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Scripta Materialia, Vol. 38, No. 7, pp. 10831089, 1998 Elsevier Science Ltd Copyright 1998 Acta Metallurgica Inc. Printed in the USA. All rights reserved. 1359-6462/98 $19.00 .00

PII S1359-6462(98)00011-6

EFFECT OF ANTIMONY ON THE GROWTH KINETICS OF HIGH PURITY Al-Si ALLOYS

Qiyang Liu
Mechanical Engineering Department II, South China University of Technology, PR China (Received April 2, 1997) (Accepted in revised form December 18, 1997) Introduction More recently antimony is extensively used as an alternative to sodium and strontium in Europe and Japan in the production of Al-Si alloys by the permanent mold process [1]. It has been found that antimony can effectively refine the Al-Si eutectic structure at relatively high cooling rates, providing a low susceptibility to gassing [2 4] and excellent casting properties [5,6]. Thermal analysis [7] has been used to relate the characteristic cooling curve to the degree of modification of Al-Si alloys by antimony. Researchers [8,9] held that antimony lowered the Al-Si eutectic solidification temperature whilst others [7] argued that thermal analysis curves did not indicate any effect by antimony. Comparison between the effects of Na, Sr and Sb on the alloy microstructure has indicated that Na and Sr produce a fibrous silicon morphology whilst Sb brings about a fine lamellar one [6,7, 10 12] which is also obtained if an insufficient amount of Na or Sr is present in the alloy [1]. Khan and Elliott [10] described that Sb refined the eutectic structure by reducing the interflake spacing. Previous work by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) analyses has indicated that Na [13] and Sr [14] adsorbed on {111}Si and {100}Si surfaces and affected the epitaxial growth of silicon from single crystal silicon substrates. This paper studied the effects of antimony on the solidification characteristics of a high purity Al-12wt%Si alloy. The adsorptivity of Sb on {111}Si and {100}Si surfaces and the influence of antinomy on the epitaxial growth of silicon phase from single crystal silicon substrates were also examined. Experimental Procedures High purity Al-12wt%Si and Al-22wt%Si master alloys were made using high purity aluminium ingots ( 99.99%Al) and single crystal silicon columns ( 99.9999%Si). Pure metallic antimony was added into the alloy melt at 0.2% Sb for the alloy containing 12%Si and at 0.35% Sb for the alloy containing 22%Si, respectively. After degassing using ZnCl2 the molten alloy was poured into high purity graphite moulds to form small ingots measuring 20 mm in diameter and 40 mm in length. Thermal analysis was conducted in a special furnace (Figure 1) having a high purity argon atmosphere containing 40 ppm of total impurities. 0.2 mm diameter chromel-alumel thermocouples

Present address: BHP Research Port Kembla Laboratories, PO Box 202, Port Kembla, NSW 2505, Australia.

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Figure 1. Schematic of the thermal analysis furnace. 1. alloy melt; 2. thermocouple; 3. high purity graphite crucible; 4. heater; 5. heat preserver; 6. tray; 7. cover; 8. crucible table; 9. insulation; 10. electrode; 11. pedestal; 12. body of the furnace; 13. power supply; 14. circulating water; 15. argon supply; 16. barometer; 17. to recorder; 18. to vacuum system.

were used in the analysis. The thermocouples were enclosed in a thin walled alumina sheath with an outer diameter of 1.2 mm. The thermocouples were connected to a recorder via a cold junction. The 0.2% Sb treated Al-12wt%Si alloy ingots were remelted, heated up to 720C and held at this temperature for 5 minutes. The molten alloy was then cooled down at a rate of 65C/min before it solidified. The temperature-time curves were recorded. In order to enhance the sensitivity of the analysis, during recording, in the temperature range 565585C, a constant offset potential of 21mV was applied to the recorder, giving a full measuring range of 5mV (corresponding to a 20C range). In addition, the heat of fusion of the alloy was detected by means of differential scanning calorimetry (DSC) in a RiGak TG-DTA/DSC-DPS8150 system under argon protection. The response rate of the system was 0.065 J/sec. Experiments were repeated at least 3 times under the same conditions to confirm consistent results. Epitaxial growth experiment was pursued in a special single-crystal-drawing furnace [14]. Samples of the 0.35% Sb treated Al-22wt%Si alloy were remelted at 720C in the furnace in a high purity argon atmosphere. The temperature was then lowered to and kept at 675C for 3 minutes before a deionized single crystal silicon seed with (111)Si or (100)Si surfaces [15] was inserted into the melt. The melt, together with the seed, was cooled down to ambient temperature at the rate of 65C/min. The solidified sample with the silicon seed was cut in the way that the section was vertical to the (111)Si or (100)Si surfaces and parallel to the [110]Si direction of the silicon seed. The microstructure of the samples was then examined by means of microscopy.

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Figure 2. Microstructure of the 0.2%Sb treated Al-12wt%Si alloy with (a) fine eutectic regions and (b) coarse eutectic regions.

The adsorptivity of Sb on {111)Si or {100}Si was investigated using the single-crystal-drawing furnace. The experimental procedure was similar to the one mentioned above for epitaxial growth except that after a single crystal silicon seed with (111)Si or (100)Si surfaces was immersed into the 0.35% Sb treated Al-22wt%Si alloy melt for 5 minutes, the seed was drawn out from the melt and cooled to ambient temperature before undertaking surface analyses by XPS in an XSAM800 system and by AES in a PHI550 system [14]. Results and Discussion Effect of Sb on the Microstructure and Solidification Curves of Al-12wt%Si Alloy The microstructure of the 0.2%Sb treated Al-12wt%Si alloy is shown in Figure 2. The alloy had a non-uniform refined microstructure: in some regions it had a very fine eutectic structure along with

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Figure 3. Thermal analysis curves of the 0.2%Sb treated Al-12wt%Si alloy in comparison with an untreated alloy.

some primary aluminium dendrites (Figure 2a) while in other regions the structure was similar to that of an unmodified alloy (Figure 2b). Figure 3 shows the thermal analysis curves of the 0.2%Sb treated Al-12wt%Si alloy in comparison with those of the Al-12wt%Si alloy without any Sb addition. The curves did not indicate any obvious change due to the antimony addition. The solidification was typically of eutectic and both the eutectic arrest temperature and the melting point remained almost identical for the alloys with and without the presence of antimony in the melt. Table 1 gives the results of DSC analysis on the 0.2% Sb treated Al-12wt%Si alloy in comparison with the untreated alloy, indicating that antimony has very little ( 7%, which could be attributed to measuring errors) effect on the heat of fusion of the alloy. The above results show that although antimony caused a non-uniform refinement of the Al-Si eutectic structure, it did not alter the overall solidification pattern of the alloy. The eutectic arrest temperature, melting point and heat of fusion of the high purity Al-12wt%Si alloy remained little changed by the addition of antimony. Effect of Antimony on the Epitaxial Growth of Silicon Figure 4 shows the as-cast microstructures of the 0.35% Sb treated Al-22wt%Si alloy in comparison with an untreated alloy. In both structures the primary silicon had a branched platelike morphology. However, in the presence of antimony, primary silicon plates appeared more developed in its preferential growth direction. This may be attributed to the constitutional cooling effect by Sb. Microscopic examination of the epitaxial growth samples revealed that there was no continuous epitaxial growth layer of primary silicon on the (111)Si and (100)Si surface (Figure 5, the silicon seed represented as dark bottom in the field of view). Instead, platelike primary silicon grew epitaxially from
TABLE 1 Heat of Fusion of the Al-12wt%Si Alloy Detected by DSC.
Antimony Addition (%) Nil 0.20 Heat of fusion (J/g) 486.25 452.43

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Figure 4. Microstructures of the high purity Al-22wt%Si alloy. (a) Untreated; (b) 0.35%Sb treated.

some particular sites of the silicon substrate surface. The epitaxial primary silicon plates had certain lattice orientation relationships with the substrates but could change their growth directions by twinning. These all remained identical to those epitaxial growth features in the untreated high purity Al-22wt%Si alloy as reported previously [15], indicating that antimony did not affect the epitaxial growth characteristics of silicon. The average number of epitaxial silicon plates per unit length along the substrate surface in the section was also similar in both the Sb treated alloy and the untreated alloy [15]. As the particular sites where epitaxial growth occurred can be considered as active substrates [13], this implies that, unlike sodium or strontium [14], antimony did not poison the active substrates. The Adsorptivity of Antimony on (111)Si and (100)Si Surfaces The surfaces of the single crystal silicon seeds withdrawn from the 0.35% Sb treated Al-22wt%Si alloy melt were first analyzed by XPS. In XPS analysis the major peak of antimony overlapped with the major peak of oxygen (O1s) and thus could not be distinguished. However, detailed scanning at other

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Figure 5. Epitaxial growth from (a) (111)Si and (b) (100)Si seeds into the 0.35%Sb treated Al-22wt%Si alloy melt.

antimony peak positions failed to detected its existence on the surfaces. In order to confirm this, 5 random dot composition analyses were made by AES on each (111)Si or (100)Si surface of the silicon seeds. Again no existence of antimony was detected. Figure 6 gives a typical AES profile achieved on the (111)Si surface (the oxygen and carbon peaks are attributed to contaminants on the surface when the seed was exposed to the air before the analyses). XPS and AES analyses failed to detect any adsorption of Sb on the (111)Si and (100)Si surfaces of the single crystal silicon seeds. This implies that the refinement mechanism by Sb may be different from those by Na and Sr. For example, the level of enrichment of Sb at the interface by constituent redistribution due to the very small partition coefficients of Sb in -Al and silicon (0.01 0.09 in -Al [16] and 0.02 in silicon [17], respectively) may be critical to the effect of refinement.

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Figure 6. Typical AES profiles detected on the (111)Si surface of single crystal silicon seed.

Conclusions (1) The addition of 0.2% Sb to the high purity Al-12wt%Si alloy resulted in a non-uniform refined microstructure but no obvious effect on the eutectic arrest temperature, melting point and heat of fusion of the alloy was detected. (2) The addition of 0.35% Sb to the high purity Al-22wt%Si alloy did not affect the epitaxial growth characteristics of primary silicon from the (111)Si and (100)Si single crystal silicon substrates. No adsorption of antimony on (111)Si and (100)Si surfaces was detected by XPS and AES. References
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