In-Situ Formation of SiC-Reinforced Al-Si Alloy Composites Using Methane Gas Mixtures

BANQIU WU and RAMANA G. REDDY Theoretical and experimental studies on the in-situ formation of an Al-Si alloy composite using a methane gas mixture were carried out. An Al-Si alloy composite with in-situ formed SiC as a reinforced phase was produced by bubbling methane gas at temperatures from 1223 to 1423 K. An optical microscope, scanning electron microscope (SEM), and electron microprobe were used for the product characterization. Primary and eutectic silicon were observed in the samples taken from the top part of the crucible, and only eutectic silicon was observed in the samples taken from the bottom of crucible. The SiC formation rate increased with the decrease in the bubble size. A silicon concentration gradient existed at different vertical positions of the liquid alloy. The silicon concentration close to the top of the liquid alloy was higher than that at the bottom. The SiC concentration was very low in the bulk alloy. The bubbling of the gas mixture in the melt resulted in the formation of a layer of foam on top of the crucible. Formed SiC particles were enriched in the foam and carried out of the crucible by the overflow foam to a composite collector located under the crucible. The foam in the composite collector was broken, and composites in the foam contained up to 30 wt pct SiC. The particle size of the SiC is in the range of 1 to 10 m. The bubbling process resulted in the unevenness of the silicon concentration and the different crystallizing processes. The SiC formation rate was found to be about 12.5 mg/(L s). A kinetic model was developed. The model-predicted results are in very good agreement with the experimental results.

I. INTRODUCTION

METAL-MATRIX composites (MMCs), especially lightweight alloy-matrix composites, have had many applications in recent decades, because of their superior properties to traditional materials. Discontinuously reinforced aluminum alloy composites (DRACs), a group of very important MMCs, are rapidly emerging as new materials for aerospace and automotive industries due to their relatively low cost compared with continuously reinforced composites.[16] For example, since late 1980s, DRACs have been used in automotive engines, brake pads, and other parts. Because 12 to 17 pct of the weight of an automobile is made of cast iron, there has been the potential to substitute DRACs for cast iron, in order to reduce automotive weight, fuel consumption, and pollutant emissions. Industrial applications depend on the economic acceptance and technological quality of DRACs. Their applications for wearing parts usually require large, reinforced particles, and those for structural parts require very fine reinforced particles. Table I shows the yield-strength dependence on reinforced particle size, which indicates that a smaller particle size, e.g., less than 10 m, can give a better yield strength. Usually, the aluminum MMC with smaller reinforced particles is much more expensive than that with larger reinforced particles. In order to achieve significant improvement in mechanical properties, reinforced particles should have an average particle size of less than 10 m. A
BANQIU WU, formerly Research Associate, Department of Metallurgical and Materials Engineering, The University of Alabama, is Senior Development Engineer, Photronics, Inc., Austin, TX 78728. Contact e-mail: bwu@austin.photronics.com RAMANA G. REDDY, ACIPCO Professor, is with the Department of Metallurgical and Materials Engineering, The University of Alabama, Tuscaloosa, AL 35487-0202. Manuscript submitted October 24, 2000.
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higher strength generally requires a higher volume fraction of these expensive small particles. Therefore, industrial application of structural DRACs is strongly dependent on significant improvements in particle production technology or in-situ formation technology. The interface between the reinforcement and matrix is one of the most important features in a composite system. It affects the mechanical properties of the composite through mechanisms such as debonding, stress damping, crack deviation, and grain-boundary pinning.[7] During its service, a composite material may experience phase transformation, changes in equilibrium composition, and chemical interaction between the matrix and the reinforcement, which would result in thermodynamic unstability at the interface. For the high-temperature MMCs such as engine materials, interfacial stability plays an important role in the properties of composite materials. It is considered that superior properties can be obtained by an in-situ formed composite with more-thermodynamically stable reinforcements by nucleation and growth from the parent matrix phase.[8] The SiC-reinforced Al-Si alloy composite is currently produced by incorporation of SiC particles into the molten alloy.[9] Although the Acheson process for industrial SiC production from silica and carbon in an electric resistance furnace is well established, the price of SiC is still high, resulting in the high costs of an Al alloy composite reinforced by SiC. Some theoretical and experimental research on the in-situ formation of SiC-reinforced aluminum alloy composites has been reported,[10,11] but reference to the successful in-situ formation of Al-SiC composites by bubbling methane into an Al alloy melt was not found. In this article, SiC-reinforced aluminum alloy composites were produced by bubbling methane gas into aluminum alloy melts.
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Table I. Predicted Overall Increase in Yield Strength[3]

Particle Size, m
0.5 10 70 250

, MPa (Predicted)
98.72 61.75 34.80 19.55

, MPa (Experimental Determined)

60 34 27 10

Fig. 2Typical optical photograph of a sample from the composite collector.

Fig. 1Experimental setup.

II. EXPERIMENTAL The experimental setup is shown in Figure 1. The reaction system was in a bottom-end-closed vertical-tube resistance furnace, in order to avoid air or oxygen. The system was protected with argon through the experiments. Premixed Al-Si powders contained in an aluminum crucible were melted in this furnace. An alumina bubbling tube with several 1 mm holes close to the end was immersed into the melt. The bubbling resulted in a layer of foam overflowing the crucible, so a composite collector was placed under the crucible to collect the foam. The experimental process was monitored through an eyehole on the top of the furnace, and the temperature was measured by a thermocouple. Experiments were carried out at temperatures of 1223 to 1423 K and with a bubbling time of 1 to 3 hours. The silicon content in the alloy was 10 to 40 wt pct. Aluminum ( 99 pct purity) and silicon ( 99.9 pct purity) were used in the experiments. Before the alloy components were introduced into the furnace, the aluminum and silicon were mixed well. A 100 mL alumina crucible containing about 100 g of the aluminum and silicon mixture was kept in the constant-temperature zone of the furnace. The furnace was flushed with argon before heating. After the furnace was heated to the predetermined temperature and held for 2 to 3 hours to completely melt the alloy, the melt was bubbled with gas containing 10 pct CH4 and 90 pct Ar. After the selected bubbling time, the furnace was turned off and the crucible was cooled in the argon atmosphere. Then, the
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Fig. 3X-ray diffraction pattern of a sample from the composite collector.

crucible and composite collector were taken out of the furnace for sampling and characterization. During the bubbling, a foam of liquid alloy enriched with SiC particles gradually spilled over the crucible rim and flowed down to the composite collector located under the crucible. The silicon carbide content of samples from the composite collector was in the range of 20 to 30 wt pct. III. RESULTS AND DISCUSSION A. Product Morphology and Structure Characterizations of samples at the typical experimental conditions (950 C for about 2.5 hours) are shown in Figures 2 through 10. The optical micrographs of samples from the composite collector are shown in Figure 2. There are mainly three phases in the figure: the light phase, medium-light phase, and dark phase. The light phase is a typical Al-Si alloy image, with matrix aluminum and slab-shaped silicon. The medium-light phase was analyzed and found to be primary silicon. The dark phase is in-situformed silicon carbide. The sample was ground and X-ray powder diffraction was done, as shown in Figure 3. It indicates that the three
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Fig. 7SEM secondary electron image of sample 6S. Fig. 4Optical microscope photograph of a sample from the top of the crucible.

Fig. 8SEM backscattered electron image of sample 6S.

Fig. 5Optical microscope photograph of a sample from the bottom of the crucible.

Fig. 9SEM backscattered electron image of 6S.

Fig. 6X-ray diffraction pattern of crucible samples.

main phases are Al, SiC, and Si, which agrees well with the results from the optical microscope image in Figure 2.
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There are significant differences in the melting points of aluminum, silicon carbide, and silicon. At experimental temperatures, there was not any solid phase in the Al-Si melt at the beginning of bubbling. After the bubbling and chemical reaction, SiC was formed. At this temperature, SiC kept its solid phase after it was formed. When the experimental system was cooling after the bubbling, the primary silicon might solidify first because the local composition of the melt might be higher than the eutectic composition (12.2 pct Si). When the primary silicon solidified, there
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Fig. 10Electron probe results of sample 6.

the SiC floated out of the crucible into a composite collector located under the crucible. The process is similar to the froth floatation used in the mineral process industry. The SiC was enriched in the foam flowing out of crucible to the composite collector, where the foam broke and the Al alloySiC composite was formed. Figures 7 through 10 show the typical scanning electron microscope (SEM) micrographs and results of microprobe analysis of samples from composite collectors. Figures 7 and 8 are SEM images from the same area, but Figure 7 is a secondary electron image and Figure 8 is a backscattered electron image. The previous figures are taken from a JEOL*
*JEOL is a trademark of Japan Electron Optics Ltd., Tokyo.

were many SiC particles in the melt, which could work as nucleation sites. After this heterogeneous nucleation, silicon would grow, resulting in primary silicon surrounding silicon carbide particles, as shown in Figure 2. Figures 2 and 3 show that aluminum is the main component in the composite, which also contains SiC and Si. There is some Al4C3, according to the X-ray diffraction pattern shown in Figure 3. Based on thermodynamic analysis from our previous studies,[10,11,12] there might be some aluminum carbide when the silicon concentration is too low. When the silicon content increases, aluminum carbide can be eliminated.[12] In this study, the silicon content was kept at a high concentration to prevent the formation of Al4C3, but it was found that there was a strong concentration distribution of silicon along the vertical position of crucible, according to optical microscope images shown in Figures 4 and 5. Figure 4 is micrograph of the sample from the top of the crucible, showing a higher silicon content with substantial primary silicon. Figure 5 is micrograph of the sample from the bottom of the crucible, showing less silicon content with a eutectic silicon composition. This indicates that the silicon content at the top of the crucible reactor was higher than that at the bottom. The silicon concentration distribution resulted from the bubbling. The Al4C3 in the product might be formed at the lower part of the crucible, where the local silicon content was too low. The X-ray diffraction patterns of typical samples from the top and bottom of the crucible are shown in Figures 6(a) and (b), respectively. They show that there are not any SiC peaks in Figure 6(a) in the sample from the bottom of the crucible, but there is a very small SiC main peak in Figure 6(a) in the sample from the top of the crucible, i.e., there is almost no SiC in the crucible samples. The three main peaks of Si, compared with those of aluminum in Figure 6(a), is higher than those of Si in Figure 6(b), which also suggests that there would be a higher silicon concentration at the top than at the bottom of the crucible. This suggestion agrees well with the microscope results shown in Figures 4 and 5. The SiC content in the composite was measured by crosssectional area measurement using a microimage analyzer. The average SiC content of the composite-collector samples was found to be 20 to 30 wt pct. The in-situ formed SiC particles were carried out of the crucible by bubbling gas, indicating the surface-energy differences between the SiC and alloy melt. On the top of the crucible, the foam was observed from a window located on the top of the furnace. Bubbling also resulted in overflow of the foam, in which
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8600 Electron Microprobe employing a spot size 1 m, voltage of 15 kV, and beam current of 20 A. Figure 7, the secondary electron image, clearly shows a typical sample morphology. At positions 6A and 6C, the surface is higher than at 6B and 6D. The composition at positions 6A and 6C in Figure 7 is SiC, according to Figures 10(a) and (c). Figures 10(b) and (d) show that the compositions at positions 6B and 6D of Figure 7 are aluminum. The reason for surface bumping is that in the SEM sample preparation, the aluminum was ground and polished more than the SiC due to the fact that SiC is much harder than aluminum. Figure 10(e) shows that position 6E of Figure 7 is composed of Al-Si alloy. The SEM backscattered electron images, shown in Figures 8 and 9, show the difference in composition by darkness. Figures 7 and 8 are different kinds of images at the same region. In Figure 8, the dark-colored phase corresponds to SiC and the light-colored phase corresponds to aluminum, according to the microprobe results shown in Figures 10(a) through (d). The SiC phase, as shown at points 6A and 6C of Figure 8, has a darker color than Al, because of the smaller atomic number of C in SiC. Point 6I of Figure 9 is Al4C3, according to Figure 10(i). In our electron probe study, carbon particles were not found, suggesting that carbon dissolving is not a slow process, i.e., not a kinetic-control step. B. Dissociation of Methane In this investigation, methane was used as a carbon source. Before the methane contacted the liquid alloy, it was heated close to the surrounding temperature by moving through a conduct pipe in the furnace. Figure 11 shows the methane system composition at different temperatures using the Gibbs energy-minimization method. Thermodynamically, methane could be completely dissociated to carbon and hydrogen when the temperature was over 1173 K. The furnace temperature for this research was over 1223 K, and methane dissociation reaction can be expressed as CH4(g) C(s) 2H2(g) G 49.585 kJ at 1273 K [1] The overall chemical reaction is proposed as Si(l) CH4(g) SiC(s) 2H2(g) G [2] 125.729 kJ at 1273 K

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Fig. 11Bubbling gas composition vs temperature at input of 1 mol methane.

Fig. 12Bubble size effect on SiC formation rate.

Table II. Calculation of Gas Heating

L (m)
0.1 0.2 0.3

Tout (K)
15.7 0.25 0.004

The hydrogen from methane dissociation will leave the melt after bubbling with argon, without becoming involved in the chemical reaction, but, from the stoichiometrical relationship, the methane dissociation would result in an increase in the total-volume flow rate of the bubbling gas. Practical dissociation of methane depends on the gas temperature and heat-transfer rate. Based on the energy balance, the heating of bubbling gas in the conduct pipe with uniform pipe temperature can be described in Eq. [3]. ln Tin Tout
LND k MCp
[3]

Fig. 13Si concentration effect on SiC formation rate.

high, dissociation usually resulted in a large carbon particles, which affects the particle diffusivity in the bubble. C. Mechanism Analysis The SiC content employed in this research is much higher than that in our previous work,[12] which was at the same experimental conditions, except for the current smaller size of the gas bubble, which was controlled by the hole size of the bubbler. The results are shown in Figure 12. The gasliquid interphase area and residence time result in this significant difference, indicating that the rate-control step for this in-situ process is not the reaction in the liquid phase. Experiments at different silicon contents were performed, as shown in Figure 13. The increase in silicon concentration does not increase the overall SiC formation rate, which suggests that the SiC formation rate is not controlled by the interphase reaction between silicon and carbon and that the overall SiC formation rate is controlled by carbon mass transfer in the gas bubble. When the bubble size decreases, the gas-liquid interphase area and residence time increase, resulting in an increase in the carbon mass transfer and overall SiC formation rate.
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where L is the pipe length, ND is the Nussel number, k is thermal conductivity of gas, M is the gas mass flow rate, Cp is the gas heat capacity, and Tout Ts Tout and Tin Ts Tin , in which Ts is the pipe temperature and Tin and Tout are the gas temperatures at the beginning and ending points of the calculation, respectively. For a uniform Ts value, ND 3.66. The calculated results are shown in Table II, which indicates that the gas residence time in the conduct pipe at the current experimental condition is long enough to heat the gas to the surrounding temperature, resulting in dissociation of methane into carbon and hydrogen. In the experiments, the bubbling gas flow rate was controlled in a predetermined range. When the bubbling gas flow rate was too high, too much alloy melt could be carried out to the composite collector. The overflow rate to the composite collector was dependent on the bubbling gas flow rate and the melt properties, e.g., silicon concentration and SiC content. When the bubbling gas flow rate was set to constant, the methane flow rate was determined by the methane concentration. When the methane concentration was too
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and silicon in liquid to form the SiC monomer, and (5) SiC nucleation and growth, as shown by the following equations: CH4(gas) C(bulk) C(border) C(l) Si(l) C(s) H2(g) [4] [5] [6] [7] [8]

C(border) C(l) SiC(monomer) SiC(crystal)

SiC(monomer)

Fig. 14Demonstration of reaction mechanism.

The entire reaction rate was controlled either by an activation (reaction) process or by a mass-transfer process. The weak affect of the rate by temperature suggestions the masstransfer control of the process. The most possible mass transfers controlling the rate are the reactants mass transfer in the liquid and gaseous phases. The almost noneffect of the rate by the liquid reactant (silicon), as shown in Figure 13, indicates that the mass transfer in liquid is not the control step. According to the previous analysis, step 2, shown in Eq. [5], is considered to be the rate-controlling step to the overall process. D. Rate Process The reaction rate (rSiC) can be expressed in Eq. [9], where nsic is the mole number of SiC, t is the time, and V is the volume of alloy melt. rSiC 1 dnSiC V dt
[9]

In order to increase the SiC content, temperature effects were investigated, and it was found that temperature did not have a significant influence on the SiC content. The higher SiC content in the composite collector than in the crucible shows that SiC was carried out of the crucible by bubbling more easily than the Al-Si alloy melt. The Si concentration distribution along the vertical position in the crucible was also a result of the bubbling. The proposed mechanism of the kinetic process is shown in Figure 14. Figures 4 and 5 show that the silicon content on the top is higher than that at the bottom. Because of the high agitation by bubbling, the gravity difference between aluminum (2.7 kg/m3) and silicon (2.33 kg/m3) should not be the reason. Therefore, it was considered that the surface energy played a role. When a bubble comes out of the conduct pipe, silicon is concentrated on the liquid side of the phase border. Then, the bubble is covered by a silicon-rich layer on the liquid side. Inside the bubble is a mixture of carbon particles, hydrogen, and argon. The carbon particles and hydrogen are from the dissociation of methane. The buoyancy drives the bubble in floating up, but there is no forced convection inside the bubble. Therefore, the mass transfer of carbon particles inside the bubble by inertial forces is neglected. At high temperatures, diffusion is important for the mass transfer of small particles. When carbon particles diffuse to the phase border, they are attached to liquid. After the wetting, attached particles are dissolved into the liquid alloy. The high silicon concentration on the phase border and high temperature make dissolved carbon react with silicon very quickly, with the formation of the monomer of silicon carbide. Due to the surface energy, the SiC monomer is still on the gas-liquid phase border. When the concentration of SiC monomers is high enough, nucleation of the SiC crystal occurs. After nucleation, the formed SiC monomer migrates to SiC particles and enters the crystal lattice. The overall kinetic process is divided into five steps: (1) methane dissociation to carbon particles and hydrogen, (2) carbon particle transfer from the bulk gas phase to liquid, (3) carbon particles entering the liquid, (4) reaction of carbon
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When methane gas is used as a carbon source for the insitu formation of SiC, the main mass transfer occurs between the gas bubble and liquid alloy. Based on Stokes Law, the terminal velocity of the bubble is shown in Eq. [10], where is a and g are the alloy and gas densities, respectively, the alloy viscosity, g is the gravity constant, and db is the bubble diameter. vt g(
a g)

18

d2 b

[10]

The residency time can be expressed as in Eq. [11], where ha is the depth of the liquid alloy. The total area of mass transfer is expressed in Eq. [12], where vg is the gas volumetric flow rate. 18 ha
g(
At
g(
a

1 2 g) d b

[11]
[12]

108
a

h a vg 3 g) d b

Methane gas dissociates into carbon and hydrogen. The carbon particle size is important to the mass transfer of carbon particles to the liquid alloy. The carbon particle size is a function of the growth process of dissociation. The mass balance of a single particle is shown in Eq. [13], where m is the molar density, dpi is the particle diameter at time t, and rA,S is the growth rate at unit area.
md

d3 pi

rA,S d 2 dt pi

[13]

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Assume that methane dissociation was completed, with a uniform carbon diameter (dp), before the gas went into the bubble. When the particle size is very small and in a free-molecule kinetic regime, the mass-transfer rate from the bulk gas to the phase boundary is high, due to the fact that the mass transfer of fine particles could be forced by gas molecules easily. When the particle is in a slip-flow kinetic regime, mass transfer of particles from the bulk gas to the phase boundary becomes difficult. The StokesEinstein equation can be used for diffusivity of a single particle through a stationary medium, as shown in Eq. [14], where Dpm is the particle diffusivity, k is the Boltzmann constant, T is the temperature, g is the gas viscosity, and C is the Cunningham factor. Dpm
3

CkT g dp

[14]

Fig. 15SiC formation rate vs time at different bubble size.

The Cunningham factor can be expressed in Eq. [15], where Kn 2 g/dp is the Knudsen number and g is the mean molecular distance.[13]
C 1 Kn (1.257 0.400 e )
1.10 Kn

Table III. Calculated Methane Efficiency vs Bubble Size

db , mm
1 2 3 4 5

[15]

Calculated Efficiency, Pct

61.90 18.44 8.44 4.80 3.08

Measured Efficiency, Pct

62.37 3.0

The particles in the gas bubble can be treated as being contained in spherical vessels for storage. While they are contained, the particles can be lost by diffusive deposition as well as by other processes. Assuming that gravitational, electrical, and other forces are negligible and the concentration of particles is small enough so that Brownian coagulation is negligible, the mass transfer of diffusive deposition is a function of the Fourier number (Fo), when Fo is small numerically. The Fourier number is defined for this purpose in Eq. [16], where R is the radius of the gas bubble.
Fo Dpm R2
[16]

With the assumption of a complete, efficient collision between the carbon particles and alloy melt, the ratios of the final to initial particle concentration by the number for highly dispersed particles and spherical gas bubbles at low Fo numbers are given[13] in Eq. [17]. NA NP
1
1/2 6Fo

The previous equations show that, at a constant methane molar flow rate, the overall rate is dependent on the Fourier number, which is proportional to the particle diffusivity and residence time. According to Eq. [14], the particle diffusivity is proportional to the temperature and inverse of the gas viscosity, which increase with temperature. Therefore, the overall affect of temperature on the SiC rate is not significant. The amount of formed SiC at time t can be expressed in Eq. [19], where MSiC is the molecular weight of silicon carbide. Calculated and experimental results are shown in Figure 15, which shows a good agreement between them.
t

3Fo

WSiC
[17]
0

rSiC VMSiC dt

[19]

The overflowing liquid alloy can be calculated as

t

Therefore, the mass-transfer rate of particles between the gas and liquid can be calculated, and then the SiC content can be calculated. Equation 17 shows that a higher carbon concentration can result in a higher conversion from C to SiC, for the process controlled by mass transfer. An increase in the methane concentration can increase the dissociated carbon concentration, but it also increases the carbon particle size, which decreases the carbon particle diffusivity. That means that the carbon particle size needs to be controlled for an effective mass-transfer rate of carbon particles. The reaction rate can be expressed in Eq. [18], where vme is the methane molar flow rate.
rSiC 1 NA vme NP V
[18]

Walloy
0

voverflow dt

[20]

where Voverflow is the liquid alloy overflow mass rate. Therefore, the average SiC content in the composite collector can be expressed as pct SiC WSiC WSiC WAlloy
NA NP 100 [21]

The methane efficiency can be expressed in Eq. [22]: 1

[22]

Based on the previous analysis, the effect of bubble size on methane efficiency is calculated, as shown in Table III.
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It indicates that the size of the gas bubble plays an important role in the SiC in-situ formation in an Al-Si alloy melt. IV. CONCLUSIONS Based on experimental results and theoretical analysis, the following conclusions were obtained. Al-Si alloy matrix composites containing SiC reinforcements were in-situ formed at temperatures from 1223 to 1423 K by the gas bubbling method, using a methane-argon gas mixture. Optical microscope, SEM, and electron microprobe analyses were used for the product characterization. Primary and eutectic silicon were observed in the samples from the top part of the crucible, and only eutectic silicon was observed in the samples from the bottom of the crucible. The SiC formation rate increased with a decrease in the bubble size. A silicon concentration gradient existed at different vertical positions of the liquid alloy. The silicon concentration close to the top of the liquid alloy was higher than that at the bottom. The SiC concentration was very low in the bulk alloy. The bubbling of the gas mixture in the melt resulted in the formation of a layer of foam on the top of the crucible. Formed SiC particles were enriched in the foam and carried out of the crucible by the overflow foam to a composite collector located under the crucible. The foam in the composite collector was broken, and composites in the foam contained up to 30 wt pct SiC. The SiC particle sizes ranged from 1 to 10 m. The bubbling process resulted in the unevenness of the silicon concentration and the different crystallizing processes. The SiC formation rate was found

to be about 12.5 mg/(L s). The kinetic-model-predicted results are in very good agreement with the experimental results. ACKNOWLEDGMENTS The authors are pleased to acknowledge the financial support for this research by the National Science Foundation (Grant No. DMI 9714321). REFERENCES
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. V.M. Kevorkijan: J. Met., 1999, Nov., pp. 54-58. B. Maruyama and W.H. Hunt, Jr.: J. Met., 1999, Nov., pp. 59-61. V.M. Kevorkijan: Adv. Mater. Processes, 1999, No. 5, pp. 27-29. B. Maruyama: Adv. Mater. Processes 1999, No. 6, pp. 47-50. A. Weaver: Mater. Today, 1999, vol. 2 (1), pp. 3-6. A. Kelly and C. Zweben: Mater. Today, 1999, vol. 2 (1), pp. 20-21. S.G. Warrier and R.Y. Lin: J. Mater. Sci., 1993, vol. 45 (18), pp. 4868-77. M.J. Koczak and M.K. Premkumar: J. Met., 1993, vol. 45 (1), pp. 44-48. H. Lagace and D.J. Lloyd: Can. Metall. Q., 1989, vol. 28, pp. 145-52. D.M. Kocherginsky and R.G. Reddy: Proc. Control of Interfaces in Metal and Ceramics Composites, TMS Symp., TMS, Warrendale, PA, 1994, pp. 71-79. D.M. Kocherginsky and R.G. Reddy: Proc. In Situ Reactions for Synthesis of Composites, Ceramics, and Intermetallics, TMS, Warrendale, PA, 1995, pp. 159-67. D.M. Kocherginsky: Ph.D. Dissertation, University of Nevada, Reno, NV, 1991, pp. 43-108. H.E. Hesketh: Fine Particles in Gaseous Media, Lewis Publishers, Inc., Chelsea, MI, 1986, pp. 55-57.

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