Chemically Induced Reduction: A Viable Process for Synthesizing -TiAl Based Intermetallic Matrix Composite Powders Containing Nanocrystalline

TiC
JIN YONG KIM, KIHO CHANG, and PRASHANT N. KUMTA A chemically induced reduction process has been developed for synthesizing intermetallic matrix composites (IMCs) consisting of titanium aluminide and titanium carbide. The process involves the reduction of metal chlorides (TiCl4 and AlCl3) with metallic lithium in polar organic solvents such as acetonitrile (MeCN) and tetrahydrofuran (THF) to form a colloidal precursor. The as-prepared precursors have been either directly heat treated in ultra-high-purity argon (UHP-Ar) or pretreated in hydrogen (H2) followed by further heat treatment in UHP-Ar. The powders have been characterized primarily using X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Results of the structural analyses conducted on the heat-treated precursors derived using MeCN as a solvent indicate the formation of either single-phase titanium carbide (TiC) or a composite mixture of -TiAl and nanocrystalline TiC, depending on the heat-treatment conditions. The formation of TiC is related to the strong interaction between TiCl4 and the polar organic solvents, resulting in the formation of adducts which contain primary Ti-C linkages. Pretreatment of the precursors derived using MeCN as a solvent in H2 promotes the removal of carbon and results in the formation of the composite mixture of -TiAl and TiC after subsequent Ar treatment at 1200 C. At this stage, washing the pretreated powders in water helps to minimize and even eliminate any impurity phases to a large extent, leaving behind phase-pure composites containing -TiAl and TiC after the final Ar treatment. However, extended pretreatment in H2 appears to be ineffective toward removal of additional carbon and leads to formation of hydride-phase impurities. On the other hand, the reductive reaction conducted using THF as a solvent results in minimizing the amount of carbon while inducing the formation of -TiAl during direct Ar treatment of the precursors. This is because of the weaker interaction between TiCl4 and THF. Transmission electron microscopy was used to characterize the size distribution of the constituent phases. The analysis shows that the composite synthesized using these chemical approaches consist of discrete nanocrystalline TiC particles ( 20 nm) that are uniformly distributed intermixed with submicron sized -TiAl (0.1 to 0.2 m). Thus, the new chemical process proposed in this study demonstrates the potential for synthesizing in situ composites containing fine distribution of -TiAl and nanocrystalline TiC. Such composites could potentially exhibit unique mechanical properties and deformation behavior useful for high-temperature structural applications.

I. INTRODUCTION

TITANIUM aluminide-based intermetallics and composites are emerging as revolutionary high-temperature materials that could very well change the shape of future jet turbines and hypersonic aircrafts.[1,2,3] The low density of titanium aluminides based on TixAl (x 1 or 3, 4.2 g/cm3 for Ti3Al and 3.9 g/cm3 for TiAl) make them particularly suitable for turbine-blade, disk, and automotive-valve applications. Recently, it has been shown that -TiAl-based alloys could be used to fabricate exhaust valves that would enable the operation of automotive engines with improved efficiencies at higher temperatures.[4] In addition, they display attractive mechanical properties such as strength, stiffness, etc. at high temperatures, which make them a desired class of materials to replace existing superalloys. There has
JIN YONG KIM, Research Fellow, and PRASHANT N. KUMTA, Professor, are with the Department of Materials Science and Engineering, Carnegie Mellon University, Pittsburgh, PA 15213. KIHO CHANG was previously a Research Assistant at the Department of Materials Science and Engineering, Carnegie Mellon University. Manuscript submitted April 27, 1999
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been extensive progress, and considerable improvements have been made in the technology of -TiAl alloys, particularly in the last decade. These improvements have been primarily aimed at manipulating the microstructure and understanding its influence on the mechanical behavior.[5] While -TiAl-based intermetallics are still being actively researched, there is also tremendous interest in studying intermetallic-matrix composites (IMCs) consisting of -TiAl matrix reinforced with ceramic-based secondary phases such as SiC, TiB2, Al2O3, and TiC to improve the strength and creep resistance at elevated temperatures.[611]

A. Existing Processing Methods These intermetallic-based materials are currently processed using conventional metallurgical techniques, such as melting, investment, or permanent mold casting, and ingot metallurgical processes. At the same time, several powder metallurgical approaches, including rapid solidification and mechanical alloying techniques, have also been examined.[12] Conventional melt-solidification approaches, while
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being useful, require extreme care to be exercised, particularly in the processing of the -alloy compositions.[13,14,15] This is largely because of the lower ductility limits of these alloys and their extreme sensitivity to both impurities and uncontrolled thermal gradients in processing. Furthermore, complications exist in controlling chemistries with great precision because melt synthesis requires both refractory metal additions and high concentrations of aluminum.[16] The use of gas atomization (GA) and plasma rotating electrode process (PREP), on the other hand, offer the potential of improved composition control and homogeneity, and enhanced hot workability for these alloys.[17,18] While the use of rapid quenching and mechanical alloying techniques provide opportunities for improved alloys and microstructure, these processes suffer from an innate lack of control over problems that exist in synthesizing reactive metal powders. Blended elemental powders on the 10 m and larger size scale suffer from agglomeration, lack of adequate control over particle size and morphology, impurities due to the tremendous oxygen affinity of these elements, and opportunities for acquiring detrimental ceramic inclusions. These problems pose significant obstacles in processing high quality aluminide and aluminide-matrix composite articles with the desired phase(s) and microstructure for high-temperature application. Therefore, there is a need to identify and develop alternative synthesis methods to process these materials. One such path is the use of chemical techniques to synthesize these intermetallic compounds and subsequently modify the surface structure to induce atmospheric stability and protection against the deleterious influence of oxygen. B. Chemical Synthesis of Materials Chemical processing of materials has gained considerable importance over the last two decades, particularly, due to its impact in the processing of advanced ceramics. These techniques involve the use of solution chemistry to form precursors comprising molecular units whose structural environment resemble the ultimately desired materials. Thus, subsequent heat treatments at temperatures lower than those used conventionally are sufficient to yield the desired material. A process that has received considerable attention over the years is the sol-gel process.[1923] The advent of the sol-gel process stimulated considerable interest in the development of solution-based chemical approaches to process precursors for advanced ceramics. A number of methodologies have evolved over the years based on aqueous and nonaqueous precipitation, colloidal processes including the Pechini process, hydrothermal, and microemulsion techniques. All these processes essentially involve the generation of a precursor using soluble starting materials which undergo condensation by catalytic polymerization of the reacting species or by the addition of polymerizing agents after the formation of the main desired molecular units. The result of these reaction steps is the formation of either a gel product, a powder consisting of ultrafine disordered, amorphous, or nanocrystalline particles, or a finely dispersed stable suspension. The use of such soluble starting materials combined with the reactions being conducted in suitable solvent systems lead to extremely good mixing at the molecular level of the individual reacting species. As a result, the mobile solvated
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molecules now need to migrate reduced diffusion distances ( 100 nm), which leads to extremely good control of composition. The use of metalorganic precursors also provide the additional advantage of generating high-purity materials. Moreover, use of proper catalysts provide the additional flexibility to generate materials exhibiting different morphologies and in both amorphous or nanocrystalline forms. In addition, by altering the surface chemistry and the extent of polymerization of the reacting species, it is possible to control the reaction kinetics to yield thin films, whiskers, or fibers. The resultant gels or ultrafine particles are extremely fine with specific surface areas in excess of 200 m2/g, which make the particles reactive, leading to considerable reduction in sintering temperatures.[2426] C. Motivation and Objectives The enormous progress and potential opportunities offered by chemical processes led us to investigate and exploit these techniques for synthesizing -TiAl-based intermetallicmatrix composites (IMCs) containing TiC. The initial idea that motivated the study was that the synthesized materials could possess novel properties which could have exciting new and unique applications. Table I compares the potential benefits of powders synthesized using chemical routes as opposed to traditional and nontraditional metallurgical routes. While chemical techniques have been explored to a significant extent in the synthesis of oxides and to a certain extent of the nonoxides, there is a scarcity of work performed in the area of synthesis of intermetallics and intermetallicmatrix composites in the Ti-Al system. Although recognized as a potentially vital area for long-range development of titanium aluminides, apart from reports on the use of plasmaassisted chemical-vapor deposition using inorganic titanium precursors and aluminum vapor[27], the entire area involving the implementation of low-temperature solution-chemical routes seems to be unexplored. In the present study, novel, low-temperature chemical approaches are proposed to synthesize -TiAl-based composites containing TiC. The chemical approach derived in this study is based on the electropositive nature of alkali metals and their strong ability to act as reducing agents. Hence, the reactions studied in the present work include reduction of the transition metal halides using alkali metal in the presence of polar solvents. The reactions are conducted in the solvent phase, leading to the formation of either a completely or partially reduced solid product of the parent metal, while the alkali metal remains in the solid precursor as an alkali halide. The schematic reaction involved in the process is indicated as follows: TiX4 AlX3 Li [Ti-Al] 7 LiX where X represents halogen group elements. The formation of the intermetallic is very strongly dependent on the ability of the alkali metal to attack titanium and aluminum halides and strip the metal salts of the halogen species, thereby reducing them to the individual metals. However, transition metal halides are known to coordinate very strongly with polar organic solvents. This tendency can be exploited very well to generate nanocrystalline carbide particles as a ceramic phase distributed uniformly in the titanium aluminide matrix. The resultant composite can be obtained by heat treating the precursor product either directly
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Table I. Comparison of Existing Methods and Chemical Routes to Process Titanium Aluminide Intermetallics and Composites
Process
Melt solidification 1. 2. 3. 4. 5. 1. 2. 3. 4. 5. 1. 2. 3. 4. 5. 6.

Characteristics
thermally induced cracking small components hot isostatic press or vacuum hot press solidification segregation unmelted inclusions of refractory additives improved homogeneity near-net shape impurities need for thermomechanical process coarse, agglomerated powders high purity good mixing at molecular level and control of stoichiometry ultrafine particles control of particle shape, morphology, and structure flexibility to obtain powders, films, and fibers control of particle size to facilitate sintering at low temperatures

Powder metallurgy and rapid solidification processes

Chemical routes

in argon or by using a combination of hydrogen and argon to form a composite mixture of titanium aluminide and titanium carbide. Control of the heat-treatment environment provides the ability to monitor the extent of formation of the carbide and the intermetallic phases. The resultant powders have been studied for their phase evolution, particle size, and morphology using X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). II. EXPERIMENTAL PROCEDURE A. Materials Synthesis Figure 1 shows a schematic of the procedures followed to synthesize the precursors that yield composites of -TiAl and TiC. All the reactions were conducted in the absence of air and moisture. Titanium tetrachloride (TiCl4, Aldrich, 99.5 pct) and aluminum trichloride (AlCl3, Aldrich, 99.99 pct) were used as sources of titanium and aluminum, respectively. Two processes were attempted using polar organic solvents such as acetonitrile (MeCN) and tetrahydrofuran (THF). In the first process, AlCl3 was dissolved in anhydrous acetonitrile (MeCN, CH3CN, Aldrich, HPLC grade) and stirred for approximately 10 minutes to completely dissolve the AlCl3. To this solution, TiCl4 was then added with a 1:1 molar ratio of AlCl3 to TiCl4, necessary to form -TiAl, and mixed for 10 minutes. After obtaining a clear solution of AlCl3 and TiCl4 in MeCN, lithium foil corresponding to the stoichiometric amount needed to metathetically extract all the chlorine was added to the solution in order to induce the reduction reaction. After the Li foil was entirely consumed, the vessel was sealed and the precipitate was allowed to settle at the bottom. The clear liquid was then decanted to collect the precipitate. The collected precursors were dried in a vacuum at 150 C. An identical procedure was followed in the second process except that tetrahydrofuran (THF, C4H8O, Aldrich, HPLC grade) was used as the solvent, while all the other materials remained the same. B. Heat Treatment and Characterization The precursors synthesized using the preceding two processes were immediately heat treated in H2 or Ar to investigate the effect of heat-treatment conditions and the
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Fig. 1Flow sheet showing the procedure followed to synthesize composite powders of -TiAl and TiC.

environment on the crystallization of titanium aluminide. The complete heat-treatment profile and the nomenclature followed for naming each heat-treated sample are shown in Table II. The powders synthesized using both processes are denoted as MeCN and THF based on the solvent used for synthesizing the precursors, namely, acetonitrile (MeCN) and tetrahydrofuran (THF). The numbers to the right of these letters correspond to the final temperature of pretreatment in H2, while the letters NP indicate that no pretreatment was conducted. Finally, both the pretreated and nontreated
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Table II. Heat-Treatment Schedule Followed for Obtaining Various Powders

Temperature of PreHeat Treatment in H2 ( C)*
not conducted 800 (10 h) 800 (10 h) 300 (24 h), 400 (24 h), and 600 (2 h) not conducted

Sample
MeCN-NP MeCN-800 MeCN-800-ww MeCN-600 THF-NP

Solvent
MeCN MeCN MeCN MeCN THF

Temperature of Heat Treatment in UHP-Ar ( C)**

1200 (10 h) 1200 (10 h) 1200 (10 h) 1200 (10 h) 1200 (10 h)

NP indicates that no pretreatment in H2 was conducted. ww represents that the precursors were washed with water after the pretreatment in H2. *Heating rate was set at 1 C/min for all pretreatments in H2. **Heating rate was set at 5 C/min up to 800 C and 1 C/min up to 1200 C. ***All samples were furnace-cooled after heat treatments.

precursor was heat treated at 1200 C using ultra-high-purity argon (UHP-Ar) for 10 hours. In order to identify the presence of the crystalline phases, X-ray diffraction was performed using a Rigaku / diffractometer. No X-ray analysis was conducted on the as-prepared precursors because of their extreme reactivity to air and moisture. Last, the powders comprising a composite mixture of -TiAl and TiC were observed under the scanning electron microscope (SEM, CamScan) and transmission electron microscope (TEM, JEOL 1200 CX) to analyze the particle size and morphology of the constituent phases. III. RESULTS AND DISCUSSION The objective of the present study, as mentioned previously, is to identify a viable chemical process for synthesizing powders comprising a composite mixture of -TiAl and TiC. Two processes were, therefore, attempted using different solvents to investigate their potential for the formation of these composites. The precursors obtained from the two processes were heat treated and analyzed for the presence of the different crystalline phases. A. X-Ray Analysis The precursors obtained by conducting the reduction reaction in MeCN were subjected to direct heat treatment in argon to investigate the crystallization and formation of the intermetallic phases. This heat treatment was conducted at 1200 C to eliminate LiCl, the only byproduct of the reaction. The MeCN-NP precursor shows the presence of only TiC as the major crystalline phase in X-ray analysis when directly heat treated in UHP-Ar at 1200 C for 10 hours (Figure 2). Although the exact mechanism for the generation of the carbide phase is unknown, a plausible explanation for its formation could be suggested. Because the starting materials do not have any primary carbon bonds in them, the only source of carbon must be the solvent phase. It is known that transition metals form coordination bonds with donor ligands. In a previous publication,[28] we have shown that MoCl5 forms two types of adducts with MeCN, depending on the manner in which Mo is coordinated to MeCN. The end-on coordinated bond is facile, while the side-coordinated bond is extremely robust and cannot be replaced in the presence of any strong nitrogen-containing nucleophiles. This bond is formed by the reaction of the halide with MeCN
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Fig. 2XRD pattern obtained on the powder derived using MeCN and heated directly in UHP-Ar at 1200 C for 10 h (MeCN-NP). Note the formation of TiC as the primary phase.

for an extended period of time. Heat treatment of these sideon-coordinated adducts, therefore, invariably results in the formation of the carbide phase (Mo2C) as an extraneous impurity. The formation of a similar bond between Ti and MeCN can, therefore, be easily envisaged. It should be noted however, that the coordination in Mo is observed only after prolonged reaction (24 hours). The formation of a similar, strong adduct in the case of Ti could be expected to be rather rapid since the solution of the halide in MeCN is attacked by metallic lithium almost immediately after dissolution. In order to break the -coordinated linkage and eliminate the presence of carbon in the precipitate, pretreatment in H2 was therefore attempted. Hydrogen heat treatment was conducted at 800 C. After the initial treatment for 10 hours, X-ray diffraction analysis was conducted on the heat-treated powder. The analysis revealed LiCl to be the major phase with the presence of a small amount of titanium hydride, TiH1.924 (Figure 3(a)). The presence of LiCl, as mentioned previously, is expected because of the ability of lithium to extract chlorine from the corresponding metal chlorides. The presence of the chloride confirms the role of Li as a reducing agent, briefly discussed previously. The byproduct of LiCl was successfully extracted by washing the precursors pretreated in H2
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(b)

(b)

(c)

(d)

Fig. 3XRD patterns obtained after heat treating the as-prepared precursors derived using MeCN in different atmospheres: (a) after pretreatment of the as-prepared precursor in H2 at 800 C for 10 h; (b) after washing the pretreated powders with water to remove the byproduct of LiCl; (c) after heat treatment of the powder in (a) in Ar at 1200 C for 10 h (MeCN-800); and (d ) after Ar treatment of the water-washed powder in (b) at 1200 C for 10 h (MeCN800-ww). Note the clear pattern showing the presence of only -TiAl and TiC.

with water. X-ray analysis conducted on the water-washed powder after the initial pre-treatment in H2 reveals very small peaks corresponding to -TiAl, TiC, and unknown phases devoid of crystalline LiCl (Figure 3(b)). Both the precursors pretreated in H2 as well as the precursors washed in water after the initial H2 treatment were then heat treated in UHP-Ar at 1200 C for 10 hours to crystallize the titaniumaluminide phase. Since a 1:1 ratio of Ti:Al is used in this study, the composition of the TiAl phase which coexists with TiC should be Al-rich. A critical TEM analysis using ALCHEMI will be done in the future to identify the exact composition of the TiAl phase. X-ray analysis conducted on both precursors indicates -TiAl and TiC to be the main phases (Figures 3(c) and (d)), in contrast with the sample directly heat treated in UHP-Ar at 1200 C for 10 hours revealing only TiC (Figure 2). The pattern displayed in Figure 3(d), however, does not contain any of the unknown phases that are seen in Figure 3(c). This suggests that the unknown phases seen in Figure 3(c) are probably related to the presence of some water-soluble impurities, perhaps related to lithium. Nevertheless, these results indicate that
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the initial pretreatment in H2 at 800 C is beneficial for minimizing the carbon content of the precursors and facilitates the formation of the crystalline -TiAl phase. At the same time, it appears to be ineffective in breaking the coordinated Ti-C bonds with the solvent. Another interesting observation is that LiCl appears to be eliminated after the Ar treatment of precursors pretreated in H2 without the need for washing with water (Figure 3(c)). This has also been observed by us in previous study related to the synthesis of AlN.[29] One possible mechanism to account for the disappearance of LiCl during Ar treatment at 1200 C is the reaction of LiCl with residual hydrogen in the precursor, which enables the extraction of Cl from LiCl to form HCl, combined with the evaporation of Li at high temperatures of 1200 C. In order to remove more carbon, the as-prepared precursors were pretreated in H2 for a longer period of time. Lower temperatures of 300 C to 600 C were selected because the reaction of C and H2 to form methane is known to be thermodynamically favorable at these temperatures.[30] Accordingly, the as-prepared powders were heat treated in
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H2 at 300 C and 400 C for 24 hours, respectively, and then at 600 C for 2 hours. After this heat treatment, the precursors showed the formation of titanium hydride (TiH1.924) and AlLi phases, while there was a decrease in the intensity of peaks corresponding to LiCl (Figure 4(a)) in comparison with the powder pretreated in H2 at 800 C for 10 hours (Figure 3(a)). The presence of AlLi and reduction in the intensity of LiCl suggest that chlorine could be removed in the form of HCl during the extended heat treatment in H2 conducted at lower temperatures. This obviously is not the case when the precursors are heat treated in H2 at 800 C for 10 hours. Figure 4(b) shows the X-ray diffraction trace obtained on the precursors after the multistep heat treatment. Despite the pretreatment of the precursor in H2 for an extended period of time, XRD analysis of the final product after Ar treatment still reveals the presence of TiC, while also exhibiting AlH3 in addition to -TiAl. At the same time (Figure 4(b)), a number of unknown phases are also observed. The peak positions for these unknown phases are similar to those seen in Figure 3(c). These unkown phases could be related to

(a)

(a)
Fig. 4XRD traces obtained on the powders derived using MeCN after heat treatment in selected atmospheres: (a) after pretreatment of as-prepared precursor in H2 at 300 C and 400 C each for 24 h, followed by further heat treatment in H2 at 600 C for 2 h; and (b) after heat treatment of the powder in (a) in UHP-Ar at 1200 C for 10 h (MeCN-600).
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lithium-containing impurities that can be removed by washing the precursor with water after the pretreatment in H2 (Figure 3(d)). The presence of TiC and the formation of hydride phases is an indication that H2 treatment for an extended period of time is not sufficient to break down the -coordinated Ti bonds with the nitrile group and also completely remove carbon, both being necessary for obtaining the single phase of -TiAl. Thus, it can be seen that the reduction reaction induced by Li does help to form -TiAl. However, it appears that the strong interaction of the solvent with TiCl4 leads to the generation of primary Ti-C bonds in the precursor. The presence of these linkages facilitates the amount of the carbide in addition to the intermetallic phase. In an attempt to reduce the formation of the carbide phase, it was decided to conduct the reactions in polar organic solvents containing polar functional groups attached to cyclic hydrocarbons rather than to open-chain aliphatic linkages as in MeCN. The rationale for this is the stability of the cyclic ring compounds containing saturated hydrocarbons. Tetrahydrofuran (THF) was therefore selected as the solvent medium despite oxygen being the only primary donor site in this solvent. It was anticipated that oxygen in THF contains a lone pair of electrons contributing to generation of the normal -coordination bond with the Ti center rather than the more robust sideon, -coordination linkage. The normal -coordinated THF group is more susceptible to being replaced in the presence of strong nucleophiles, as reported by Sriram et al. in a previous publication.[28] Thus, THF was used as a solvent for conducting the very same reductive reactions that were initiated in MeCN. As mentioned earlier, the polar center in THF contains oxygen, which has a partial negative charge. The dissolution of TiCl4 in THF comprises the coordination of oxygen to the positive Ti-metal center, thus minimizing the risk of formation of metal-carbon bonds, as in the case of MeCN, although increasing the possibility of forming TiO2. However, the presence of lithium would help in the reduction of the oxide during subsequent heat treatment, thereby enabling the stabilization of the intermetallic as indicated by the previous results. The precursors derived using THF as the solvent medium were directly heat treated in UHP-Ar at 1200 C for 10 hours. X-ray analysis in this case, however, also reveals a mixture of -TiAl and TiC as the major phases (Figure 5), similar to the powders obtained after Ar treatment of the precursors derived using MeCN that were pretreated in H2 (Figures 3(c) and (d) and 4(b)). There are also some unknown phases whose peak positions appear to be similar to those displayed in Figures 3(c) and 4(b). This once again suggests that the reaction mechanisms involved in this process are probably similar to the reaction conducted in MeCN. However, there is still a noticeable difference between the two processes when the reaction products are compared after direct heat treatment in UHP-Ar at 1200 C. In the case of precursors derived using MeCN, X-ray analysis reveals the presence of only single-phase TiC after direct heat treatment in UHP-Ar at 1200 C (Figure 2). On the other hand, the powder derived using THF that was directly heat treated in UHP-Ar at 1200 C indicates phases similar to the powder obtained using MeCN as the solvent and heat treated in UHP-Ar at 1200 C after an initial pretreatment in H2 (compare XRD patterns in Figures 3(c), 4(b), and 5). Similar
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Fig. 5XRD trace obtained on the precursor derived using THF after direct heat treatment in UHP-Ar at 1200 C for 10 h (THF-NP).

pretreatment of the THF-derived precursor in H2 could have perhaps destabilized the intermediate product formed as a result of the reaction between TiCl4 and THF, thereby minimizing the carbide phases further. However, the possibility of hydride formation could increase the complexity of the process, as in the case of MeCN. Nevertheless, these results indicate that the use of THF as a solvent, in contrast to MeCN, does help to lower the interaction of coordinating polar solvents with TiCl4, minimizing the extent of Ti-Ctype linkages formed in the precursor (Figures 2 and 5). It is known that TiCl4 forms a 1:1 (TiCl4 C4H8O) and 1:2 (TiCl4 2C4H8O) type of adducts with THF. Most of these are known to decompose at temperatures of 140 C.[31] However, the fact that carbide is still seen in the present approach leads us to believe that stable adducts are formed which do not completely decompose. At the same time, there could also be a ring-opening reaction induced by the presence of AlCl3, in which case the subsequent formation of organotitanium compounds cannot be discounted. In any case, it therefore appears that the formation of TiC is linked to the generation of adducts due to the interaction between the metal chlorides and the polar organic solvent. The use of the polar organic solvents precludes the formation of the pure titanium-aluminide phase, although some reduction in the carbide phase appears to be possible. Nevertheless, the rapid kinetics of the reduction reaction at room temperature leads to the formation of reactive precursors which offer the unique possibility of generating nanocrystalline -TiAl- and TiC-phase composites. It was therefore decided to analyze the microstructure of the composites. B. Microstructure In order to observe the microstructure and particle size of the composite phases, SEM was performed on the sample MeCN-800-ww, which represents the composite mixture comprising only -TiAl and TiC with minimum impurities as seen in the XRD patterns (Figure 3(d)). Figure 6 is an SEM micrograph taken from a representative area of these powders. The micrograph shows the morphology of the heattreated powders containing a mixture of -TiAl and TiC.
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Fig. 6SEM micrograph showing the morphology of the -TiAl matrix composite powders containing TiC derived using MeCN (MeCN-800-ww). The micrograph shows agglomerated clusters 1.5 to 2 m containing fine primary crystallites, which are not clearly resolved in the preceding micrograph.

These powders consist of agglomerates of -TiAl and TiC in the 1.5 to 2 m size range. It should be noted that the agglomerated clusters seen in the micrographs are essentially composed of aggregates of individual primary crystallites. Careful observation of the micrograph clearly reveals several particles that are extremely fine and in the submicron range. In order to observe the actual crystallite sizes and the morphology of the constituent phases, the composite powders were observed using a transmission electron microscope. Figure 7 shows the diffraction patterns, the brightfield image, and the dark-field images obtained from the Ar-treated sample MeCN-800-ww. The powder shows a combination of ring and spot diffraction patterns (Figure 7(a)). The ring pattern was indexed to the TiC phase (Figure 7(a)). It was difficult to index the spots that were not superimposed by the ring patterns because it was hard to set a specific zone axis due to the fine crystallite size. However, since this powder reveals only two phases of -TiAl and TiC, it can be safely assumed that the spots off the TiC ring patterns are derived from the -TiAl phase. These spots could be indexed to certain planes of -TiAl (see the indices enclosed within {} in Figure 7(a)). The bright-field image in Figure 7(b) shows a uniform distribution of fine particles less than 20 nm in size. To identify the morphology and crystallite size of the constituent phases, dark-field images were taken from region A of the brightest ring of the diffraction patterns in Figure 7(a), corresponding to TiC, and from the spot located as B in Figure 7(a), which is seen off the ring patterns corresponding to -TiAl. The dark-field image collected from location A, corresponding to TiC, exhibits a homogeneous distribution of nanocrystalline particles less than 20 nm in size (Figure 7(c)), while the dark-field image obtained from the spot B, corresponding to -TiAl, shows the larger -TiAl crystals ranging in size from 0.1 to 0.2 m (Figure 7(d)). Therefore, the nanocrystalline particles shown in the bright-field image (Figure 7(b)) can be identified as the TiC phase. The diffraction patterns, bright- and dark-field images collected on the composite powders indicate that the TiC particles are extremely fine and are well distributed. Furthermore, the bright-field image reveals that
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Fig. 7TEM micrographs of powders corresponding to MeCN-800-ww sample showing the diffraction pattern and the morphology of the constituent phases: (a) selected area diffraction patterns (SADPs) showing the diffuse ring pattern corresponding to fine TiC and the spot pattern of -TiAl; (b) brightfield image showing the nanosized TiC dispersed in -TiAl; (c) dark-field image obtained from region A in the SADP centered on the brightest ring showing nanosized ( 20 nm) particles of TiC; and (d ) dark-field image obtained from region B in the SADP centered on a spot off the ring pattern showing the submicron-sized ( 0.1 to 0.2 m) -TiAl particles.

the interparticle distance observed for TiC is much smaller than the -TiAl particles shown in the dark-field image (Figure 7(d)). These results imply that the nanocrystalline TiC particles are probably located within the -TiAl grains. It is possible that dense compacts processed from these powders consisting of fine grains of -TiAl and uniformlydistributed nanocrystalline TiC could exhibit some unique mechanical behavior because the nanocrystalline TiC particles could serve as inhibitors of grain growth as well as pinning sites for dislocations. In summary, it can be seen that the two chemical approaches described in this work offer a novel way to fabricate composite powders containing TiC and -TiAl. The intrinsic affinity of TiCl4 to coordinate with the polar organic solvents precludes, by and large, the synthesis of single-phase -TiAl. However, in combination with the reducing power of Li, the process offers a unique way to synthesize these composite powders. The uniform distributions of these fine-scale, nanometer-sized TiC particles in the submicron-sized clusters of -TiAl could exhibit some unique opportunities for use of these composites in structural applications. These studies and extension of the approach
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for the synthesis of either single-phase or composite mixtures of other intermetallic systems are currently in progress. IV. CONCLUSIONS Chemical processes based on the reaction of Ti and Al halides with lithium, utilizing its electropositive and reducing power, have been investigated to analyze their potential for synthesizing composites of -TiAl and TiC. Two different polar organic solvents, acetonitrile (MeCN) and tetrahydrofuran (THF), were used for the present study. The reactions conducted in MeCN result in the formation of either singlephase TiC or a composite mixture of -TiAl and TiC, depending on the heat-treatment conditions. The formation of carbide (TiC) is probably related to the strong interaction between TiCl4 and MeCN, leading to the formation of adducts containing strong primary Ti-C linkages. The interaction of the halide with the solvent is reduced when the same reaction is conducted in THF. Thus, direct heat treatment of the precursor in Ar itself results in the formation of the -TiAl phase with TiC phase. Electron microscopy analysis shows that the composites synthesized
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using these chemical approaches consist of submicron-sized -TiAl (0.1 to 0.2 m) grains containing uniformly distributed nanocrystalline TiC ( 20 nm) particles. Subsequent processing of these powders into dense composites and evaluation of their mechanical properties could offer some unique opportunities for these materials to be used in hightemperature structural applications. Thus, the reductive chemical approach described in this study represents a novel approach for the formation of in situ composites containing -TiAl and TiC. ACKNOWLEDGMENTS This research was primarily conducted with the help of a grant from the Air Force Office of Scientific Research (AFOSR), Grant No. F49620-95-1088. The authors acknowledge Dr. M.A. Sriram and Mr. K.S. Weil, whose initial experiments were very helpful in the execution of the present work. Financial support from NSF (Grant Nos. DMR-9301014 and CTS-9309073) is also acknowledged. REFERENCES
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VOLUME 31B, FEBRUARY 2000159