Scripta METALLURGICA V o l . 28, pp. 5 4 9 - 5 5 2 , 1993 Pergamon P r e s s Ltd.

et M A T E R I A L I A Printed in t h e U . S . A . All rights reserved

PREPARATION OF AI/RLINIlUg-AI/RgINA IN-SITU PARTICLE CONPOSITE BY ADDITION OF

TITANIA TO ALUMINID~ MELT

P.C. Maity, S.C. Panigrahi and P.N. Chakraborty

National Institute of Foundry and Forge TechnoloE~,, Ranchi 834003 INDIA
Indian Institute of Technology, Kharagpur 721302 INDIA

(Received October I, 1992)

(Revised December 8, 1992)

Introduction

Aluminium-alumina particulate composites are materials of recent interest (1-4)

for their improved mechanical properties as compared to the unreinforced alloys. Generally
the powder metallurgy or liquid metallurgy techniques are followed to prepare such composites
where alumina (A120^) particles are directly incorporated either into solid or liquid aluminium,
respectively. In t~e present study, a different approach has been employed to prepare A1-
A120-a particulate composites where TiO particles have been added into molten A1. TiO particles
are %hermodynamically unstable at th~ temperature of molten AI, and the formatio~ of Al^O^
particles is possible by the reaction between the TiO^ particles and A1 melt. Such in-s~t~
formed Al^O 3 particles may be more compatible with ~he matrix and the interfaces may be
cleaner ({) as compared to the composites produced conventionally. The reduced Ti from TiO 2
is expected to dissolve into the A1 melt and to produce an additional strengthening effect.
With the objective of producing A1-A1203 in-situ particle composites, TiO 2 particles have
been added into molten A1 by the vortex method, and the products of reaction have been identi--
fled by x-ray diffraction study and electron probe microanalysis (EPMA). The microhardness
and hardness of the composite have been measured to observe the effect of in-situ AI203
particle formation on the mechanical properties.

Experimental Procedure

Commercial pure A1 was used as the matrix material. The size of the TiO_ particles
2
(AR Grade) was determined in a MALVERN particle size analyser. The size analysis of the
TiO 2 particles is shown in Table 1. The A1-Ti02 particle composite was prepared by the vortex
method where a required amount of Ti02 particles were slowly added into the vortex formed
in molten A1 at 700oC by stirring it ~ith a graphite impeller. The composite melt was sub-
sequently solidified in a crucible in air. A specimen for EPMA was taken from the top of
the composite ingot, where the particles were found to be segregated. The specimen was polished
in a conventional manner. The EPMA study was carried out in a JEOL JCXA 733 analyser. As
the visual observation of the macrostructure showed the segregation of the particles at
the top of the composite ingot, a representative sample was taken for x-ray diffraction
study by sectioning the ingot vertically. It was remelted at 700C and was treated with
0.3 wt~ hexachloroethane to extract the particles. The extracted particles were analysed
with a PW 1840 x-ray diffractometer in the 2e range 15 to 80 using CuK~ radiation. The
microhardness of the composite was measured in an LECO microhardness tester using 25 g load,
and Vicker's Hardness was measured with a 1 kg load.

Results and D i s c u s s i o n

I. X-Ray Diffraction and EPMA study

The x-ray diffractograms of the TiOp particles (heat-treated to 700C for 30 min)
and the extracted particles from the A1-2TiOp- composite are shown in Fig.l(a) and Fig.l(b),
respectively. The peaks corresponding to T i ~ 2 are very weak in the x-ray diffractogram of
the extracted particles from the composite. ~Most of the major peaks in the diffractogram

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 550 ALUMINIUM-ALUMINA COMPOSITE Vol. 28, No. 5

correspond to those of ~ - A l o O c . In addition, the peaks of AI3Ti and AITi are also observed
in the diffractogram (Fig.l.b~.~The absence of peaks of TiO 9 and comparable peak intensities
of ~ - A I 2 0 3 and AI^Ti/AITi in the diffractogram indicates- that the reaction between TiO~
particles and moltenJAl is almost complete. Fukunaga et al. have also reported (6) the formatio~
of ~ - A I 0 , TiAI , TiAI and unreacted TiO 2 in AI-TiO 2 composite where molten pure A1 has
3
been l n f ~ ; a t e d into a preform of TiO 2 parti61es or whiskers.

TABLE I

Size Analysis of TiO 2 Particles

Size range (pms) 118-88 87-49 48-20 19-5 4-I < 1

Wt% 6.16 14.30 13.29 0.00 14.96 51.3

The theoretical amount of reduced Ti from the AI-2TiOo composite is 1.2%, assuming a complete
reaction between the TiO 2 particles and the melt. F~om AI-Ti phase diagram (7), at 1.2 wt%
Ti in AI, the AI3Ti phase should exist in the liquid metal at 700C. As the particles were
extracted spontaneously from the composite melt at 700C by treatment with hexachloroethane,
the presence of AI3Ti in the extracted particles is obvious. However, AITi intermetallic
compound can exist only above 56 wt.% Ti in A1 (7). Therefore, the presence of AITi in the
extracted particles indicates that the Ti concentration becomes very high at the interface
of liquid A1 and TiO 2 particles, probably because of reduced Ti from TiO 2 do not get dissolved
immediately into liquld A1 at 700C.

The secondary electron image of the AI-2TiO_ composite is shown in Fig.2(a) and
the x-ray images of Ti, AI and 0 are shown in Fig.2(~), 2(o) and 2(d), respectively, A few
AI~O^ particles of about 3 ~ m size are observed in the micrograph, as shown with arrow marks.
A qarge cluster of Ti02 p'articles is observed (Fig.2.a) at the center of the micrograph.
Though the TiO 2 particles are very fine and most of the particles are less than i ~ m in
size (Table i), it is possible that the particles form clusters and some of those exist
as such without deflooculation during stirring of the melt. Balsubramanian et al. have reported
(8) the presence of TiO 2 particles in the form of clusters in forged A1 alloy-TiO9 particle
composite. However, such clusters of unreacted TiO 2 were rarely observed at other-locations
of the miorostructure of the present work.

2. Microhardness and hardness

The microhardness and hardness value of the unreinforced AI and the AI-2TiO_ composite
are shown in Table 2. The microhardness is improved marginally with the additio~ of 2 wt~
TiO_ particles to the A1 matrix, whereas the hardness is improved appreciably. The increase

in microhardness can be attributed to the dissolution of Ti in A1 matrix and to the generation

of higher dislocation density in the matrix due to differential thermal contraction of the

TABLE 2

Microhardness and Hardness of AI-TiO 2 Particle Composite

Material Microhardness (VPN) Hardness (VPN)

Pure A1 37.4 25.7

A1-2TiO 2 43.3 38.2

Vol. 28, No. 5 ALUMINIUM-ALUMINA COMPOSITE 551

particles and the matrix (9,10). On the other hand, the increase in hardness can be caused
by the matrix hardening (as reflected in the minor increase in microhardness) and because
of restricted flow of metal due to presence of hard AI~O 3 particles. Surappa et al. have
reported (ll) such an increase in hardness by the incorporation of AI20 s particles up to
3 wt~ into pure A1 matrix. The 2% TiO~ particles can produce 1.7 w t ~ - 6 f AI~O~ particles
in the matrix, if a complete reaction between the Ti09 particles and the matri~ is assumed.
The hardness of pure A1 has increased from 27 Bhn to-35 Bhn by incorporation of 2 wt~ of
AI20 (ll). In the present work, the hardness increase from 25.7 to 38.2 VPN by the addition
of ~ wt~ of TiO 2 is probably due to additional effect of solid solution hardening of the
matrix and the presence of AI3Ti particles.

Conclusion

TiO~ particles added into molten A1 react with the latter to form oc-A1203 particles.
The initial -trial shows the possibility of producing A1-A120 s in-situ partCcle composite
by the addition of TiO_ particles into A1 melt. The hardness -of A1-Al_O_ in-situ particle
composite prepared by t~is method is more than that of the conventional~Y~produced AI-A1203
particle composite.

Aclo~owled~ement
One of the authors wishes to express his gratitude to Dr. Amitava Ray, Dr. P.C. Das and
Mr. B.B. Patra of RDCIS, Steel Authority of India Ltd, Ranchi for their help in the EPMA
work.

References

i. S.V. Namat, J.P. Mirth and R. Mehrabian, Acta Metal. 37, 2395 (1989).
2. S.V. Kamat, A.D. Rollet and J.P. Hirth, Scr. Metall. 25, 27 (1991).
3. P.N. Kalu and T.R. McNell~ Scr. Metall. 25, 853 (1991).
4. M. Ferry, P. Munroe, A. Crosky and T. Chandra, Mater. Sci. & Tech. 8, 43 (1992).
5. D. Lewis, III, in Metal Matrix Composites : Processing and Interfaces, R.K. Everett
and R.J. Arsenault (eds.) Academic Press, San Diego, 141 (1991).
8. H. Fukunaga, X. Wang and Y. Aramaki, J. Mater. Sci. Letts. 9, 23 (1990).
7. Metals Handbook, Vol.8, (8th Ed.) P.264, American Society for Metals, Ohio (1973).
8. P.K. Balsubramanian, P. Srinivasa Rao, K.G. Sivadasan, K.G. Sathyanarayana, B.C.
Psi and P.K. Rohatgi, J. Mater. Sci. Letts., 8, 799 (1989).
9. Y. Flom and R.J. Arsenault, Mater. Sci. E n ~ . , 75, 151 (1985).
I0. R.J. Arsenault and N. Shi, Mater. Sci. E n ~ . 81, 175 (1986).
ii. M.K. Surappa and P.K. Rohatgi, J. Mater. Sci., 16, 983 (1981).

,m,-~ 20 3
AI3Ti i
AITi II

30 35 z,0 "5

2 8 (Oeg)
Fig.l X-ray diffractograms of a) TiO^ particles
b) extracted particles from AI-2TiO 2 composite
552 ALUMINIUM-ALUMINA COMPOSITE Vol. 28, No. 5

Fig.2 a) Secondary electron image

b) Ti x-ray image c) A1 x-ray image, and
d) 0 x-ray imaEe of AI-2TiO 2 composite