ScriptaMatcrialia. Vol. 37, No. 2, pp. 199-204.1997 Elxvier Science Ltd Copyright 0 1997 Acta Metallurgica Inc.

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EVA:LUATION OF THE MICROSTRUCTURE OF IN-SITU REACTION PROCESSED A13Ti-A1203-Al COMPOSITE

H.X. Peng, D.Z. Wang, L. Geng and C.K. Yao
School of Materials Science and Engineering, Harbin Institute of Technology, 150001, China

J.F. Mao
Laboratory of Atomic Imaging of Solid, Institute of Metal Research, Academic Sinica, Shenyang, 1100 15, China (Received January 11,1996) (Accepted December 8, 1996) Introduction In the last decade, new in-situ techniques for fabricating metal and intermetallic matrix composites have been developed, such as DIMOXTM, XDrM, VLS, SHS and MA (l-6). It is expected that the in-situ reaction formed composites may reveal not only excellent dispersion of fine reinforcing particles, clean interface, but also high thermodynamic stability and good high temperature performance (l-4). These in-situ techniques involve various chemical reactions and, therefore, the microstructure and composition of the products are quite different from those of the raw materials. In order to optimize the microstructure and achieve good overall properties, it is important to understand the formation mechanisms of the reacted products and to investigate the possibility of structure control during the fabricating process. Unfortunately, in many previous works, the formation process of microstructure was usu,ally illustrated with a simple reaction formula and the details of the formation process was ignored (7,8)1. In this paper, an AhTi-A120s-Al in-situ composite was synthesized by reaction between TiOl powder and molten Al via squeeze casting route. The microstructure of the composite and the mechanisms of its evolution were examined. A mechanism diagram for the formation of the microstructure is presented. Experimental Details Firstly, the 117~01% (35wt%)TiOz/A1 bulk material was prepared by squeeze casting method (7) using anatase Ti02 powder with average diameter of 0.6pm and pure Al ingot as the raw materials. X-ray diffraction (XRD) analysis indicated that no reaction occurred during this process (Fig. la). Subsequently, the squeeze-cast TiOz/Al bulk material was heat treated according to the differential thermal ana.lysis (DTA) results, the reaction between TiOz and Al occurred to form the final
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2.001 kr-

-t

. Al
* Ti02

1.00

ZOOk

Figure 1. X-ray diffraction pattern of the raw material (a) and the composite (b).

AlpTi-A120j-AI in-situ composite. This technique combined squeeze casting with combustion synthesis. The microstructure of the composite was systematically examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). SEM and TEM examination were carried out using a S-570 and a Philips EM420, respectively. The samples were prepared via conventional methods. Results and Discussion Composition and Microstructure of the In-Situ Composites The results of XRD analysis of both the squeeze-cast TiO*/Al bulk materials and the composite synthesized after reaction are shown in Fig. 1. The in-situ composite contains AbTi, ~AlzO~and Al

Figure 2. A typical SEM micrograph of the

in-situ

composite. (white = AllO3,dark = Al + AI,Ti).

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Figure 3. TEM images of (a,b,c) AI,Ti phase in the Al matrix and (d) A&Ti precipitates in AlpTi phase.

only (Fig. lb). No other phase was detected by XRD, this indicates that all the TiOz is reduced after the reaction. Fig. 2 is a typical SEM micrograph of the in-situ composite. The in-situ reaction formed a-Al~0~ particles with a size of about ll,trn are uniformly distributed in the matrix. The dark zone was aluminium matrix contains AbTi phase. TEM observations showed that both whisker-like and particulate-shaped AlsTi phase formed in the composite (Fig. 3a,b,c). A little amount of AlzTi precipitates in the ALTi blocks can be occasionally observed (Fig. 3d). These precipitates have been studied in detail by other investigators (9,lO). The distribution of AlzOs particles in the composite was also revealed by TEM. A number of AlzOj particles with a size of OSprn in the Al matrix are shown in Fig. 4a. The interfaces in the in-situ composite are atomically flat, smooth, free of any interfacial phases (Fig. 4b).There are also a few ALO particles in AbTi blocks (Fig. 4~). Many Al203 particles are distributed near the surfaces of the AlITi phase or at the ends of whisker-like ALTi (Fig. 4d). It can be noted that the distribution of the AbTi blocks and Al203 particulates in aluminium matrix is non-uniform on the micro-scale (Fig. 4d). No TiOz phase is observed.

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Figure 4. TEM images of the distributionof a-A1203 particles in the composites.

The Formation Mechanism of the Microstructure Based on the results presented above and thermodynamic calculations, the following is believed to be the mechanism for the formation of the microstructure of this composite during in situ processing: First, a reaction process according to the following formula produces A1203 particles and [Ti] atoms: TiOz + Al + ALO1 + [Ti] The result of thermodynamic calculations indicate that the heat released from this reaction may raise the melt temperature to about 2300K. At this temperature, Al and Ti are in liquid state, in which the content of Ti is about 2Oat% as shown in Fig. 5, but the ff-A1203remains solid. Subsequently, the Ti-Al solution solidifies, and according to the aluminium-titanium equilibrium diagram (Fig. 5)( 1l), the following occurs:

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Al.%Ti

Figure 5. The aluminium end of AI-Ti equilibrium diagram.

As the temperature drops, the large AbTi blocks form first (Fig. 3b,c).Due to the high cooling rate and relatively high Ti content, the solidification process does not follow according to equilibrium condition as shown in Fig. 5, the Al2Ti phase will form inside the Al3Ti blocks occasionally (Fig. 3d), this phenomena has been evidenced by previous work (9). Below 938K, the decreasing solubility of Ti in Al results in the formation of needle-like AbTi precipitates (Fig. 3a). During the solidification process, the distribution of the fine Al203 particles produced by the first reaction process can be changed. Due to the poor wettability between Al203 and molten Al, the Al203 particulates either move to the surface of AlsTi phase or agglomerate in the Al matrix in order to reduce the interface energy (Fig. 4a,d). In addition, they may be pushed aside by the growth of Al3Ti blocks and a few of them become surrounded by A13Tiblocks (Fig. 4~). The formation of the AljTi-A&03-Al in situ composite is illustrated by the following diagram:

_ Reaction

=+

Exothermic reaction =>Temp. = 2300K Ti, Al in liquid

AlsTi form and Al*Ti precipitates Peritectic reaction: liq.+Al,Ti-+Alss

Alss-+Al --_Solidification

+ A&Ti (needle-like) of A&O3 particulates:

Redistribution

process

agglomeration in Al matrix, moving to the surface of AlsTi phase, surrounded by AlsTi blocks

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Summary 1. Differential thermal analysis (DTA) of squeeze-cast TiOJAl bulk indicates that an exothermic reaction occurs after the ahuninium melts. A high temperature combustion synthesis process was achieved to produce a fully dense AlxTi + IX-A1203+ Al in situ composite. Very fine-scale dispersion of the AlJTi and a-Al203 reinforcing phases, ranging from 0.4 to 1.Opm, was obtained in the Al matrix. The AlsTi phase, some containing AhTi precipitates, form in the shape of block and whisker. The nanometer scale a-AhOX particles are found near the AlJTi phase and in the Al matrix, and, occasionally, within the AGTi phase. Analysis of the microstructural evolution indicates that the in situ processing involves two steps: (1) a reaction process between the molten aluminium and TiOz to produce alumina particulates and liquid Ti. (2) a subsequent solidification process of remained Al and Ti displaced from the reaction with decreasing temperature to produce Al + AlsTi blocks and then the smaller AlsTi precipitates form as the solidcools. References
1. K. Subhash and K. Michael, Mater. Sci. Eng., A162, 153 (1993). R.W. Rice, J. Mat. Sci., 26,6533 (1991). A. Stanislav and AS. Nagelberg, J. Am. Ceram. Sot., 75,447 (1992). A.K. Kuruvilla, K.S. Prasad and Y.R. Mahajan, Scripta Metall., 24,873 (1990). I. Gotman and M.J. Koczak, Mater. Sci. Eng., A187, 189 (1994). K.M. Lee and I.H. Moon, Mater. Sci. Eng., A185, 165 (1994). H. Fukunaga and X.G. Wang, J. Mat. Sci. Lett., lo,23 (1991). D.Z. Wang, Z.R. Liu, C.K. Yao and M. Yao, J. Mat .Sci. Lett., 12,142O (1993). Z.L. Wu and D.P. Pope, Acta Metall., 42(2), 509 (1994). 10. M.B. Winnicka, Z. Witczak and R.A. Varin, Met. Mater. Trans., ZSA, 1703 (1994). 11. L.F. Mondolfo, Aluminum Alloys: Structure and Properties, ~338, Butterworths, London-Boston (1976).

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