for computer hard
discs and in position sensors.
Electrical properties:
Nanomaterials can hold considerably more energy than conventional coarse-
grained
materials because of their large grain boundary (surface) area.
They are materials in which an optical absorption band can be introduced, or an
existing band can be altered by the passage of current through these materials,
or by the application of an electric field.
Conventional and rechargeable batteries are used in many applications that need
electrical energy.
The energy density (storage capacity) of these batteries is usually quite low,
requiring frequent recharging.
Nanocrystalline materials are good candidates for separator plates in batteries
because they can hold considerably more energy than conventional ones.
Nickel– metal hydride batteries made of nanocrystalline nickel and metal hydrides
are envisioned to require far less frequent recharging and to last much longer.
The dielectric properties are significantly enhanced by making these
nanocrystalline.
The dielectric constant of lead zirconium titanate (PZT) can be increased to
35,000 when it is made in the nanocrystalline state in comparison to a value of
2000 in the microcrystalline PZT (Fig.)
Exceptionally high dielectric constant in nanocrystalline PZT. The

nanocrystalline PZT with an average particle size of about 10 nm shows a
dielectric constant of about 35,000 at Tc. In contrast, bulk PZT has a dielectric
constant of only about 1000 at the same temperature.
When ferroelectric and ferromagnetic phases are brought together in a
nanocrystalline state, there can be high magneto-electric effect in the material,
which is demonstrated in Fig. 2.17.
There are examples where the electrical nature of materials changes on
nanocrystallization.
Figure is an example for this behaviour; a metallic Al–Cu–Fe alloy is converted to
a semiconductor with a negative temperature coefficient of electrical resistivity
in the nanoquasicrystalline phase, the explanation for which is still inconclusive,
providing scope for further work.
OPTical properties:
Nanocrystalline systems have attracted much interest due to their novel optical
properties, which differ remarkably from bulk crystals.
Key contributory factors include:
 Quantum confinement of electrical carriers within nanoparticles,

 Efficient energy and charge transfer over nanoscale distances and,
 In many systems, a highly enhanced role of interfaces.
The linear and non-linear optical properties of such materials can be finely
tailored by
 Controlling the crystal dimensions and

 The chemistry of their surfaces.
Fabrication technology becomes a key factor for the applications.
OPTical properties:
Plasmons :
 These are quasiparticles obtained by quantization of plasma oscillations, similar
to photons, which form by quantization of light and sound waves.
 Plasmons can couple with a photon to create another quasiparticle called
plasma polariton.
 Surface plasmons (SP) are plasmons that are confined to surfaces and interact
strongly with light resulting in a polariton.
 SPs are responsible for the colour of nanomaterials.
 An SP is a natural oscillation of the electron gas inside a given nanosphere.
 If the nanosphere is smaller than the wavelength of light, the frequency of
which is close to that of the SP, then the SP will absorb energy.
 The frequency of the SP depends on the dielectric function of the nanomaterial,
and the shape of the nanoparticles.
 For spherical particles of gold, the frequency is about 0.58 of the bulk plasma
frequency.
OPTical properties:
Plasmons :
The bulk plasma frequency is in the UV region, the SP frequency is in the visible
range (wavelength close to 520 nm).
Suppose we have a suspension of nanoparticles in a host and a wave of light is
applied, the local electric field may be hugely enhanced near an SP resonance.
If so, one expects various non-linear susceptibilities, which depend on higher
powers of the electric field to be enhanced even more.
The ultrafast optical emission of nano-sized diamond crystallites has been detected
under the picosecond (ps) laser excitation of 300 nm through ultrafast
fluorescence spectroscopy.
This optical emission and photoluminescence (PL), induced at a laser wavelength
of 300 nm, confines blue light.
It has not been observed under the same experimental conditions from samples of
a natural single crystal.
The PL phenomenon of nano-diamond can be understood considering the effects
of the surface states and the enlarged surface-to-volume ratios in nanoscale
OPTical properties:
Plasmons :
Figure shows the image of Don Quixote made with nanocrystalline VO2.
When the temperature is below 341 K, the material is transparent and the image
is not visible. When the temperature rises above this point, however, the material
becomes reflective and the image appears.
OPTical properties:
Plasmons :
Richard Haglund, the Vanderbilt physics professor, has clocked the transition of
VO2 nanoparticles from a transparent to a reflective mirror-like state, at less
than 100
femtoseconds (a tenth of a trillionth of a second), leading to the world’s fastest
optical shutter.
VO2 can switch from a transparent to a reflective state in less than the time taken by
a beam of light to travel a tenth of a millimeter.
Phase transitions in solids generally occur at the speed of sound in the materials;
however, this transition in VO2 occurs 10 times faster.
The reasons for such a rapid change are not yet known.
Thermal properties:
Increasing the number of grain boundaries will enhance phonon scattering at

the disordered boundaries, resulting in lower thermal conductivity.
However, as the grain sizes assume nanodimensions, their size becomes comparable
to the mean free paths of phonons that transport thermal energy.
Thus, nanomaterials can show widely different properties compared to coarse-
grained materials, due to the photon confinement and quantization effects of
photon transport.
It has been observed that in addition to the grain size, the shape also has an
influence on the thermal properties of nanomaterials.
For example, one-dimensional nanowires may offer ultralow thermal
conductivities, quite different from that of carbon nanotubes.
In nanowires, quantum confinement of phonons in 1D can result in additional
polarization modes compared to that observed in bulk solids.
Thermal properties:
The significant reduction in thermal conductivity of nanostructures due to:
 Strong phonon–phonon interactions and
 Enhanced scattering at grain boundaries
Silicon nanowires are known to exhibit thermal conductivity at least about two
orders of magnitude smaller than that of bulk silicon.
In contrast, the tubular structures of carbon nanotubes result in an extremely
high
( 6600 W/mK) thermal conductivity along the axial direction.
However, high anisotropy in their heat transport property is observed, making the
thermal transport direction dependent.
In multilayered coatings, many collective modes of phonon transport may appear
besides the phonon modes in each single layer;
when the phonon coherence length becomes comparable to the thickness of each
layer, the transport properties are significantly influenced.
When the mean free path of phonons spans multiple interfaces, the phonon
dispersion relation is modified, resulting in enhanced scattering due to decrease in
Thermal properties:
If the multilayer is designed to have a superlattice structure, and alternate films

have a large mismatch in the phonon dispersion relations, it is possible that
phonons in a certain frequency range may not propagate to the neighbouring layers
unless there are mode conversions at the interface.
Also, the presence of interface dislocations and defects can contribute to
enhanced boundary scattering.
All these factors can contribute to the lower thermal conductivity of multilayered
nanostructured films.
Nano fluids:
The use of a nanofluid to enhance thermal transport is another promising
application of the thermal properties of nanomaterials.
Nanofluids represent the class of liquids that have a stable colloidal dispersion
of nanoparticles distributed uniformly in the medium.
It has been observed that dispersion of a wide variety of nanoparticles of oxides,
nitrides, metals, metal carbides and nanofibres, such as single- and multi-walled
carbon nanotubes, can significantly enhance the thermal conductivity of the fluid.
Thermal properties:
To obtain stable colloidal suspensions, the particle size should normally be in the
range of 1–100 nm and an anti-coagulant may also be added to enhance the
stability of the nanofluid.
The idea of enhancing the thermal conductivity of liquids using solid dispersions is
not completely new.
Maxwell proposed the possibility of enhancing the thermal conductivity of

fluids using particle dispersions as early as 1873.
This is because we know that solids in general have much higher thermal
conductivity than liquids and gases.
For example, while air has a conductivity of the order of 0.03 W/mK, water has a
conductivity of the order of 0.6 W/mK, and metals like silver and copper have a
conductivity of 400 W/mK, while materials like carbon nanotubes (CNT) have
extremely high conductivity of 2300 W/mK.
Thermal properties:
It is obvious that thermal conductivity of a fluid can be enhanced by having particles

of better heat transport properties dispersed in it.
However, in the early years of development of particle dispersed fluids,
microcrystalline dispersoid particles were used.
Draw Back of Nano fluids:
 These fluids suffered from inferior stability of suspension, leading to their
coagulation and precipitation.
Erosion of the walls of the pipes by the particles was also observed to be a
major problem.
With the advent of techniques to synthesize nanoparticles with controlled grain size,
nanofluids with improved stability have been developed.
For dilute fluids with spherical dispersoids, the effective thermal conductivity
(keff) of the fluid is expected to follow the equation:
where kp and km are the thermal conductivity of the particles and the medium,
respectively, and φ is the volume fraction of the particles.
Thermal properties:
The relation suggests that the thermal conductivity of a fluid will increase by about
three times the effect expected from volume fraction effects.
However, it may be noted that this equation does not suggest the dependence of
thermal conductivity of the fluid on the particle size.
However, in practice, the thermal properties of nanofluids are known to depend
on particle size, volume fraction and the type of dispersoid employed.
The first heat transfer enhancement with nano-sized particles was reported by
Masuda and his group in Japan.
They demonstrated that the thermal conductivity of ultrafine suspensions of
alumina, silica and other oxides in water increased by a substantial amount
(maximum of 30%) for a particle volume fraction of 4.3%.
Choi and his group at the Argonne National Laboratory proposed to construct a
new class of engineered fluids with superior heat transfer capabilities in 1995.
An approximately 20% improvement in effective thermal conductivity has been
reported when 5 vol.% CuO nanoparticles are added to water.
Thermal properties:
The effective thermal conductivity of ethylene glycol increased by 40% for a

nanofluid containing 0.3 vol.% Cu nanoparticles of mean diameter <10 nm.
High thermal conductivities in nanofluids can be due to a number of factors
such as:
 Brownian motion of the nanoparticles
 molecular-level layering of the liquid at the liquid/particle interface
 the nature of heat transport in the nanoparticles and
 the effects of clustering of nanoparticles.
It is postulated that ballistic, rather than diffusive mechanisms account for the rapid
heat transport in nanofluids.
Apart from enhancing the thermal conductivity of the medium, the use of
nanofluids can also aid reduction in pumping power to attain equivalent heat
transfer coefficient.
An increase in pumping power by a factor of 10 results in doubling of thermal
conductivity of conventional fluids.
In contrast, nanofluids can achieve improved thermal transport properties without
Thermal properties:
BALLISTIC AND DIFFUSIVE HEAT TRANSPORT:
Heat transfer, in general, occurs by vibrations of atoms in solids (Conduction).
Based on quantum mechanics, the vibrations in solids can be mathematically
treated as a convolution of phonons (normal modes) and photons (normal
vibrations).
Generally, heat transfer occurs by diffusive mechanism, which follows Fourier’s
equation for conduction and convection.
However, when the particle size becomes comparable to the mean free path of
phonons, ballistic heat transfer mechanism becomes predominant.
For example, the mean free path of a phonon in a Cu particle ranges from 20 nm
at 323 K to 16 nm at 423 K.
When the particle size becomes smaller than these values, ballistic heat
transport mechanism takes over.
Under these circumstances, the heat flux would be proportional to the fourth
power of temperature rather than linear dependence observed in diffusive heat
transfer.
Thermal properties:
BALLISTIC AND DIFFUSIVE HEAT TRANSPORT:
This is depicted in the table given below, where q is heat flux, k is thermal
conductivity, l is the mean free path of a phonon and L is the grain/particle size.
MECHANICal properties:
The tensile, work hardening, creep, fatigue and deformation behaviour of

nanocrystalline materials are significantly different from that of their bulk
counterparts due to the complex interaction of the defect structures.
The major factors contributing to the difference in the mechanical behaviour of
nanostructured materials are the following:
1. Very high fraction of atoms residing at grain boundaries and triple
junctions exert a strong influence on the behaviour of these defects on
application of stress. The influence of grain size on dislocation stability, also has
significant influence on dislocation dynamics for material design and
mechanical properties of materials. Since dislocation interactions are the
predominant deformation mechanisms that influence the mechanical property
of coarse-grained materials, the plastic deformation mode of nanomaterials
could be significantly different.
2. Due to the above reasons, alternate deformation mechanisms like grain
boundary migration/sliding, crack growth, etc. become important.
3. The porosity level in nanomaterials is strongly dependent on the processing

technique and can also be significant, for example, in the case of mechanically
alloyed specimens. Even after agglomeration, the pore size can be smaller
than or equal to grain size. The presence of porosity can have a significant
effect on the mechanical behaviour of nanomaterials.
4. Finally, there can be segregation of different solutes at the grain boundaries
in nanomaterials, which can influence the mechanical properties.
Some of the peculiar mechanical properties :
• Elastic moduli were found to be 30%–50% lower than in conventional grain
size materials.
• Hardness and strength were found to be very high, with hardness values for
nanocrystalline pure metals (~10 nm grain size) up to seven times higher than
those for conventional coarse-grained (>1 μm) metals; in general, tensile and
compressive strengths in nearly all materials show significantly high values
at the nanometre scale.
Some of the peculiar mechanical properties :

• Nanoscale multilayers made of metallic or ceramic materials exhibited
ultrahigh hardness.
• The Hall–Petch slope is negative below a critical grain size, showing that
hardness decreases with decrease in grain size in the nanoscale grain size
regime.
• Ductility (possibly superplastic behaviour) is observed at low temperature in

brittle ceramics or intermetallics with nanoscale grain size, possibly due to
diffusional deformation mechanisms–an area to be explored.
Hardness and strength:
The hardness and strength of conventional grain size materials (grain diameter d
>1 μm) have been known to be a function of the grain size.
It is known in general that grain boundaries act as barriers to dislocation motion
and can thereby strengthen a material.
With decreasing grain size, the surface area of grain boundaries per unit volume
increases and therefore can result in an increase in hardness and strength.
For ductile polycrystalline materials, a semiempirical relationship, called the Hall–
Petch equation, has been found to express the grain size dependence of the flow
stress at any plastic strain, up to ductile fracture.
where σy is the yield stress, σ0 is a friction stress opposing dislocation motion, k is a

constant and is material dependent, and d is the grain diameter.
The same behaviour has been found to hold for hardness, as shown below, and for
wear resistance too.
It is known that the yield stress–grain size exponent for relatively large grains
appears to be very close to −0.5 and generally this trend continues until the very
fine grain regime (~100 nm) is reached.
For instance, for nanophase Cu (d = 6 nm), the hardness is five times greater than
that in the corresponding bulk metal (d = 100 μm).
This behaviour substantially derives from the difficulty in creating dislocations and
from the existence of barriers to dislocation motion.
Significant improvement in the tensile strength of nano-palladium in comparison
to micrograined palladium has also been observed.
In some cases, exceptionally high hardness has been observed in the nanocrystalline
state, for example, in Al-based nanocomposites, prepared by mechanical alloying,
as shown in Fig.
Copper-based nanocomposites have also shown very high hardness in

comparison to micro-composies (Right fig).
In fact, in these Cu-based nanocomposites, the ratio of hardness to electrical
conductivity is three times that of oxygen-free high conductivity Cu-
luminiumbased
nanocomposites also show retention of their hardness at higher temperatures, up
to 773 K, in comparison to commercially available age hardened Al–Cu alloys, which
The mechanical behaviour is mainly determined by the type of bonding in the
materials.
Metals with highly delocalized bonds are ductile and are thus usually soft; ionic
solids are more difficult to deform (due to charge neutrality);
covalent solids have strong localised bonds, so that ceramics and intermetallics
are subject to brittle fracture.
In a crystalline structure, dislocations can be introduced and atomic planes can
slide over one another.
In the nanophase, both these behaviours are altered.
In nanophase metals, the hardness increases with decreasing grain size because
defects and dislocations are required for deformation to occur, and they are
almost absent in nanostructured materials, although regenerative sources of
dislocations exist.
Therefore, the dislocations needed for easy deformation are frozen andnew ones
are prevented from forming in nanomaterials.

In nanocrystalline materials, as the grain size is reduced below a critical limit, the
response tends to deviate from the Hall–Petch relation described earlier (Fig. ).
In fact, a close analysis of experimental Hall–Petch data in a variety of materials has
shown that although the plot of τ versus d−1/2 forms a continuous curve, three
different regions can be seen:
1. A region A region from single crystal to a
grain size of about a micrometre (μm)
Where the classical Hall–Petch description
Can be used;
2. A region for grain sizes ranging from
about 1 μm to about 30 nm where the
Hall–Petch relation roughly holds, but
deviates from the classical − 0.5 exponent
to a value near zero;
3. A region beyond a very small critical grain
size where the Hall–Petch slope is nearly zero with no increase in strength on
decreasing grain size or where the strength actually decreases with decreasing

It is known that below a critical grain size, the ratio of the volume fraction of
triple junctions to grain boundaries increases significantly.
As the triple junctions are known to be weak regions, it is expected that at this
stage, the strength of the material decreases.
For large grain sizes, the dependence of stress can be rationalised in terms of a
dislocation pile-up model.
In deriving the Hall–Petch relation, the role of grain boundaries as a barrier to
dislocation motion is considered in various models.
In one type of model, the grain boundary acts as a barrier to pile-up of
dislocations, causing stresses to concentrate and activating dislocation sources in
the neighbouring grains, thus initiating slip from grain to grain.
In the other type of model, the grain boundaries are regarded as dislocation
barriers limiting the mean free path of the dislocations, thereby increasing strain
hardening, resulting in a Hall–Petch-type relation.
Lack of dislocation activity in the interior of the grains decreases the tendency for
Clearly, at sufficiently small grain sizes, the Hall–Petch model, based upon
dislocations may not be operative, except possibly in the grain boundaries.
It has been postulated that at very small grain sizes, a new mechanism of
deformation may operate, which is similar to Coble creep or grain boundary
diffusional creep occurring at room temperatures.
Coble creep causes homogeneous elongation of grains in the tensile direction.
Chokshi and his group at Indian Institute of Science, Bangalore, were the first to
propose room temperature Coble creep as the mechanism to explain the so-
called inverse Hall–Petch effect seen in nanocrystalline specimens.
It should be noted that any artifacts of the specimen preparation methods can also
contribute to negative Hall–Petch slopes and this is even more true for
nanomaterials.
One should therefore take great care during experimentation and interpretation
of the mechanicalproperties of nanomaterials.
Tensile ductility and strain hardening:
For microcrystalline materials, decrease in grain size not only increases the
strength but also the ductility.
Grain size strengthening is perhaps the only mechanism that can enhance the
hardness as well as ductility/toughness of a material.
With decrease in grain size, crack deflections at grain junctions can result in
enhanced constraint to crack propagation and thereby increase the fracture
toughness and ductility of the material.
When GB/triple junction migration is a more dominating mechanism of plastic
deformation compared to dislocation, particularly as the grain size approaches close
to the limit of instability of dislocations.
It can result in early GB/triple junction crack interaction and crack propagation due
to GB sliding even at low temperatures.
When the grain size is reduced to nanocrystalline dimensions, one would
expect an increase in the ductility of the material.
However, the ductility of nanocrystalline materials is often observed to be reduced
Kochidentified three major sources of limited ductility in nanocrystalline
materials:
 artifacts from processing (e.g., pores)
 tensile instability
 crack nucleation or shear instability
Nanocrystalline bulk specimens synthesized for tensile testing usually contain a large
fraction of porosities and other artifacts due to the synthesis technique.
It is difficult to prepare bulk nanostructured materials free from such artifacts
through consolidation.
Theoretical and experimental studies suggest the existence of three regimes:
 Grain size d > 1 μm regime in which unit dislocations and work hardening
control plasticity;
 Smallest grain size d < 10 nm regime, where limited intragranular dislocation
activity occurs and grain boundary shear is believed to be the mechanism of
deformation;
Nanocrystalline and ultrafine grained materials cannot generally sustain uniform
tensile elongation.
They do not show strain hardening after an initial stage of rapid strain hardening
over a small plastic strain regime (1%–3%), which is different from the response
of coarse-grained polycrystalline metal.
This is because the dislocation density saturates in nanocrystalline materials due to
both dynamic recovery as well as annihilation at grain boundaries.
After large additional strains, work hardening is observed in these materials.
Room temperature dynamic recovery is also common in nanocrystalline samples.
An increase as well as a decrease in strain rate sensitivity with decreasing grain size
in metals has been reported by different research groups.
Iron, which is normally strain rate sensitive, with a strain rate exponent m of the
order of 0.04, goes down in value to 0.004 when the grain size is 80 nm.
Creep and superplastic behaviour:
the creep behaviour of nanocrystalline materials is better than that of materials
with conventional grain sizes.
At lower stress and higher temperatures, where the main mechanism governing
creep is diffusion, creep generally occurs faster in materials with grain sizes in the
nanometre range, i.e., where more high diffusivity paths are present.
In fact, the creep rates of nanocrystalline materials are often lower than that
predicted by the diffusion mechanisms along the grain boundaries alone.
For example, doping a titanium oxide ceramic with yttrium oxide prevents grain
growth during the test.
According to a recent study, the creep rates of doped titanium oxide, at

temperatures which are normally quite low for that material (973 and 1073 K), are
lower than those of the non-doped one, i.e., with non-stabilised grains.
Creep in nanophase materials is expected to occur quickly because of the larger
volume fraction of grain boundaries and the short diffusion distances.
Diffusion along the grain interfaces is rapid in nanophase metals, which promotes
sintering and neck formation and hence enhanced creep rates are observed even
close to room temperature.
Creep rates may be influenced by the level of porosity in nanophase samples,

because free surfaces tend to increase diffusion rates relative to grain boundary
rates.
If a compressive stress is applied to a system of equiaxed grains, there is diffusional

flow in the boundary regions. Therefore, changes in the external shape occur;
but the grains remain equiaxed and maintain their size and orientation, sliding over
one another by diffusional accommodation at the interfaces.
The Karch model relates the strain/creep rate to grain boundary diffusion
where σ is the applied stress, Ω is the atomic volume, d is the grain size, b is
Burger’s vector, k is the Boltzmann constant, and T is the grain boundary diffusion
coefficient.
When the grain size is decreased from 1 μm to 10 nm, dε/dt is increased by 106 or
more.
Eventually, exceptional ductility due to diffusional creep in nanocrystalline brittle

ceramics or intermetallics at temperatures less than 0.5 Tm has not been realised,
while effective enhanced ductility has been obtained at somewhat higher
temperatures, and an improvement of creep properties by lower ‘activation’
temperature for superplasticity and a higher strainrate regime.
The ductile–brittle transition temperature in conventional mild steel can be lowered
by about 300 K by reducing the grain size by a factor of 5.
The brittleness can be defined in terms of the strain rate sensitivity, m, as given
below, and its values are 0 (perfectly brittle) and 1 (perfectly ductile).
As grain size decreases, it is found that the temperature at which superplasticity

occurs is lowered, and the strain rate for its occurrence is increased.
Superplastic behaviour might be observed in nanocrystalline materials at
temperatures much lower than 0.5Tm, but instead have shown creep rates
comparable to or lower than those in coarse-grained samples of the same material.
A little enhancement in ductility or superplastic behaviour has been observed for
nanocrystalline materials at temperatures <0.5Tm.
This provided evidence for the enhancement of superplastic behaviour in
nanocrystalline materials at temperatures >0.5Tm.
Superplasticity means the capability of polycrystalline materials to exhibit very large
tensile deformations without showing fracture or necking.
It is observed only above a certain critical temperature in the materials that present
this behaviour and also when they are coarse-grained.
These ‘activation’ temperatures are usually higher than 0.5Tm, where Tm is the
melting temperature.
When the grain size is decreased, it is found that the threshold temperature can be
lowered; an increase in the strain rate for the occurrence of superplasticity is
observed.
It was believed that creep rates could be enhanced by many orders of magnitude
by reducing the grain size below 100 nm, and that superplastic behaviour could be
observed in nanocrystalline materials at temperatures much below 0.5Tm.
It must be observed that tensile superplasticity is limited to materials that already
exhibit superplasticity in coarser grain sizes (1–10 μm), e.g., for ZrO2and TiO2 , m =
0.02 at 300 K for d = 100 nm, but m increases almost exponentially below 50 nm for
both the oxides.
Fracture and toughness:
In practical applications of materials, a significant limitation is represented by the
fracture strength, and not by the yield strength.
A material can yield & with this mechanism sustain itself against an imposed stress.
This is possible because of behaviour dislocations and grain boundaries, which
prolong plasticity.
The results of the bending test for compacted NiP showed that by decreasing the
grain size, an enhancement of the fracture stress and the strain-to-fracture can be
realised.
For microstructured materials & nanomaterials, improvements in toughness and a
lower brittle-to-ductile transition temperature are obtained by decreasing grain size.
However, in brittle intermetallics such as TiAl (grain size ~ 100 nm to 70 μm),
the toughness was found to decrease with decreasing grain size, as intragranular
cracking gave way to intergranular fracture.
Mechanical failure, which limits ductility, can be viewed as a competition between
dislocations and nucleation or propagation of cracks, depending on the grain size.
Corrosion properties :
The corrosion investigations of nanocrystalline materials showed a more intensive
active anodic dissolution, compared with conventional materials.
This difference in behaviour due to the small grain size, which results in a larger
fraction of high-energy grain boundary defects in the material.
Such high-energy grain boundary sites act as preferred anodic dissolution
sites and can thus result in increased corrosion rates of nanocrystalline alloys.
Grain boundaries being easy diffusion paths can facilitate enhanced surface
diffusion coefficients, resulting in the early formation of a well-adherent and dense
oxide layer, thereby passivating the surface.
In contrast, electrochemical polarization tests on nanocrystalline Ni (grain sizes of
500 and 20 nm) indicated that they exhibit higher passive current densities than
their coarser-grained conventional Ni
XPS investigations of the passive film on these materials showed no difference in the
thickness of the passive film between the nanocrystalline material and conventional
material.
These passive films on the nanocrystalline specimens were, however, more
defective than those on conventional Ni.
The defect density of the film was found to increase with decreasing grain size,
which in turn allowed for easier Ni cation diffusion through more defective film,
leading to higher current densities in the passive potential range for the
nanocrystalline specimens.
It was also observed that when the grain size is in the nanoscale range, the number
of atoms at the grain boundaries becomes comparable to the number of atoms
inside the grains.
The amount of impurities per unit grain boundary is therefore lower in
nanomaterials than larger-grained materials with the same bulk impurity
concentration, because the grain boundary area increases.
This higher purity of the grain boundaries has been associated with more uniform
corrosion morphology and higher intergranular corrosion resistance for
nanomaterials as compared to larger-grained materials.
One more factor which affects the corrosion behaviour of nanocrystalline material
is the porosity of the coating.
If the coating is less porous in nature, it will show high corrosion resistance.
Contribution of triple junctions to the structure and properties of nanocrystalline
materials may affect the corrosion properties of these nanocrystalline materials.
Copper-based nanocomposites show significantly better corrosion resistance
when compared to the microcomposites, as shown in Table .
94

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NANO TECHNOLOGY (OE) - Unit II

Unique Properties of Nanomaterials

DEPARTMENT OF CHEMICAL ENGINEERING

The microstructural features of importance in nanomaterials include:

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

Any imperfection leading to disruption of periodicity is referred to as a ‘crystalline

 The condition for dislocation stability can be given by, F image ≤ b σP

where b is Burger’s vector and σP is Peierl’s stress

where G is the shear modulus.

Dislocation stability in typical FCC and BCC metals

Twins in nanocrystalline Cu particles

• Voids in nanocrystallites may be situated at either triple

• Both types of voids influence the behaviour of the

• It is suggested that triple junction voids arise as a result of

Nanocrystalline materials typically contain a high number of interfaces with

where subscripts cr and ic refer to the crystalline and intercrystalline components

 The triple junctions may be considered to form a network of disclinations.

 Theoretical calculations have shown that triple junction energies are

 Compensating disclinations play a significant role in the properties of

 This role may be particularly important in nanocrystalline materials, where

 In 1957, Segall observed pentagonal grains of pyramidal shape in cold rolled

where β is a constant, while E and Eo correspond to the measured and

The chemical potential is related to pressure by the following equation:

It should be recognised that the bulk melting temperature is related by:

It can be seen that the change in melting temperature is inversely proportional

where μ is the shear modulus of the matrix, κ is a dimensionless factor that

 It is fascinating to observe that the melting temperature does not

 This is in contrast to the behaviour of nanograined solids with grain size in

It is known that the diffusion coefficient obeys an Arrhenius-type relation with

where Q is the activation energy for diffusion.

If log (D) is plotted as a function of (1/T),

As the grain sizes reduce to nano-dimensions, the second term has a

Diffusivities in nanomaterials (in m2/s at 300 K)

Grain growth restriction in Cu–W nanocomposites heated to 500°C in (a) Cu–10%W

Grain growth restriction in Ag–Cu nanoparticles:

Figure shows a schematic of how the hydrogen

Figure (Next slide) demonstrates this phenomenon in the Fe–Si system.

Solubility of Si in Fe as a function of crystallite size of Fe. The figure demonstrates

Magnetic nanoparticles applications:

The strength of a magnet is decided by its coercivity and saturation

 Exchange coupling allows crystallographically isotropic materials to exhibit

 The Fe-rich compositions (e.g., Fe90Nd7B3)

Magnets made of nanocrystalline Y–Sm–Co grains possess unusual magnetic

The magnetic properties of the Sm2Co17 hard magnet can be significantly

Typical applications for these highpower rare earth magnets:

Improvement in magnetic properties in Sm2Co17–FeCo nanocomposites in

 This phenomenon is usually observed in bulk composites consisting of

 A significant decrease in resistance from the zero-field state is evident in these

 It was observed in both nanocrystalline thin films and equiaxed granular

Schematic diagram showing GMR effect in magnetic ultrathin films.

 The effect can be up to 100% in multiple stacks of ultrathin films.

Exceptionally high dielectric constant in nanocrystalline PZT. The

Key contributory factors include:

 Quantum confinement of electrical carriers within nanoparticles,

 Controlling the crystal dimensions and

Increasing the number of grain boundaries will enhance phonon scattering at

If the multilayer is designed to have a superlattice structure, and alternate films

Maxwell proposed the possibility of enhancing the thermal conductivity of