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c. Suryanarayana
.' ..·..._'-"J", .
crystalline phases in a variety of materials, gas con-
densation, mechanical alloying, crystallisation of
amorphous alloys, chemical precipitation, and spray
conversion processing techniques have been most
. .,. -- .... main vacuum
C
chamber
commonly employed to produce 3D equiaxed nano-
.v ' .. ':-.:' .'.
crystallites while vapour deposition, sputtering, and A B
electrodeposition techniques have been used to syn- ~
evaporatlon
thesise the 1D-Iayered nanocrystals; the sol-gel pro- sources
cess has been commonly used to generate clusters.
Among all the techniques mentioned above, the gas
vacuum pumps --
condensation (or its modifications), mechanical
alloying, and spray conversion processing techniques fixed piston
have been most commonly employed to produce large low pressure
quantities of nanocrystalline materials. SbdE:I--I--anvii compaction unit
recorded from a nanocrystalline Cu specimen syn- ordered structural units representative of the bulk
thesised by the gas condensation method. 58 From material suggesting that the atoms in nanocrystalline
such micrographs (as well as from field ion micro- materials have sufficient mobility to rearrange them-
graphs and by small angle X-ray or neutron scattering selves into low energy configurations. Further, since
data), grain sizes and their distributions have been the densities of nanophase materials consolidated
determined. The grains exhibit typically narrow log- from equiaxed clusters extend beyond the 780/0 limit
normal size distributions, i.e. they exhibit a single for close packing of identical spheres, Siegef" con-
peak when the frequency is plotted on a linear scale cluded that an extrusionlike deformation of the clus-
against the log of the particle size. ters occurred during the consolidation process (but
The following features may be noted from high no preferred orientation was observed). This could
resolution electron micrographs of nanocrystalline occur because of a combination of local deformation
materials: and diffusional processes that allow low energy con-
1. Most of the ultrafine grains are equiaxed and figurations to result. Recent STM observations on
exhibit fringe contrast. The grains are randomly ori- nanocrystalline Ag and Pd also confirm this hypo-
ented with respect to one another and there is no thesis. Complementing the above results from Raman
apparent preferred orientation, irrespective of the spectroscopy and small angle neutron scattering
method of preparation. experiments, Siegel and Thomas 70 concluded that the
2. The fringes abruptly stop in each grain at the grain boundaries in nanocrystalline materials and
grain boundary, 59 indicating that there is little or no conventional coarse grained polycrystalline materials
atomic disorder perpendicular to the imaged planes. have similar structures. Similar conclusions were
3. The grain boundary planes are basically flat but reached based on observations in nanocrystalline Cu
exhibit some local faccting.'" probably to bring the and 440C martensitic steel produced by sliding wear.'"
planes from both grains into registry. Fe alloys produced by high energy ball milling," and
4. Neither voids nor dislocations have been (Fe,Moh8Si9B13 nanocrystals prepared by crystallis-
observed in many investigations, even though posi- ation of an amorphous ribbon." Thus, these data did
tron annihilation spectroscopy.i'''?' and precise den- not reveal any evidence for grain boundary disorder
sitometry and porosimetry'v'v" measurements have of the type and extent suggested by earlier studies.'!
clearly indicated the presence of porosity in nanocrys- The results of high resolution TEM have to be
talline metals. Nieman et ai.,58 however, reported interpreted with care.'! First, electron microscopic
observation of abundant twinning and low index, characterisation of nanocrystalline materials has been
faceted crystal regions, while Wunderlich et ai.64 done under less than DHV conditions, making the
reported detection of isolated dislocations or dipoles. influence of impurities an important consideration.
Li et ai.59 reported observation of grain boundary Further, the influence of the high energy electron
dislocations, fivefold twins, and edge and 60° beam on the shape and stability of the nanostructures
dislocations. is yet to be defined. Second, since very thin specimens
High resolution TEM investigations have been (usually the thickness is less than the crystal diameter)
carried out on nanocrystalline Pd (Refs. 59, 60, 64), are required for ultrahigh resolution TEM, the 3D
440C martensitic steel (Fe-17Cr*),65 Fe-Mo-Si-B crystal arrangement of a bulk nanocrystalline speci-
crystals, 59 and Ti-AI compacts." Wunderlich et ai.64 men gets transformed into a 2D arrangement. This
noted that the grain boundaries in nanocrystalline process may change the boundary structure as it
Pd appeared to be different from conventional coarse alters the forces between neighbouring crystals and
grained Pd, and with a smaller grain boundary thick- induces new forces due to the energy of the free
ness of 0,4-0,6 nm as against the accepted value of surface. In fact, thin foil specimen preparation may
1 nm. A qualitative difference in the contrast in a modify the internal stresses and hence the free energy
vicinity of > 0·6 nm at general grain boundaries (com- of the entire system. Recent results using STM and
pared with conventional polycrystalline material) was atomic force microscopy have shown that the struc-
observed. This was attributed to the high energy ture of nanocrystalline materials is significantly affec-
states of the grain boundaries in nanocrystalline ted." For example, it was shown that the grain
. materials, a situation not observed in conventional boundaries in nanocrystalline materials are highly
materials. They also noted that in the nanometre mobile far below the melting point and results in
sized crystals ordering of the grain boundary structure structural rearrangement. Further, because of the high
to minimise the interfacial energy does not take place diffusivity in nanocrystalline materials, atoms may
since the curvature of the grain boundary has a much diffuse from the free surface of a thin specimen into
different effect on the energy. the grain boundaries at ambient temperatures within
Based on Raman spectroscopy studies on nanocrys- a time much shorter than the time for specimen
talline Ti02 (Refs. 67-69) and high resolution TEM preparation, leading to changes in the boundary
combined with image simulations on nanocrystalline structure.
Pd (Refs. 60, 70), it was suggested that the grain It has recently been shown that the method of
boundary structures in nanocrystalline materials are preparation and the time-temperature history of
no different from those observed in conventional nanocrystalline materials have a significant effect on
coarse grained polycrystalline materials." By com- their structure and properties. For example, Tong
puter simulation methods it was shown that the et al." and Wurschum et ai.75 have shown that the
nanocrystalline grain boundaries contain short range structure of the grain boundary strongly depends on
the crystal size and external pressures. The pressure
* All compositions are in weight- % unless stated otherwise. effect in nanocrystalline materials seems to be of
0,3
general significance because coarse grained crystalline
and glassy solids are far less sensitive to pressure ~
0 0,2
effects. In other words, the P~ V term in Gibbs free ctf
<l
energy may play an important role in nanocrystalline 0.1
materials. 0
Atomistic simulation results on nanocrystalline Fe
suggest that the structure of the boundary component eft. -0,1
.s
is different from that of the amorphous or gaseous <l
-0,2 Ni3P
substances." Recent Mossbauer spectroscopy results (a)
on nanocrystalline ZnO also suggest that the bound- -0,3
ary atoms exhibit a non-recoil free y-absorption, i.e. 0 20 40 60 80 100
they behave like almost free, isolated atoms."? AVERAGE GRAIN SIZE, nm
From the above it is ·apparent that the question of 0,3
whether the structure of the grain boundaries in
nanocrystals is different from the coarse grained crys-
tals is not answered clearly. However, it is clear that
• •
0.2
nanocrystalline materials are not just polycrystals with ~
0
a reduced grain size. Once the crystal size and bound- :>
<l
ary dimensions become comparable with certain
length scales new physical effects are to be expected. 0.1
equilibrium values for coarse grained materials. The up to 450°C (Ref. 84).
isomer shift and half-line width measurements con- The kinetics of normal grain growth under iso-
firmed these results. These lattice distortions have thermal annealing conditions can be represented by
been explained on the basis of a supersaturation of the equation
the constituent elements or vacancies.I"
d2-d6=Kt
Grain growth where d is the grain size at time t, do the mean initial
Grain growth occurs in polycrystalline materials to grain size (at t = 0), and K a constant. Theoretical
decrease the interfacial energy and hence the total predictions also agree with the above trend. The
energy of the system. Since nanocrystalline materials above equation is obeyed only at temperatures
have a highly disordered large interfacial component close to the melting point. Assuming that d» do, the
(and therefore they are in a high energy state), the empirical equation
driving force for grain growth is high. However,
contrary to the expectations, experimental obser-
d = K'tl/n
vations suggest that grain growth in nanocrystalline where K' is another constant and n the grain growth
materials, prepared by almost any method, is very exponent, better represents the grain growth behav-
small (and almost negligible) up to a reasonably high iour in metals at lower temperatures. n has been
temperature. found to have values ranging between 2 and 3.
The inherent stability of the nanocrystalline grains The activation energy for grain growth Q, can be
has been explained on the basis of structural factors calculated from the equation
such as narrow grain size distribution, equiaxed grain
K'=Kbexp(-Q/RT)
morphology, low energy grain boundary structures,
relatively flat grain boundary configurations, and where Kb is a pre-exponential constant, and R is the
International Materials Reviews 1995 Vol. 40 No.2
48 Suryanarayana Nanocrystalline materials
50
,- _/0 »-:
9 Electron micrographs of mechanically alloyed Ti-24AI-11 Nb (at.-%) powders hot isostatically pressed
(207 MPa, 2 h) (after Ref. 108)
The measured diffusivities .in nanocrystalline Cu nanocrystalline state.111 A dramatic example is the
are about 14-20 orders of magnitude higher than achievement of 17 at.-% (40 wt-%) solubility of Hg
lattice diffusion and about 2-4 orders of magnitude in nanocrystalline Cu, against an equilibrium value
larger than grain boundary diffusion. For example, of < 1 at.-% (Ref. 121). The enhanced solid solubility
the measured diffusivity at room temperature is limits in these systems have been explained on the
2·6 x 10- 20 m2 s -1 for 8 nm grain sized Cu samples basis of elastic strains at the interfaces; demonstrated
compared with 4·8 x 10-24 m2 S-l for grain boundary earlier to be the reason both theoretically and exper-
diffusion and 4 x 10- 40 m2 s - 1 for lattice diffusion.I':' imentally for various alloys. Thus, nanostructure pro-
Similarly enhanced diffusivities were also observed cessing appears to be a novel way of forming solid
for solute diffusion in other metals. However, it was solution alloys in systems in which alloying has not
noted 116 that hydrogen segregation at grain bound- been possible by any other technique.
aries in Pd had to be described by a spectrum of site The high diffusivity of nanocrystalline materials
energies or segregation energies. This causes the results in alloying by diffusion along the grain bound-
diffusion coefficient to become concentration depen- aries resulting in the formation of stable and meta-
dent, being lower than the single crystal value at low stable phases at relatively low temperatures. For
hydrogen concentrations and higher for higher hydro- example, formation of the Pd3 Bi intermetallic has
gen concentrations. The enhanced self and impurity been found to occur at 120°C, a temperature much
diffusivities in nanocrystalline materials appear to be lower than normally observed.P" Similarly, nanocrys-
strongly linked to the porosity present in the samples. talline mixtures of Cu and Er crystallites formed
Averback et al.101 showed that diffusion coefficients the equilibrium CuEr compound by compaction.F"
could be reduced to conventional values by sintering Li et al.123 detected two new polymorphs of erbium
the samples to full density. However, in the light of oxide in the nanocrystalline state.
the more recent results.I'" the difference in diffusion Another important consequence of the increased
coefficients seems to be caused by differences in diffusivity is that sintering of nanocrystalline powders
relaxation states rather than by porosity. can occur at temperatures lower than those required
The increased diffusivity (and consequently the for sintering coarse grained polycrystalline powders.
reactivity) leads to increased solid solubility limits, Significant improvements in the sinterability and
formation of intermetallic phases (at temperatures mechanical properties (hardness and fracture charac-
much lower than those required for coarse grained teristics) have been obtained in nanocrystalline Ti02
materials and sometimes new phases), and increased (rutile) in comparison with conventionally synthesised
sinterability of nanocrystalline powders. coarse grained rutile.61,99,124 For example, Ti02 with
Solid solubility limits are usually enhanced when a grain size of 12 nm could be sintered at ambient
the material is in the nanocrystalline state. In extreme pressures at temperatures 400-600 K lower than those
cases, solid solutions can also form in alloy systems required for ball milled 1·3 urn powder (Fig. 10), and
which exhibit miscibility gaps both in the liquid and without the need for any compacting or sintering aid,
solid states. Typical examples of this phenomenon are such as polyvinyl alcohol, which is usually required.
the Ag-Fe (Refs. 117,118), Ti-Mg (Ref. 119), and Additionally, the fracture characteristics of sintered
Cu-Fe (Ref. 120) systems. While the solid solubility nanocrystalline Ti02 appear to be significantly differ-
of Mg in Ti under equilibrium conditions is ent from those of sintered commercial powder. The
<0·2 at.-%, it could be increased to 6 at.-% when Ti sintering temperature for trans granular fracture of
grains are in the nanometre range. Similarly, the solid nanocrystalline Ti02 (12 nm grain size) has been
solubility of Bi in Cu is < 10-4 at.-% under equi- shown to be 200 K lower than that for sintered
librium and this has been increased to 4 at.-% in the commercial coarse grained (1·3 urn grain size) powder.
International Materials Reviews 1995 Vol. 40 No.2
Suryanarayana Nanocrystalline materials 51
c-.IE 1600
E
C\I
'E 200
z
~ --e- 14nm grain size
en
en --£1 50/J.m grain size
w
~ 100
en
-a- 8--0 --a --a --e
reports of yield strength measurements on materials and this could explain the abnormal Hall-Petch
with a grain size of < 100 nm) with grain size. behaviour.
1. Generally, the hardness increases with a decrease Unlike the situation in equiaxed nanocrystalline
in grain size. materials, the Hall-Petch type relationship appears
2. At very small grain sizes, the hardness decreases to be obeyed always with a positive slope in layered
with a decrease in grain size, referred to as the inverse nanocrystalline materials when the microhardness is
Hall-Petch relationship.l'" The critical grain size at plotted as a function of the layer thickness. This
which this reversal takes place is dependent on the observation has been verified in vacuum deposited
rnaterial. In some materials, the hardness increases AI-2-15'3Fe alloys with the Fe layer spacing vary-
linearly with d-1/2 and then reaches a plateau at ing between 0·2 and 2·9 nm (Ref. 6) and also in
small grain sizes. Cu-15-60Fe alloys.P'' The layer thickness here is
3. The Hall-Petch slope kH is much smaller in the defined as the sum of the individual layer thicknesses
nanometre range than is observed at more normal of the constituent metals. However, it should be
grain sizes. remembered that hardnesses have been measured for
4. Annealing a sample to produce grain growth layer thicknesses of 24-2000 nm only, which are con-
resulted in hardness values greater than those of as siderably larger than the sizes at which a transition
prepared samples with similar grain sizes. in the Hall-Petch slope is expected to occur. It will
Consider now the possible reasons for the deviation be interesting to produce layered nanocrystals with a
from the Hall- Petch relationship in nanocrystalline layer thickness of about 10 nm or less and see whether
materials. The Hall-Petch relationship was derived the Hall- Petch slope is negative in this range.
using the concept of dislocation pile-ups in individual Apart from the sign of the Hall- Petch slope, there
grains.r" However, since in very fine grained mater- are also reports that the grain size exponent n can
ials, e.g. nanocrystalline materials, pile-ups cannot have very different values (i.e. the traditional Hall-
form when the grain size is less than a critical value Petch equation may not be valid at all). Christman 'P"
de (Ref. 146), weakening mechanisms (e.g.viscous type presents data for both coarse and nanograined
flow) operate and lead to a decrease in hardness with polycrystalline materials to show that the yield
decreasing grain size, i.e. a negative value for the strength or hardness variation with grain size can be
slope kH (Ref. 147). The value of de can be calculated equally well explained assuming that n = -1, -1/2,
by equating the repulsive force between the dislo- -1/3, and -1/4. Each of these values, obtained from
cations and the applied stress using the relation theoretical estimates, is based on different mechanisms
3Gb and/or modelling for dislocation-grain boundary
d =---- interaction mechanisms. Christrnanv" also suggests
e n(l- v)H that a correspondence could exist between the crystal
where G is the shear modulus, b the Burgers vector, structure and n. Assuming that the dislocation pile-up
v the Poisson's ratio, and H the hardness. model is valid even in nanocrystalline materials,
The above model could explain the reversal in Pande et ai.155 considered the effect of a smaller
hardness with grain size in nanocrystalline Cu and number of dislocations in the pile-up and also the
Pd. The negative slope in Ni-P has been explained effect of anisotropy and suggested that the grain size
on the basis of precipitation hardening due to the exponent could be modified from the traditional value
formation of Ni3 P on thermal annealing. However, of -1/2. Other investigators have modified the
this reasoning does not explain all of the results." A normal Hall-Petch equation by modifying either the
more convincing explanation for the negative slope grain size exponent and/or the slope of the plot k«.
can be offered by taking into account the volume Different values of kH have also been reported above
fraction of triple junctions,27,131,148since it has been and below the critical grain size.128,156-158
earlier reported 149that an increased triple junction Instead of a dislocation pile-up, another Hall-Petch
volume-fraction leads to softening and enhanced bulk model assumes a characteristic dislocation network
ductility in polycrystalline materials. density within the grains to transfer slip through the
Many investigators now accept that there exists a otherwise impenetrable grain boundaries. Assuming
critical grain size in nanocrystalline materials above that the dislocation line tension is size scale depen-
which the Hall- Petch slope is positive and below dent, Scattergood and Koch 156identified the critical
which it is negative; different reasons have been put grain size de with a transition from cutting to Orowan
forward for its presence. According to Palumbo bypassing of the network dislocations. They calcu-
et ai.,148 the transition from a positive to a negative lated the variation of hardness with grain size under
slope occurs when the triple junctions in the micro- these two conditions and arrived at the following
structure begin to comprise a significant volume relationshi ps
fraction of the bulk specimen value. Fougere H = Ho + kHd-1/2 for d ~ de
et ai.127,150 and Liu et ai.151 observed that the harden-
ing or softening of nanocrystalline materials can and
depend on the method used to vary the grain size.
Annealing a sample to produce grain growth resulted H = kH _1_ [In(~)J d-1/2 for d < de
2na reff
in hardness values greater than those of as prepared
samples with similar grain sizes. Lu and SUi,152on where a is a dimensionless constant (= (J/Gb2, where
the other hand, felt that thermal annealing of the as (J is applied shear stress, G the shear modulus, and
prepared sample will relax the interfacial structure b the Burgers vector) and reff an effective cut-off
leading to a reduction in interfacial excess energy radius. Thus, a straight line with a slope m = kH/2na
International Materials Reviews 1995 Vol. 40 No.2
Suryanarayana Nanocrystalline materials 53
was obtained when the hardness was plotted against lead at room temperature. However, no superplas-
[In(d/rerr)]d-1/2. A good agreement was reported ticity has yet been observed in nanocrystalline mater-
between kHxPt and kn
t (= 2nam) for nanocrystalline ials at room temperature, which would yield strain
materials with a grain size d < de and gives an rate sensitivity values about an order of magnitude
adequate description of the grain size softening higher than the maximum so far observed. Never-
transition. theless, superplastic behaviour is expected to be exhib-
ited by these ultrafine grained materials at least at
Ductilisation of ceramics and intermetallics elevated tcmperatures.l'"
The enhanced strain rate sensitivity appears to
The fine grain sizes and the high rates of diffusivity
arise from a combination of several factors - grain
observed in nanocrystalline materials suggest that
boundary sliding, presence of porosity, ultrafine grain
considerable ductility can occur in these materials
size, and rapid short range diffusion. These can lead
even at room temperature. This follows from the
to enhanced formability of intermetallics, ceramics,
expression for strain rate (ds/dr), during diffusional
and semiconductors. It has been recently demon-
creep
strated that near net shape forming of nanocrystalline
de aQ ( B2f1Db) Ti02 can be achieved at 800-900°C with excellent
dt = d2kT B1Dy + -d- detail.165
The fine grain size and its effect on improved
where a is the applied stress, Q the atomic volume, forming characteristics is an advantage for many
d the grain size, k the Boltzmann cons tan t, T the structural materials. However, the ultrafine grain size
temperature, B1 and B2 constants, D; and Db, respect- may not be compatible with good elevated temper-
ively, the volume and grain boundary diffusion ature creep performance. A way out of this dilemma
coefficients, and f1 the grain boundary width. At low can be that the nanostructured grains can be used to
temperatures, where boundary diffusion dominates, enhance processing (forming) and the grain size of
de/dt can be rewritten'P? as the final product could be subsequently increased
de B2aQf1Db using a suitable heat treatment.
It should be realised that enhanced ductility (and
dt - d3kT
hence formability) is generally associated with low
Thus, the diffusional creep rate of a polycrystalline hardness (and strength) and the presence of sufficient
sample is increased by reducing the grain size and/or number of slip systems to satisfy the von Mises
by increasing the grain boundary diffusivity. The criterion for plasticity. Since nanocrystalline materials
grain size of nanocrystalline materials is reduced by are very hard (and strong), it is doubtful whether the
three orders of magnitude compared with conven- formability can be substantially improved (at least in
tional polycrystalline materials (from about 10 urn tension), especially in non-cubic intermetallic com-
to 10 nm), and the boundary diffusivity is higher pounds. This may, however, be possible if the mechan-
by three orders of magnitude. Accordingly, nanocrys- isms of deformation in nanocrystalline materials are
talline ceramic and intermetallic compounds are entirely different from those in conventional coarse
generally expected to exhibit a 12 orders of magni- grained polycrystalline materials. Irrespective of the
tude increase in diffusional creep. And this has, in reasons for the high strength of nanocrystalline mater-
fact, been observed'P? when nanocrystalline CaF2 ials, several investigations are being conducted to
and Ti02 deform plastically at room temper- optimise the strength and ductility of these materials.
ature. However, there have been very few reports of It has been noted that a uniform dispersion of about
the expected dramatically increased ductility in 20 vol.-% of a nanocrystalline phase in an amorphous
nanocrystalline intermetallic compounds. matrix increases the strength of the material signifi-
Jain and Christman'?' consolidated mechanically cantly while maintaining an adequate level of ductility
alloyed Fe-28AI-2Cr (at.-%) powder by shock wave in the composite (Fig. 12).166 This appears to be a
compaction and produced fully dense compacts with fruitful line of research investigation.
a grain size of rv 80 nm. These compacts were brittle Metals are usually soft, ductile, and tough while
in tension, with a failure strength of 0·65 GN m - 2, ceramics are strong, hard, and brittle. However,
comparable to the coarse grained intermetallic. through nanostructure processing, it appears to be
However, the compact exhibited superplastic-like flow possible to make metals hard and strong like ceramics
in compression at room temperature with true and ceramics can be made ductile like metals.
strains > 1·4.
Wang et ai.,162 conducted creep experiments on
nanocrystalline (28 nm) and coarse grained (257 nm) Electrical properties
Ni-20 at.-%P samples and noted that the creep rate Because of the increased volume fraction of atoms
at 280°C was 3·7 times higher for the nanocrystalline lying at the grain boundaries, the electrical resistivity
sample than the coarse grained one. Based on the of nanocrystalline materials is expected to be higher
analysis of the creep data, the authors concluded that than that in the corresponding coarse grained
creep in the two different samples originated from polycrystalline materials. Actual measurements of
different mechanisms. electrical resistivity on the nanocrystalline materials
Recent nanoindenter measurements on 12 nm Ti02 have been carried out only recently.
(Ref. 124) and 7 nm ZnO (Ref. 163) have demon- The electrical resistivity p of nanocrystalline mater-
strated that the strain rate sensitivity increases dra- ials has been found to be higher than that in both
matically to about 0·04, approximately 1/4 that for coarse grained polycrystalline metals and amorphous
•• •• •
CJ) [J • 50nm
0
....J C
W CD
....J W
• •
enZ
5 40 - •• • • 90nm
•• ••••
W
I-
•
500
20 -
.- • ••
'--_-'--_--1..._---&. __ .1..--_-'--_--1...--1 0 I I I
300 350 400 450 500 550 600 50 100 150 200 250
TEMPERATURE, K
TESTING TEMPERATURE, K
* Amorphous,
International Materials Reviews 1995 Vol. 40 No.2
Suryanarayana Nanocrystalline materials 55
may lead to a wide range of interesting device 500/0 in some cases) and of even the amorphous
applications. material. While most of the investigators'P'v'"
The relations between conductivity and temper- reported a non-linear (parabolic) variation of specific
ature, composition, and compaction pressure were heat with temperature, Lu et al.182 reported a linear
recently studied175 for a series of nanocrystal- variation. Hellstern et al.181 also noted that the specific
line oxide samples - LaFe03, LaCo03, and heat increase at a constant temperature was linear
Lal-xSrxFel-yCOy03' The results show that though with the reciprocal crystal size.
the conductivity is lower, the slope of the conductivity The specific heat of a material is closely related to
temperature curve is higher for the nanocrystalline its vibrational and configurational entropy, which is
materials in comparison with the coarse grained significantly affected by the nearest neighbour con-
materials. figurations. Thus, the increase in specific heat of
The magnitude of the electrical resistivity (and nanocrystalline materials has been attributed to the
hence conductivity) in composites can be changed by small crystal size (and consequent large interfacial
altering the size of the electrically conducting com- component). If this is so, grain growth should reduce
ponent. For example, by changing the size of the Fe the specific heat of the nanocrystalline material. This
particles and the volume fraction occupied by iron, was, in fact, observed.180,181
the electrical properties can be varied in a continuous
fashion in an iron-silica system. By changing the
Thermal expansion
volume fraction alone, the electrical conductivity
could be increased by 14 orders of magnitude. Measured thermal expansion coefficients (J. of nano-
The phenomenon of giant magnetoresistance crystalline Cu, Pd, Fe-B-Si, and Ni-P alloys were
almost twice the value of single crystals.9,138,170,182
(G MR) (decrease of electrical resistance of materials
when exposed to a magnetic field) has been reported For example, (J. for nanocrystalline (8 nm) Cu has
in a number of multilayer systems.l?" Giant mag- been reported to be 31 x 10- 6 K - 1 in comparison
netoresistance has been recently observed in equiaxed with 16 x 10-6 K-l for Cu single crystals." Similar
(3D) nanocrystalline materials.V'>'?? Whereas the enhancements were observed in nanocrystalline Pd,
resistance drop is only 1-20/0 in conventional coarse Ni-P, Fe7sB13Si9, and Ti02 samples. The thermal
grained materials, the drop is as large as 50-800/0 in expansion coefficients of different materials in the
the case of a nanocrystalline material. Giant mag- nanocrystalline, amorphous, and coarse grained con-
netoresistance has been shown to occur in magnet- ditions are compared in Table 5. As the crystalline
ically inhomogeneous media containing non-aligned component for a nanocrystalline material contributes
ferromagnetic entities on a microscopic scale and insignificantly to the enhancement of (J., the average
(J. of the boundary component has been proposed
scales inversely with the average particle diameter.
to be about 60 x 10-6 K -1; agreeing with direct
mcasurernents.l'" Thus, by varying the interfacial
Specific heat volume (by changing the grain size), one can
Since the specific heat of a material is directly related 'tailor' the coefficient of thermal expansion to any
to the atomic structure, measurements of the specific predetermined value.
heat as a function of temperature of nanocrystalline
materials should reveal differences in comparison with Optical properties
glassy or crystalline materials of comparable chemical
Only a limited amount of information is available on
composition. Specific heat measurements have been
the optical properties of nanocrystalline materials.
made on nanocrystalline materials prepared by gas
In spite of this, the results are interesting and show
condensation, 180 mechanical alloying.l'" and crys-
that the optical transparency can be changed by
tallisation of amorphous alloys prepared by rapid
controlling the processing parameters.
solidification methods.l'"
Figure 14 shows two ceramic Y203 samples syn-
The specific heats of different nanocrystalline
thesised by the gas phase condensation technique.
materials with their coarse grained polycrystalline
Even though both the samples have approximately
counterparts, and also with the amorphous material
the same grain and pore size (8 nm), the sample on
of the same composition, wherever available, are
the right is transparent, while the one on the left is
compared in Table 4. It may be noted that the specific
opaque. The reason for the different transparencies is
heat in the nanocrystalline state is much higher than
that there is very little aggregation of pores between
that in the coarse grained material (by as much as
the nanocrystals in the specimen on the right; accord-
ingly, the pores (which are much smaller than the
Table 4 Comparison of specific .heats
(J mol"? K-1) of nanocrystalline, amor-
Table 5 Thermal expansion coefficients (10-6 K-1)
phous, and coarse grained polycrystalline
of nanocrystalline, amorphous, and
materials measured at 250 K
coarse grained materials
Coarse grained
Condition
Material Nanocrystalline Amorphous polycrystalline Temp.
range, Coarse
Cu 26 24
Pd 37
Material K Nanocrystalline Amorphous grained Ref.
27* 24
Ni-20 at-%Pt 25 24 22 Ni-P 300-400 21-6 14·2 13·7 182
Fe7SB,3Sig 300-500 14·1 7·4 6·9 138
* Extrapolated to pure Pd based on values for amorphous Pd72Si,sFe,o.
t Measured in temperature range 310-400 K.
Cu 110-293 31 16 9
103.-------.-----,r----_.__----,
f=50Hz
Fe-3.5Si ~
Ta = 993K t:
-
'0)
~
~ 10-1
en
en
s
w
a:
o
o
-
(a) (b)
10-3 '----'----II...-_-'----L_.&--.a-- .•.....•.
.-L-L-_-'----J r I
16 Comparison of core losses of conventional coarse grained Fe-3'5Si, amorphous Fe-9Si-13B (at.-%),
and nanocrystalline Fe-7Zr-6B-1Cu (at.-%) alloys as function of a maximum induction field 8m and
b frequency f; Ta is annealing temperature (after Ref. 195)
surface area available can be accurately tailored by Rofagha et al.208,209 studied nanocrystalline Ni-P
controlling the porosity in the samples. One can alloys produced by the electrodeposition technique.
obtain full theoretical density to achieve the best The average dissolution rate of nanocrystalline Ni
mechanical properties, produce a highly porous was found to be higher than that for coarse grained
material to obtain very large surface areas, or have material. However, while coarse grained Ni suffers
an intermediate value of porosity. excessive intergranular corrosion in acidic media,
Beck and Siegcl''?" have recently shown that the nanocrystalline Ni exhibited more uniform corrosion
chemical reactivity of nanocrystalline Ti02 which has morphology.i'" Superior localised corrosion .resist-
been only lightly consolidated (to maximise the ance in HCI was observed for sputter deposited
porosity and hence the surface area) is significantly nanocrystalline 304 stainless steel (Fe-18Cr-8Ni) in
higher than that in other commercially available Ti02 comparison with conventional material. This is attri-
samples. Figure 17 shows the catalytic activity for buted to the fine grain size and homogeneity of the
S removal from H2 S via decomposition for several °
nanocrystalline material. 21 A similar behaviour was
forms of Ti02 having either the rutile or anatase noted in the Fe-Ni-Cr-P-B alloy and the improve-
structure with different surface areas. It can be seen ment was explained in terms of Cr enrichment of the
that the nanocrystalline sample is far more reactive specimen surface as a result of having more rapid
than any of the other samples, both initially and even grain boundary diffusion paths.i'"
after exposure for 7 h; the activity for nanocrystalline Nanocrystalline Ni-P alloys were non-passivating
Ti02 is about 5 times greater than for the next most in O·lM H2S04, Their enhanced dissolution rates
active materials. This greatly enhanced activity was over those of conventional polycrystalline Ni was
shown to result from a combination of unique and explained as due to the presence of P and the
controllable features of the nanocrystalline material high volume fraction of grain boundaries and triple
- its high surface area combined with its rutile struc- junctions. Further, anodic polarisation of the nano-
ture and its oxygen deficient composition. Annealing crystalline material resulted in the formation of
this material in an oxygen atmosphere decreased the non-protective surface films.
number of anion vacancies and lowered the activity.
z
w
•.... U5
z -c
20Co 1-2~m
00.2 • catalyst A T catalyst D
ffi<i 300 •
o 6Co1-2~m
w o catalyst 8 o catalyst E •
o .•. catalyst C
I o catalyst F 200-r--f"'-,.-r---r---r-~--,r__~___r____,___r-_r__~~
o,
.....J
1000 1200 1400 1600 1800 2000 2200 2400
~ 0.1 HARDNESS, kg mm-2
1-2% in a Ni-Fe (Permalloy) magnetoresistive sensor characterised material with reproducible properties;
in a weak magnetic field. Thus, materials exhibiting and this needs to be done economically. A solution
this large G MR can be promising candidates for the to these barriers can be identification of well defined
reading heads of the next generation of information applications for these nanocrystalline materials and
storage systems. However, it should be noted that the this can be a driver for accelerated research. In this
large GMR can be observed only when the applied context, development of novel techniques is an urgent
magnetic field is about 1 T whereas in a Permalloy it necessity. Developments in this field thus parallel
can be observed at a field of only 1 mT. those of rapidly solidified (RS) metals.l? Even though
The excellent combination of soft magnetic prop- the RS materials exhibited a very interesting combin-
erties can be useful in producing tape wound cores ation of properties, industrial exploitation of these
for common mode chokes, saturable reactors, .high materials had to await innovations of new techniques
frequency transformers, and magnetic heads. Another - the melt spinning and planar flow casting methods.
useful property of nanocomposites is the magneto- A similar revolution can be expected in the field of
caloric effect. On cycling (applying and removing the nanocrystalline materials, especially with the launch-
magnetic field), the magnetocaloric effect can be used ing of new companies to produce large quantities of
for transferring heat from one thermal reservoir to the powders and making them easily available for
another. Thus, the magneto caloric effect can be used characterisation and exploitation.
for magnetic refrigeration (solid magnetic materials Consolidation of the fine powders and the thermal
rather than compressed gases - and also avoiding the stability of the nanometre sized grains is another
harmful chlorofluorocarbons). Materials being used concern of materials scientists. It is gratifying to note
for this purpose include Gd3 Ga3·2SFe1.7S 012' y-Fe203 that optimisation of process parameters to consolidate
stabilised in an ion exchange resin, etc.; and these can these materials to full density has been reported
be used at temperatures of 65-70 K in comparison recently. 53 Although the mechanisms are not clear,
with < 15 K for the current magnetic refrigerator the grain growth appears to be minimal and this
substance Gd3Ga5012' augurs well for the future of nanocrystalline materials.
The majority of investigations on nanocrystalline
materials to date have been concerned with materials
Concluding remarks having a grain size of 10-100 nm. Conventional fine
Nanocrystalline materials are novel materials which grained polycrystalline materials have grain sizes of
are not only scientifically interesting but also hold about 10 000 nm or larger. Hence, materials with
great potential for varied applications. Their prop- grain sizes of about 100-1000 nm and also those in
erties are different from and often superior to those the 1-2 nm range should be evaluated to determine
of conventional coarse grained polycrystalline the full range of possible properties as a function of
materials and also amorphous alloys of the grain size.
same composition. The optical, electrical, and magnetic properties of
It has been shown that by decreasing the grain size nanocrystalline materials can now be tailored by
to nanometre levels, traditionally soft and ductile controlling the grain size and porosity heralding in
metals can be made very hard and strong (and brittle?) the principles of alloy design into this new class of
and conventional ceramics which are brittle can be materials. For this line of investigations to grow
made to deform plastically like metals. The enhanced rapidly, it is essential that improved characterisation
diffusivity in these materials results in increased solid techniques become available so that the crystalline
solubilities, and synthesis of alloy phases from nor- and interfacial components can be fully characterised.
mally difficult to alloy metals and also allows the Additionally, characterisation of the material with
sintering of powder compacts at temperatures much respect to porosity is important since this has been
lower than those required for coarse grained poly- shown to affect the diffusivity, grain growth, and
crystalline materials. The electrical, optical, chemical, zechanical properties. Work on modelling of these
and magnetic properties have also been found to be materials also has just begun.212
superior in the nanocrystalline state in comparison Two exciting possibilities using the nanocrystalline
with the coarse grained material. materials are being explored now. One of these is
Most of the early results were based on materials nanoglasses wherein nanometre sized glassy particles
produced by the gas condensation technique, and are produced and these are consolidated to a bulk
porosity (very often an undetermined quantity in the shape.213-215Since glassy materials have been shown
early studies) was an integral part of the material. to have properties vastly improved over their crystal-
The properties of these materials were interpreted on line counterparts, nanoglasses can be expected to
the basis of a two component mixture - crystalline exhibit properties superior to those of even nanocrys-
and interfacial components - whereas they should talline materials. Another possibility is the synthesis
have been interpreted by taking the porosity into of nanocomposites - even more important in cer-
account as well. In fact, reduction in Young's modulus amics. Here, one can disperse nanometre sized
values.P" increased diffusivities and, in general, vari- particles inside the grains, along the grain boundaries,
ations in mechanical and physical properties have or both, of coarse grained or nanocrystalline ceramics
now been ascribed to the presence of porosity in these and such materials have been shown to have an
materials. excellent combination of strength and ductility.
Widespread use and search for technological appli- This review is concerned essentially with the struc-
cations of nanocrystalline materials requires the ture and properties of three-dimensional nanocrys-
availability of large (tonnage) quantities of well talline materials. Exciting developments are also
International Materials Reviews 1995 Vol. 40 No.2
Suryanarayana Nanocrystalline materials 61
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