Bulk Nanostructured Materials

Bulk nanostructured materials are solids having a nanosized

microstructure.
The basic units that make up the solids are nanoparticles.
The nanoparticles can be disordered w.r.t. each other, where
their symmetry axes are randomly oriented and their spatial
positions display no symmetry.
The particles can also be ordered in lattice arrays displaying
symmetry.
Fig.6.1a illustrates a hypothetical 2-D ordered lattice of Al12
nanoparticles.
Fig.6.1b shows a 2-D bulk disordered nanostructure of the
same nanoparticles.
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SOLID DISORDERED NANOSTRUCTURES

Methods of Synthesis

Compaction and consolidation:

As an example, consider Cu-Fe alloys.
Mixtures of iron and copper powders having the composition
Fe85Cu15 are ball-milled for 15h at room temperature.
The material is then compacted using a tungsten carbide die at
a pressure of 1GPa for 24h.
This compact is then subjected to hot compaction for 30 min at
temperatures in the vicinity of 400C and pressures up to
870MPa.
The final density of the compact is 99.2% of the maximum
possible density.
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Figure presents the distribution of grain sizes in Fe-Cu.
Nanoparticle size ranges from 20 to 70nm.

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 Figure 6.3 shows a stress-strain curve for this Fe-Cu.

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 Its Young’s modulus, which is the slope of the curve in the
linear region, is similar to that of conventional iron.
 The deviation from linearity in the stress-strain curve shows
there is a ductile region before fracture where the material
displays elongation.
 The data show that fracture occurs at 2.8GPa which is about
5 times the fracture stress of iron having larger grain sizes,
ranging from 50 to 150m.
 Making materials with nanosized grains has the potential to
provide significant increases in yield stress and has many
useful applications such as stronger materials for automobile
bodies.

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Rapid solidification:
 Chill block melt spinning method.
 RF heating coils are used to melt a metal.
 The melt is then forced through a nozzle to form a liquid
stream.
 This stream is continuously sprayed over the surface of a
rotating metal drum under an inert gas atmosphere.
 The process produces strips or ribbons ranging in thickness
from 10 to 100m.
 The parameters that control the nanostructure of the
material are nozzle size, nozzle-to-drum distance, melt
ejection pressure and speed of rotation of the metal drum.

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 Need for light weight, high strength materials has led to the
development of 85-94% aluminum alloys with other metals
such as Y, Ni, and Fe.
 A melt spun alloy of Al-Y-Ni-Fe consisting of 10-30 nm Al
particles embedded in an amorphous matrix can have a
tensile strength in excess of 1.2GPa.
 The high value is attributed to the presence of defect free
aluminium nanoparticles.

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Gas atomization:
 This is another method of making nanostructured materials.
 A high velocity, inert gas beam impacts a molten metal.
 The apparatus is illustrated in Fig 6.5. A fine dispersion of metal
droplets is formed when the metal is impacted by the gas.
 This method can be used to produce large quantities of
nanostructured powders, which are then subjected to hot
consolidation to form bulk samples.

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Electrodeposition:
 Example: A sheet of nanostructured Cu can be fabricated by
putting two electrodes in an electrolyte of CuSO4 and applying a
voltage between the two electrodes.
 A layer of nanostructured Cu will be deposited on the
negative titanium electrode.
 A sheet of Cu 2mm thick can be made by this process, having
an average grain size of 27nm and an enhanced yield
strength of 119MPa.

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Failure Mechanisms of Conventional Grain-Sized Materials

Nanosized grains affect the bulk structure of materials.

First, look at how conventional grain-sized materials fail
mechanically.
A brittle material fractures before it undergoes an
irreversible elongation.
Fracture occurs because of the existence of cracks in the
material.
Figure 6.6 shows an example of a crack in a two-dimensional
lattice.

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A “crack” is essentially a region of a material where there is no
bonding between adjacent atoms of the lattice.
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If such a material is subjected to tension, the crack interrupts
the flow of stress.
The stress accumulates at the bond at the end of the crack,
making the stress at that bond very high, perhaps, exceeding
the bond strength.
This results in a breaking of the bond at the end of the crack,
and a lengthening of the crack.
Then the stress builds up on the next bond at the bottom of the
crack and it breaks.
This process of crack propagation continues until eventually the
material separates at the crack.
A crack provides a mechanism whereby a weak external
force can break stronger bonds one by one.

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Another kind of mechanical failure is the brittle-to-ductile
transition, where the stress-strain curve deviates from linearity,
as seen in Fig. 6.3.

In this region, the material irreversibly elongates before

fracture.

 When the stress is removed after the brittle-to-ductile transition,

the material does not return to its original length.

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The transition to ductility is a result of another kind of
defect in the lattice called “dislocation”.

Figure 6.7 illustrates an edge dislocation in a 2D lattice.

There are also other kinds of dislocations such as screw

dislocation.

Dislocations are essentially regions where lattice deviations

from a regular structure extend over a large number of lattice
spacings.

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Atoms in the region of the dislocation are bonded to each
other, but the bonds are weaker than in the normal regions.
In the ductile region, one part of the lattice is able to slide
across an adjacent part of the lattice.
This occurs between sections of the lattice located at
dislocations where the bonds between the atoms along the
dislocation are weaker.
One method of increasing the stress at which the brittle-to-
ductile transition occurs is to impede the movement of the
dislocations by introducing tiny particles of another
material into the lattice.
This process is used to harden steel, where particles of iron
carbide are precipitated into the steel.

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Mechanical Properties

Elastic modulus of a nanostructured material differs from bulk

when the grain size becomes very small.
Figure 6.8 is a plot of the ratio of Young’s modulus E in
nanograined iron as a function of grain size.
E decreases below ~20 nm.

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 The yield strength σy of a conventional grain-sized material
is related to the grain size by the Hall-Petch equation
σy = σo + Kd-(1/2)
where σo is the frictional stress opposing dislocation movement,
K is a constant and d is the grain size in micrometers.

 Figure 6.9 plots the measured yield strength of Fe-Co alloys as

a function of d-(1/2), showing the linear behavior predicted by the
above equation.

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Assuming that the equation is valid for nanosized grains, a
bulk material having a 50nm grain size would have a yield
strength of 4.14 GPa.
The reason is that the materials having smaller grains have
more grain boundaries which block dislocation movement.
Deviations from the Hall-Petch behavior have been observed
for materials made of particles less than 20nm in size.
The deviations involve no dependence on particle size (zero
slope) to decrease in yield strength with particle size (negative
slope).
It is believed that conventional dislocation-based
deformation is not possible in bulk nanostructured
materials with sizes less than 30nm because mobile
dislocations are unlikely to occur.
TEM of small-grained bulk nanomaterials, during deformation
does not show any evidence for mobile dislocations. 26
Most bulk nanostructured materials are quite brittle and
display reduced ductility under tension, typically having
elongations of a few percent for grain sizes less than 30nm.
For example, conventional coarse-grained annealed
polycrystalline copper is very ductile, having elongations of
up to 60%.
Measurements in samples with grain sizes less than 30nm
yield elongations no more than 5%.
Most of these measurements have been performed on
consolidated samples, which have large residual stress and
flaws, which restricts dislocation movement.
However, nanostructured copper prepared by
electrodeposition displays almost no residual stress and has
elongations upto 30% as shown in Fig.6.10.
These results emphasize the importance of the choice of
processing procedures and the effect of flaws and
microstructure on measured mechanical properties. 27
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Nanostructured Multilayers

 This bulk nanostructure consists of periodic layers of

nanometer thickness of different materials (such as alternating
layers of TiN and NbN).
 The layered materials are fabricated by various thin film
preparation methods.
 Interfaces are formed at the planar boundary between
adjacent layers.
 For example, a square centimeter of a 1m thick multilayer film
having layers of 1 nm thick TiN and 1 nm thick NbN has an
interface area of 1000 cm2.

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B
A
B
A
B NbN
A
B TiN
A

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The multilayers have very large interface area densities.
The material has an average density of about 6.5 g/cm3. The
interface area density is 154 m2/g.
The interfacial regions have a strong influence on the
properties of these materials.
These layered materials have very high hardness and good
wear resistance.
Hardness is measured using an indentation load depth sensing
apparatus which is commercially available and is called a
nanoindenter.
A pyramidal diamond indenter is pressed into the surface of the
material with a load L. The area of the indentation is A.
Hardness = L / A.
Typically measurements are made at a constant load rate of
~20mN/s. 31
Figure shows a plot of the hardness of a TiN/NbN
nanomultilayered strucutre as a function of the bilayer period (or
thickness) of the layers.
As the layers get thinner in the nanometer range there is a
significant enhancement of the hardness until ~30nm, where it
appears to level off and become constant.

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It has been found that a mismatch of the crystal structures
between the layers actually enhances the hardness.
The compounds TiN and NbN both have the same rock salt or
NaCl structure with the respective lattice constants 0.4235
and 0.5151nm, so the mismatch between them is relatively
large. Thus, the measured hardness is also large.
Harder materials have been found to have greater differences
between the shear modulus of the layers.
Interestingly, multilayers in which the alternating layers have
different crystal structures were found to be even harder.
In this case, dislocations moved less easily between the
layers and essentially became confined in the layers, resulting
in an increased hardness.

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Electrical Properties

For a collection of nanoparticles: To be a conductive

medium, the particles must be in electrical contact.
One of the bulk nanostructured materials that is conducting
consists of gold nanoparticles connected to each other by
long molecules.
This network is made by taking the gold particles in the form of
an aerosol spray and subjecting them to a fine mist of a thiol
such as dodecanethiol RSH, where R is C12H25.
These alkyl thiols have an end group-SH that can attach to a
methyl -CH3 and a methylene chain 8-12 units long that
provides steric repulsion between the chains.

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The chain like molecules radiate out from the particle. The
encapsulated gold particles are stable in aliphatic solvents such
as hexane.
However, the addition of a small amount of dithiol to the
solution causes the formation of a three-dimensional
cluster network that precipitates out of the solution.
Clusters of particles can also be deposited on flat surfaces
once the colloidal solution of encapsulated nanoparticles has
been formed.
A fabricated device allowing electrical measurements of such an
array is illustrated in Fig.6.12.
In-plane electronic conduction has been measured in 2D
arrays of 500nm gold nanoparticles connected or linked to
each other by conjugated organic molecules.
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 Figure gives a measurement of the current versus voltage for a
chain without linkage (line a) and with linkage (line b) by a
conjugated molecule.

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 Figure 6.14 gives the results of a measurement of a linked
cluster at different temperatures.

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 The conductance G = I/V.
 The data in Fig. 6.13 show that linking the gold nanoparticles
substantially increases the conductance.
 The temperature dependence of the low-voltage conductance
is given by

where E is the activation energy.

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The conduction process for this system can be modelled by
a hexagonal array of single crystal gold clusters linked by
resistors, which are the connecting molecules, as
illustrated in Fig.6.15.
The mechanism of conduction is electron tunneling from one
metal cluster to the next.
The tunneling process is a quantum-mechanical phenomenon
where an electron can pass through an energy barrier larger
than the kinetic energy of the electron.

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Thus, if a sandwich consisting of two similar metals
separated by a thin insulating material is constructed, as
shown in Fig. 6.16a, under certain conditions an electron can
pass from one metal to the other.

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For the electron to tunnel from one side of the junction to
the other, there must be available unoccupied levels on the
other side of the band.

For two identical metals at T = 0 K, the Fermi energies will

be at the same level.

As shown in Fig. 6.16b, the tunneling cannot occur because

there are no available states.

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Application of a voltage across the junction increases the
electronic energy of one metal w.r.t. the other by shifting one
Fermi level relative to the other.
The number of electrons that can then move across the
junction from left to right (Fig. 6.16c) in an energy interval dE
is proportional to the number of occupied states on the left
and the number of unoccupied states on the right.
Left to Right,

Right to Left,

Here N1 is the density of states in metal 1, N2 is the density of

states in metal 2 and f(E) is the Fermi-Dirac distribution of
states.

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The net flow of current I across the junction is the difference
between the currents flowing to the right and the left, which is

Here K gives the probability of tunneling through the barrier.

Assume that the DOS is constant over an energy range eV.

Then for small V and low T, we obtain

This can be rewritten in the form,

Here

Gnn is identified as the conductance.

Thus, the junction behaves in an ohmic manner,
i.e. with I  V.
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Other Properties

Many other properties of bulk ferromagnetic material made of

nanosized grains is quite different from the same material
made with conventional grain sizes.
In a previous chapter, we saw that the reactivity of
nanoparticles depends on the number of atoms in the cluster.
It might be expected that such behavior would also be
manifested in bulk materials made of nanostructured
grains.
This is a possible way to protect against corrosion and the
detrimental effects of oxidation.

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Example: The nanostructured alloy Fe73B13Si9 has been
found to have enhanced resistance to oxidation at
temperatures between 200 and 400oC.
The material consists of a mixture 30nm particles of FeSi and
Fe2B.
The enhanced resistance is attributed to the large number of
interface boundaries and the fact that atomic diffusion
occurs faster in nanostructured materials at high
temperatures.
In this material, the Si atoms in the FeSi phase segregate to
interface boundaries where they can then diffuse to the
surface of the sample.
At the surface, the Si interacts with the oxygen in the air to
form a protective layer of SiO2. This hinders further oxidation.

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Melting temperature of nanostructured materials is also
affected by grain size.
It has been shown that indium containing 4nm nanoparticles
has its melting temperature lowered by 110K.

In the superconducting phase there is a maximum current that

a material can carry called the critical current Ic.
When the current exceeds Ic, the superconducting state is
removed and the material returns to its normal resistance.
It has been found that in the bulk granular superconductor
Nb3Sn, decreasing the grain size of the sample can increase
the critical current.

In Chapter 4, we saw that the optical absorption properties of

nanoparticles. Transitions to excited states, depend on their
size and structure.
Therefore, it is possible to engineer the optical properties of
bulk nanostructured materials. 49