Materials Science and Engineering A301 (2001) 44 – 53

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Synthesis of nanocrystalline materials — an overview

F.H. (Sam) Froes *, O.N. Senkov 1, E.G. Baburaj
Institute for Materials and Ad6anced Processes, Uni6ersity of Idaho, Moscow, ID 83844 3026, USA

Received 23 February 2000; received in revised form 7 March 2000

Abstract

This paper reviews research work at the Institute for Materials and Advanced Processes (IMAP), University of Idaho, on the
synthesis of nanocrystalline materials and their consolidation. Nanocrystalline materials have been synthesized by a number of ‘far
from equilibrium processes’, including mechanical alloying (MA), mechanochemical processing (MCP), supercritical fluid
processing (SCFP), and severe plastic deformation (SPD). Examples of the materials include the Ti – Al based intermetallic
compounds and composites produced by MA and SPD, Ti base alloys and metal carbides synthesized by MCP, thin film Cu
produced by SCFP, and Al–Fe alloys produced by SPD. Details of the processes used and the enhancement of properties due to
the nanoscale structures in consolidated material will be presented. The potential of these processes to substitute for conventional
methods of production will also be discussed. © 2001 Elsevier Science B.V. All rights reserved.

Keywords: Synthesis; Nanocrystalline materials; Mechanical alloying; Mechanochemical processing; Supercritical fluid processing

1. Introduction similar high temperature properties to the superalloys

Nanocrystalline materials have high potential for use
in structural and device applications in which enhanced
mechanical and physical characteristics are required. In
this paper work at the Institute for Materials and
Advanced Processes (IMAP), University of Idaho on
the synthesis of these types of materials is reviewed with
an emphasis on processes, which are scalable to large
commercial quantities rather just being laboratory
curiosities.
2. Synthesis and characterization of titanium aluminide
based alloys and composites with nanocrystalline and
submicrocrystalline structures
Gamma TiAl-based alloys are potential candidates to
replace Ni-based superalloys currently used in thermal
protection systems and engine components at tempera-
tures up to 900°C as they have half the density and
* Corresponding author. Tel.: +1-208-8857989; fax: + 1-208-
8854009.
E-mail address: imap@uidaho.edu (F.H.S. Froes).
1
Current address: UES, Inc., 4401 Dayton-Xenia Rd., Dayton,
OH 45432-1894, USA.
[1–3]. However, there is a limitation in the forming
methods, which can be used with TiAl alloys because of
their brittleness at temperatures below 600°C. Attempts
to improve ductility of the alloys by chemistry modifi-
cations or microstructural control have shown limited
success [3,4].
It has been shown [5] that generally very brittle
ceramics exhibit a fair degree of ductility at room
temperature if they have a nanocrystalline structure. A
critical grain size has been theoretically predicted [6,7]
below which ceramic and intermetallic materials can
become ductile. This has been supported experimentally
on NiAl [8] and Ti3Al [9]. Grain refinements to a
nanoscale range also open up possibilities of a consider-
able decrease in temperatures for compaction or super-
plastic forming as the rates of these diffusion-related
processes increase dramatically when the grain or parti-
cle size decreases [10–14].
2.1. Production of nanocrystalline and
submicrocrystalline structures
Two approaches have been used at IMAP to produce
titanium aluminides with a nanocrystalline (grain
size5100 nm) or submicrocrystalline (grain size51

0921-5093/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
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 F.H.S. Froes et al. / Materials Science and Engineering A301 (2001) 44–53 45

Table 1
Powders and processes used to produce nanocrystalline materials

Goal composition Powders used MA duration (h) HIP conditions Final grain size (nm)

Ti–47Al–3Cr Gas atomized Ti–47Al–3Cr 15 725°C, 207 MPa, 2 h 42

850°C, 207 MPa, 2 h 88
975°C, 105 MPa, 2 h 180
Blend of TiH2, Al and Cr 15 725°C, 207 MPa, 2 h 45
Ti–48Al–2Nb–2Cr Gas atomized Ti-48Al–2Nb–2Cr 15 850°C, 207 MPa, 2 h 92
Ti–47Al–3Cr/30vol.% Ti5Si3 Blend of Ti–47Al–3Cr, TiH2 and Si 15 850°C, 207 MPa, 4 h 140
1050°C, 105 MPa, 4 h 580

mm) structures. One approach is production of amor- developed for hot working (Ti–47Al–4[Mn,Cr,Nb,Si,
phous or nanocrystalline powders by mechanical alloy- B] [18]). The smallest grain size achieved by this method
ing (MA) [12–14], a high-energy-input process in which was 100 nm (Table 2).
heavy working of powder particles results in intimate
alloying by repeated deformation, fracturing and weld- 2.2. Grain growth
ing. Once amorphous or nanocrystalline phases are
synthesized, reliable methods are needed to consolidate The main problem of a nanocrystalline structure is its
these materials. The interest lies in producing a instability at high temperatures. Because of the large
nanocrystalline structure in the compacted material excess free energy, significant grain growth has been
from the amorphous or nanocrystalline powders by observed in several nanocrystalline materials [19,20].
compaction under controlled conditions. Hot isostatic On the other hand, stabilization of the nanocrystalline
pressing (HIP’ing) has effectively been used for com- grain structure was observed in many materials after
paction of a number of fully dense nanocrystalline continuous annealing [20]. The Ti5Si3 phase has the
titanium aluminide based alloys and composites (Table closest coefficient of thermal expansion to that of TiAl,
1). A decrease in the HIP’ing temperature from 975 to which, together with its high stiffness and strength,
725°C led to a decrease in the final grain size from 180 makes Ti5Si3 an attractive potential reinforcing phase in
to 40 nm. TiAl [21]. Considerable grain growth occurred during
Another approach for grain refinement in titanium the initial stages of annealing of the HIP’d samples
aluminides is multi-directional isothermal forging with (Fig. 1) with a tendency to reach a saturation stage
a forging temperature decreasing from 1050 to 750– where grains grew very slowly. After annealing for 500
800°C [15]. High formability at 1000 – 1100°C has been h at 850 and 975°C, for example, the average grain size
shown to be due to extensive dynamic recrystallization in Ti–47Al–3Cr was 170 and 415 nm, respectively. The
(DRX) [16,17]. The grain refinement in a whole part same tendency for grain growth was observed in the
results in further improvement in the formability of the
g-alloys. This makes possible subsequent working at Table 2
lower temperatures which, in turn, leads to further Alloy compositions, processing conditions, and grain sizes of work-
pieces [15]
microstructure refinement. This approach developed in
the Institute for Metals Superplasticity Problems Composition, initial Processing Grain size (nm)
(IMSP), Russian Academy of Sciences, allows produc- type of microstructure,
tion of submicron-sized grains in large-scale billets [18]. grain/colony size (mm)
The initial microstructure and chemical composition
Ti–50Al, cast, duplex, 3–5-Stage 400
affect much the easiness of production and homogene- rg =20%, a–b–c-forging at
ity of the fine g-grained structure. As seen from Table d =100/1000–2000 1000/800°C
2, different processing parameters are required for dif- Ti–46Al, PM, near g 2-Stage a–b-forging at 200
ferent titanium aluminide alloys to produce almost the equiaxed, d =20–30 1000°C and 750°C
same submicrocrystalline structure. For example, it was Ti–48Al–2Cr–2Nb, 20-Stage a–b–c-forging 300
Cast+HIP, at 1000/750°C
very difficult to obtain a submicron grain size in the lamellar, d =500
Ti –48Al–2Cr–2Nb and Ti – 46Al – 2Cr – 2Nb – 1Ta cast Ti–46Al–2Cr–2Nb–Ta, 15-Stage a–b–c-forging 300
alloys with initial coarse-grained non-homogeneous Cast+HIP, at 1000/740°C
structure. However, in the P/M alloy with micron-sized lamellar,
grains, the submicrocrystalline structure was easily d =300–400
Ti–25Al, Cast, 6–8-Stage 100
formed even in large-scale billets, for example, by 2- lamellar, a–b–c-forging at
stage a–b-forging. The submicrocrystalline structure d =200–300 1050/650°C
can also be easily obtained in the cast alloys specially
46 F.H.S. Froes et al. / Materials Science and Engineering A301 (2001) 44–53
Fig. 1. Dependence of the mean grain size on the annealing time and
temperature in the two nanocrystalline TiAl-based alloys.
nanocrystalline Ti – 48Al – 2Nb – 2Cr alloy (Fig. 1) and
Ti –47Al–3Cr/Ti5Si3 composite [22,23].
Grain growth was described by the equation [24],
D n −D n0 = K0 exp
−Q
t (1)
RT
where D0 and D are the initial and current grain sizes,
t is the annealing time, T the absolute temperature, R a
gas constant, Q the activation energy for grain growth,
and n and K0 are material constants. Fitting this equa-
tion to the experimental data gave the values n=4,
K0 = 1.2–2.4× 1022 nm4 h − 1 ( =3.3 – 6.5 ×10 − 18 m4
s − 1), and Q = 330 kJ mol − 1 to be the same for Ti–
47Al–3Cr, Ti–48Al – 2Nb – 2Cr alloy and Ti–47Al–
3Cr/Ti5Si3. The same temperature dependencies of the
kinetic parameter K =(D 4 – D 40)/t were obtained for the
alloys and composite (Fig. 2). These results indicate
that the Ti5Si3 phase has a little effect on grain growth.
The value of the grain growth exponent n = 4 is twice
that of predicted for normal grain growth in high
purity metals when no dragging or pinning forces are
present [24]. However this value (n = 4) is frequently
observed in two-phase alloys when the grain growth is
limited by a permanent pinning force on grain
boundaries [25], which probably is the case for the
alloys studied in the present work.
Fig. 2. Temperature dependence of the kinetic parameter K=
K0exp( −Q/RT), Eq. (1), for the submicrocrystalline TiAl/Ti5Si3
composite and nanocrystalline TiAl alloys.
2.3. Superplasticity
Titanium aluminides with submicrocrystalline and
nanocrystalline structures showed a high elongation to
rupture (above 200%) and high strain rate sensitivity
(m\0.3), features characteristics of superplastic (SP)
behavior at temperatures 700–900°C [26,27], that is
200–400°C lower than that for the alloys with micron-
sized grains [28]. The activation energy for SP flow of
titanium aluminides with grain size B 1 mm was deter-
mined to be 180–195 kJ mol − 1 suggesting that grain
boundary diffusion was the rate controlling mecha-
nism. Superplastic characteristics of the titanium alu-
minides with a submicrocrystalline structure produced
by multi-step isothermal forging [15,27] are given in
Table 3.
3. Nanocrystalline aluminum–iron alloys
Aluminum–iron alloys are attractive for applications
at temperatures beyond those normally associated with
aluminum alloy use. Alloying aluminum with iron in-
creases the high temperature strength due to a disper-
sion of second-phase particles [29]. Unfortunately, the
equilibrium solubility of iron in the aluminum lattice is
very low and even at high temperatures it does not
exceed 0.03 at.% [30], and these alloys cannot be dis-
persion-strengthened with the use of conventional solid
state heat treatments. The strengthening effect can be
enhanced by increasing the solid solubility of iron in
the aluminum matrix by ‘far-from-equilibrium’ tech-
niques such as rapid solidification [31,32], MA [33–36]
or severe plastic deformation (SPD) [37]. SPD can
refine the microstructure of metals and alloys into the
nanometer-sized range [37,38] and lead to formation of
metastable phases [38–41] including supersaturated
solid solutions [40–42]. These novel constitutional and
microstructural effects can enhance physical and me-
chanical properties. SPD was used to extend the iron
solubility in aluminum and to produce a nanocrys-
talline dispersion-strengthened structure after aging.
3.1. Effect of se6ere plastic deformation
The cast Al–(5–16wt.%)Fe alloys had a typical den-
dritic type microstructure and contained a face cen-
tered cubic aluminum matrix, and monoclinic Al13Fe4
phase. The average grain size in the aluminum matrix
was  15 mm. Virtually no iron was in solution in the
aluminum matrix in agreement with the equilibrium
Al–Fe phase diagram [30].
A very fine microstructure was produced in the alloy
samples after severe plastic deformation. The transmis-
 F.H.S. Froes et al. / Materials Science and Engineering A301 (2001) 44–53 47

Table 3
Superplastic characteristics of titanium aluminides with a submicrocrystalline structure produced by multi-step forging [27]

Alloy D (nm) T (°C) o (s−1) d (%) m

Ti–50Al (TiAl, ingot metallurgy) 400 750 8.3×10−4 180 –

800 8.3×10−4 225 0.46
850 8.3×10−4 260 0.47
900 8.3×10−4 220 –
Ti–46Al (powder metallurgy) 200 700 6.4×10−4 170 –
800 6.4×10−4 415 –
900 6.4×10−4 695 0.36
900 1.3×10−3 710 0.48
900 1.3×10−1 265 –
950 6.4×10−4 460 –
400 850 6.4×10−4 460 –
Ti–46Al–2Cr–2Nb–1Ta (ingot metallurgy) 250 750 6.7×10−4 310 –
800 6.7×10−4 520 –
850 6.7×10−4 350 –
Ti–48Al–2Cr–2Nb (ingot metallurgy) 300 750 8.3×10-4 195 –
800 8.3×10−4 355 0.56
850 8.3×10−4 270 –
Ti-25Al (Ti3Al, ingot metallurgy) 100 500 6.4×10−4 120 –
600 6.4×10−4 680 –
300 600 6.4×10−4 300 –
700 6.4×10−4 780 –
800 600 6.4×10−4 170 –
800 1.3×10−4 640 0.80
800 6.4×10−4 580 0.30
950 6.4×10−2 660 0.60
950 1.3×10−1 190 0.31

sion electron microscopy (TEM) analysis revealed two
phases in the deformed alloys — a fcc Al-rich matrix
and monoclinic Al13Fe4 particles. The aluminum-rich
phase had a homogeneous grain structure with a mean
grain size of about 100 nm (Fig. 3a). The diffraction
pattern obtained from a region of 300 nm in diameter
(Fig. 3b) indicated that the grains are randomly ori-
ented and have high angle grain boundaries. EDS
analysis of the Al-rich phase revealed that it contained
1.3–2.4 wt.% Fe in solid solution. An even higher
concentration of iron (up to 6.2 wt.%) was detected in
matrix grains adjacent to Al13Fe4 particles.
The Al13Fe4 phase was homogeneously distributed in
the deformed alloys as particles of less than 1 mm in size
(Fig. 4a). Very often these particles had diffuse
boundaries with the aluminum-rich matrix. EDS analy-
sis of the particles shows that they contain of 35.0–38.0
wt.% iron, which is between the Al3Fe and Al4Fe
compositions.
The as-cast Al – 11%Fe alloy had a Vicker’s micro-
hardness Hv of 75. After severe torsional straining, the
microhardness increased to 175, an increase of 2.3×
compared with the cast state. This large increase in the
microhardness may result from several effects including
grain refinement, increased dislocation density and in-
ternal stresses, fragmentation of the second-phase parti-
cles, and formation of a supersaturated solid solution
of iron in the aluminum matrix.
3.2. Effect of aging
Aging at room temperature for more than 3 months
did not change the microhardness of either the as-cast
or deformed Al–11%Fe alloy. Artificial aging at 100°C
for 5 h decreased the microhardness of the as-cast alloy
from 75 to 60 and no further changes in microhardness
occurred at longer annealing times. This decrease in
microhardness was probably due to relaxation of inter-
nal stresses typical of the as-cast material. In contrast,
artificial aging at 100°C of the as-deformed alloy led to
a significant increase in microhardness, with a maxi-
mum value of Hv = 302 being reached after 5 h of aging
(Fig. 5a). This large increase in the microhardness
during aging was apparently caused by precipitation of
second phase particles on dislocations and grain
boundaries (Fig. 6), although some relaxation also oc-
curred probably. Further increase of the aging time up
to 12 h led to a continuous decrease of the microhard-
ness, however, the values were still higher than that in
the as-deformed state.
The results clearly indicate that conventionally non-
heat-treatable Al–Fe alloys become heat treatable after
severe plastic deformation. The potential for heat treat-
ment occurs because severe plastic deformation results
in a supersaturated solid solution of iron in the alu-
minum matrix. The strengthening effect produced by
aging is very high so that microhardness can be in-
48 F.H.S. Froes et al. / Materials Science and Engineering A301 (2001) 44–53
creased by a factor of 4 compared with the cast state
and it significantly exceeds the microhardness of con-
ventional aluminum alloys. The property changes in the
deformed specimens during the artificial aging (see Fig.
5a) follow a general trend [43]. An increase in the
microhardness at the beginning of aging is probably
due to a local redistribution of the iron in the supersat-
urated solid solution leading to formation of small
precipitates, which are coherent with the matrix [43]. A
decrease in the microhardness after 5 h of aging is
caused by a coarsening of the second-phase particles
that become incoherent with the matrix. Grain coarsen-
ing of the matrix phase and relaxation of the internal
stresses occurring during aging at 100°C may also
contribute to the microhardness decrease.
Once decomposition of the supersaturated solid solu-
tion is initiated during holding at 100°C, the aging
process can continue at room temperature. Fig. 5b
shows the effect of natural aging on the microhardness
of a specimen, which has been severely deformed fol-
lowed by aging at 100°C for 5 h (peak aging). The
microhardness increased to a maximum value of Hv =
510 after subsequent holding at room temperature for 6
h, and then remained almost constant during further 50
h of aging, and then decreased continuously with the
aging time (Fig. 5b). This additional age-hardening
during holding the specimen at room temperature is
probably due to further decomposition of the solid
solution and growth of coherent precipitates. The mi-
crohardness decrease at longer holding times is appar-
ently due to a coherency loss between the matrix and
particles [43]. Additional experiments are required to
further investigate this behavior.
4. Synthesis by mechanochemical process
The mechanochemical process (MCP) is broadly the
use of mechanical energy to cause reactions, which
Fig. 3. TEM micrograph of as-strained Al–7.5%Fe alloy, aluminum-rich matrix, (a) bright field and (b) selected area diffraction pattern.
normally require elevated temperatures, to occur at
ambient temperatures [44,45]. For example, reduction
reactions, which are normally carried out at tempera-
tures close to 1000°C, can be achieved at ambient
temperatures through MCP. Normally, the reaction
products formed by MCP are ultrafine powders with a
wide distribution of particle size ranging from few
nanometers to one micron. A number of metals, alloys
and inorganic compounds have been prepared in ul-
trafine (nanometer sized particles) form at the Univer-
sity of Idaho [46–49] and elsewhere [50–52] by MCP
including titanium aluminides, and titanium carbides.
4.1. Titanium aluminide
The basis for the synthesis of titanium– aluminum
alloys is the co-reduction reaction:
6TiCl4 + 2AlCl3 + 7CaH2 + 8Mg
“2Ti3Al(H)+7CaCl2 + 8MgCl2 (2)
induced by mechanical milling. The reaction product
after leaching is Ti3Al(H) [53,54] with the hydrogen
appearing to occupy interstitial sites in the Ti3Al struc-
ture. The reaction shown above differs from conven-
tional reduction processes in which metallic elements
are used for reduction reactions. The use of CaH2 as a
reducing agent in the present case results in the forma-
tion of Ti3Al(H), which is more passive to oxidation
than Ti3Al. Fig. 7 shows the X-ray diffraction (XRD)
pattern along with the TEM photomicrograph of the
alloy synthesized by MCP. The alloy powder thus
produced can be dehydrided and consolidated by hot
isostatic pressing.
4.2. Titanium carbide
Nanocrystalline TiC has been synthesized by the
displacement reaction
 F.H.S. Froes et al. / Materials Science and Engineering A301 (2001) 44–53 49

Fig. 4. (a) TEM photomicrograph and (b) corresponding selected area diffraction pattern of an Al13Fe4 particle in the aluminum-rich matrix.
Al– 11%Fe alloy after severe plastic deformation.

TiCl4 + 2CaC2 “ TiC + 2CaCl2 +3C (3) characteristics. Diffusivities are typically an order of
magnitude higher than the corresponding liquid; vis-
The reaction has also been modified to avoid the
cosities are usually many times lower than those of
liberation of free carbon, by the addition of Mg,
ordinary liquids providing appreciable penetrating pow-
2TiCl4 + CaC2 + 3Mg “ 2TiC +CaCl2 +3MgCl2 (4) der into a solid matrix resulting in an efficient extrac-
tion. These factors along with low surface tension allow
The Ti produced by reduction of TiCl4 with Mg, and
SF to have mass transport characteristics of a gas while
the C generated by the reaction between TiCl4 and
CaC2 combine to form TiC. Experiments involving
stoichiometric amounts of reactants produced
nanocrystalline TiC [55]. This was very encouraging, as
an incomplete reaction would have resulted in unre-
acted TiCl4 or sub-chlorides. Fig. 8 is an XRD pattern
from TiC formed through the reaction involving Mg
indicating no detectable impurities. The TEM examina-
tion showed a wide distribution of TiC particles in the
size range of 10– 200 nm (inset in the figure) [56].

5. Synthesis by supercritical fluid processing

Supercritical fluid processing (SCFP) for the synthe-

sis of metals and metal oxides is a recent addition to the
list of modern processing techniques [57]. Recent work
at the University of Idaho has demonstrated the feasi-
bility of coating metal and oxide films on silicon sub-
strates [58]. This process involves the dissolution of
organic compounds containing the metal ions in super-
critical fluid (SF) and reducing or oxidizing the com-
pound to generate an ultrafine metal or oxide as desired
[59].
Any substance at a temperature above its critical
temperature, Tc, and pressure above its critical pres-
sure, Pc, is defined as a SF. The critical temperature is
the highest temperature at which a gas can be converted
to a liquid by increasing the pressure. The critical
pressure is the highest pressure at which a liquid can be Fig. 5. Dependence of Vicker’s microhardness of the Al –11%Fe alloy
converted to a gas by an increase in temperature. In the on aging time (a) at 100°C after severe plastic deformation and (b) at
supercritical region, the dense fluid has many useful 25°C after severe deformation and aging at 100°C for 5 h.
50 F.H.S. Froes et al. / Materials Science and Engineering A301 (2001) 44–53

state at a temperature as low as 31.1°C. Ease of dissolu-

tion of organometallic compounds in the SF facilitate
chemical reactions in reducing or oxidizing environ-
ment at low temperatures resulting in the nucleation
and growth of ultrafine solids.

5.1. Example of sub-micron size copper particles

An example of metal particles produced by hydrogen

reduction of copper hexafluoroacetylacetone,
Cu(HFA)2 in supercritical carbon dioxide are the cop-
per particles in Fig. 9. This fluorinated copper com-
pound has high solubility in the supercritical carbon
dioxide [60] and can be reduced to copper metal ac-
cording to the following reaction:

In the presence of hydrogen gas at elevated tempera-

tures, Cu(HFA)2 can be reduced to copper metal in
supercritical fluid carbon dioxide. Because of the high
solubility of HFA in supercritical carbon dioxide, it will
remain in the fluid phase while copper atoms displaced
by hydrogen condense on the substrate at 250°C. Wai
et al. [61] have recently also produced nanocrystalline
silver by the SCFP technique.

Fig. 6. Microstructure of the severe deformed Al–11%Fe alloy after

aging at 100°C for 5 h, (a) bright field and (b) dark field images. 6. Conclusions

A number of ‘far from equilibrium processes’ includ-

retaining liquid-like solvating strengths. To carry out ing MA, SPD, MCP and SCFP have been utilized to
reduction or oxidation reactions, CO2 has been found synthesize nanocrystalline materials.
to be an ideal SF, because it is nontoxic, non-reactive Titanium aluminide based alloys and composites
and inexpensive. In addition, CO2 can be kept in the SF with nanocrystalline and submicrocrystalline structures

Fig. 7. XRD pattern taken from nanocrystalline Ti3Al. TEM micrograph of the fine particles is shown in the inset.
 F.H.S. Froes et al. / Materials Science and Engineering A301 (2001) 44–53 51

Fig. 8. XRD pattern taken from nanocrystalline TiC. TEM micrograph of the fine particles is shown in the inset.

can be produced using MA or extensive plastic defor- Acknowledgements

mation. MA resulted in complete amorphization of the
powders; after hot isostatic pressing to compact the This work was supported by the Idaho State Board
powders, crystallization and grain growth occurred so of Education, Grant No. S96-016 (Dr R. Dodson,
that the minimum grain size produced in a fully dense Chief Academic Officer), US Army Research Office,
compact was around 40 nm. Extensive deformation by Contract No. DAAG55-98-1-0008 (W.M. Mullins, Pro-
multi-directional isothermal forging led to a minimum gram Officer), US Army Research Laboratory, Con-
grain size in the bulk material of around 100 nm. tract No. DAAD 17-99-R-9029 (Dr M.G.H. Wells,
Grain growth in nanocrystalline titanium aluminide Project Officer), and NATO Linkage Grant No.
alloys occurred with a saturation stage and even after HTECH.LG 961178. The authors would also like to
100 h annealing at 1100°C the grain size did not exceed extend their appreciation to M. Martonick and S.
1 mm. Senkova for their help in typing and formatting. Special
Titanium aluminides with nanocrystalline and submi- thanks go to G. Salishchev, M. Shagiev, R. Imaev and
crocrystalline structures showed superplastic behavior A. Kouznetsov, Institute for Metals Superplasicity
at temperatures in the range 700 – 900°C, that is 200–
400°C lower than that for alloys with micron-sized
grains.
A nanocrystalline dispersion-strengthened structure
was produced in aluminum – iron alloys by severe plas-
tic deformation, which refined the microstructure and
extended the solubility of iron in aluminum. After aging
the, alloys showed a very high hardness equivalent to
the hardness of high strength 7XXX series aluminum
alloys.
Nanocrystalline particles of titanium aluminide and
titanium carbide were produced using the inexpensive
MCP, which initiates chemical reactions between reac-
tants at room temperature. The particle size ranged
from few nanometers to one micron.
Submicron size copper and silver particles were pro-
duced by reduction of organometallic compounds dis- Fig. 9. SEM micrograph of copper particles produced by reduction of
solved in supercritical carbon dioxide. Cu(HFA)2 in supercritical CO2.
52 F.H.S. Froes et al. / Materials Science and Engineering A301 (2001) 44–53
Problems, Ufa, Russia; C. Wai, Chemistry Department,
University of Idaho; J. Qazi and M. Cavusoglu, Uni-
versity of Idaho graduate students; former University
of Idaho graduate student N. Srisukhumbowornchai,
Salt Lake City, Utah; J. Hebeisen and P. Tylus, An-
dover, Massachussetts; Bodycote IMT, Inc.; M.L.
Ovecoglu, Chemical and Metallurgical Engineering, Is-
tanbul, Turkey; R.Z. Valiev and V.V Stolyarov, Ufa
State Aviation Technical University, Ufa, Russia; and
J. Liu, Alcoa, Pittsburgh, Pennsylvania for their contri-
butions to various aspects of the work reported.
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