This invention relates to an aluminium casting alloy and more particularly to a hypoeutectic aluminium silicon alloy for use in shape casting.
Aluminium silicon alloys containing less than about 12% silicon are referred to as hypoeutectic alloys. In addition to alleviating the formation of defects such as hot tearing and porosity due to the shrinkage and gases, and also to minimising the presence of inclusions, two very significant ways in which the strength, ductility and performance of an aluminium casting alloy can be improved are through grain refinement of the primary aluminium phase and modification of the eutectic Al+Si structure. Upon cooling of molten hypoeutectic alloys, aluminium crystals form first through nucleation and growth, and later the second important event is the formation of the Al+Si eutectic mixture. It is understood that the (Al+Si) eutectic is an irregular and coupled eutectic, and it grows in the form of eutectic colonies, with silicon radiating from a single nucleating point and the tips of the silicon plates grow ahead of the aluminium, leading into the cooling liquid. It has been demonstrated that the (Al+Si) eutectic can nucleate on existing aluminium dendrites or substrate particles in the melt such as AlP, AlSiNa, Al2Si2Sr and other unidentified particles.
Grain refinement of primary aluminium is simply the process of adding nuclei and solutes with a strong constitutional undercooling effect to the melt prior to pouring such that upon the freezing process (i.e. solidification) the casting will expedite a refined microstructure with small equiaxed aluminium crystals. Grain refinement of primary aluminium crystals is accomplished generally by adding master alloys containing titanium and/or boron to the melt.
Eutectic modification on the other hand is the process of changing the morphology of the cast structure and in particular, that portion of the cast structure which freezes as a eutectic mixture of aluminium and silicon towards the end of solidification. Unmodified hypoeutectic aluminium silicon alloys are relatively non ductile or brittle and consist of primary aluminium dendrites with eutectic composed of coarse acicular or plate-like silicon phase in an aluminium matrix. The morphology of these silicon rich crystals in the eutectic mixture can be modified by small additions of elements such as sodium, strontium or antimony to the melt to alter the eutectic structure and to yield silicon rich crystals having fine, fibrous structure. However the addition of modifiers has been found to neutralise the potent nuclei for the eutectic colonies in the melts resulting in a significant increase of the undercooling in eutectic nucleation and depression of the eutectic growth temperature. This in turn increases the eutectic grain size and reduces nucleation frequency in forming modified aluminium silicon alloys. Furthermore, modification of the aluminium silicon alloys has also been reported to cause pore redistribution and an increase in casting porosity.
It is an object of the present invention to provide a hypoeutectic aluminium silicon alloy having an improved microstructure with good castability and improved porosity characteristics.
Accordingly, in one aspect the invention provides a hypoeutectic aluminium silicon alloy wherein the eutectic is modified by a master alloy consisting of an element selected from strontium, sodium, antimony, barium, calcium, yttrium, lithium, potassium, ytterbium and rare earth elements such as europium, mischmetal, such as lanthanum, cerium, praseodynium and neodynium and further refined by the addition of a master alloy containing nucleant particles for the eutectic colonies. It is preferable that the nucleant particles are selected from the group consisting of TiSix, MnCx, AlP, AlBx, and CrBx which are added as particles or formed in situ in the melts. These nucleant particles promote a small eutectic grain size without altering fine fibrous silicon crystal structure.
In a preferred embodiment of the invention, the nucleant particles have a particle size of less than 100 μm and preferably less than 10 μm. The nucleant particles are preferably added to the melt by way of a master alloy containing the nucleant particles or formed in situ in the melts through preferred reactions, such as reactions between melt and master alloys.
In one aspect of the invention, there is provided a method of forming a hypoeutectic aluminium silicon alloy including the steps of:
The applicant has found that by the addition or in situ formation of these nucleant particles into a hypoeutectic aluminium silicon alloy modified by one of the elements referred to above, a modified aluminium silicon alloy having reduced porosity is produced. Furthermore, fine silicon rich crystals having a fibrous eutectic structure are produced.
In the case of CrBx, the addition rate of these particles to the melt was preferably greater than 2 wt %.
The applicant has found that the above mentioned colony refining additions are not affected by the presence of eutectic modification additions or vice versa if the addition conditions are controlled properly. Hence the TiSix, MnCx, AlP, CrBx and AlBx present are able to act as nucleant particles for eutectic colonies.
In another aspect of the invention, there is provided an aluminium silicon alloy including:
In a further aspect, there is provided use of a hypoeutectic alloy to produce an as cast material, the alloy consisting essentially of:
a)-1(d) show micrographs of quenched and fully solidified samples.
a)-6(d) are macrographs of samples quenched from different addition levels of B as Al-3% B to Sr modified alloy.
a)-7(d) are micrographs of the fully solidified samples of those shown in
It will be understood that the invention disclosed and defined in this specification extends to all alternative combinations of two or more of the individual features mentioned or evident from the text or drawings. All of these different combinations constitute various alternative aspects of the invention.
An Al-10% Si-0.35% Mg alloy unless otherwise specified, was selected as a base alloy and it was prepared from commercial purity aluminium, silicon and magnesium in an induction furnace. After being held at about 750° C. for 10 minutes for homogenization, the base alloy melt was transferred to an electric resistance furnace, which was held at 730° C. After reaching thermal equilibrium, the melt was modified first by the addition of a refining element such as Sr, to neutralize the potent nuclei present in the melt. Weighted trial master alloy was then added to introduce or form new nuclei in situ in the melt. The melt was stirred twice after each addition. All additives were dried in an oven at 300° C. and then wrapped in aluminium foil before addition to ensure that they dissolved properly and evenly throughout the melt.
Thermal analysis and quenching trials were usually performed prior to and after eutectic modification as well as after addition of trial master alloys. Thermal analysis was performed first using a preheated graphite crucible and a centrally located, stainless steel-sheathed Type N thermocouple to help develop a strategy for the following quenching trials. The cooling rate for thermal analysis was about 1° C./s just prior to nucleation of the first solid. Two interrupted quenching tests, corresponding to the beginning and middle stages of eutectic solidification, were then carried out using a special stainless steel quenching cup sitting either in an insulation brick or in the air.
Samples for chemical analysis were also collected after each addition and prepared according to Australian standard (AS 2612) and analysed using a bench top spark optical emission spectrometer. For microstructural observation, the quenched samples were sectioned vertically along the thermocouple line while fully solidified TA samples were sectioned horizontally at the level of the thermocouple. Metallographic samples were mounted in resin and prepared using a standard procedure with a final polishing stage of 0.05 μm colloidal silica suspension. The macrographs were taken from etched samples using a high-resolution digital camera under indirect illumination conditions. The micrographs were taken in the median region of the section, 10 mm away from the bottom of the unetched samples.
Potential Nucleating Particles and Trial Master Alloys
It is understood that the (Al+Si) eutectic is an irregular and coupled eutectic, and it grows in the form of eutectic colonies, with silicon radiating from a single nucleating point and the tips of the silicon plates grow ahead of the aluminium, leading into the cooling liquid. It has been demonstrated that the (Al+Si) eutectic can nucleate on existing aluminium dendrites or substrate particles in the melt.
Since Si is generally believed to be the leading phase in (Al+Si) eutectic, the nucleation of the eutectic therefore comes to the nucleation of Si. Based on our knowledge of known nucleants and lattice mismatch, a list of potential nucleating particles for the eutectic colonies were compiled. Three particles including TiSix, CrBx, MnCx were further selected from the list, and trial master alloys containing these three particles have been manufactured. During the implementation of this project, two more particles, AlBx, and AlP, have been further included in the test. Table 1 lists all the potential nucleating particles tested and the corresponding trial master alloys. While most nucleating particles are assumed to be present in the trial master alloys, some others have to form in-situ in the melts after addition of trial master alloys.
A number of tests have been conducted with different addition levels of three trial alloys separately containing the nucleant particles TiSix, CrBx and MnCx. Among these master alloys, the alloy with CrBx particles appears effective in nucleating the eutectic Si. Three repetitive tests have been conducted for this master alloy alone. It appears this master alloy is effective only at an addition level exceeding 2 wt % (or according to calculation, there is about 2.5 wt % CrBx in the master alloy. Therefore it is expected to have 0.5 g CrBx in 1000 g melt at this addition level). This is likely because the number of potent nuclei is not very high in the master alloy itself. Nevertheless this demonstrates the potency of the CrBx particles present in this particular trial master alloy. These particles measured using laser diffraction technique had a volume weighted mean diameter of 5 μm. While the general trend was found in all three tests (ie. volume weighted mean diameter of 5 μm), the degree of increase in nucleation frequency achieved varies. This may also suggest that the master alloy is not very uniform.
From the results in
While the CrBx-bearing trial alloy has demonstrated its effectiveness in promoting eutectic nucleation, both TiSix and MnCx-bearing master alloys have shown negligible effect. The trial master alloys have also been characterized. Table 1 summarizes the chemical compositions of these trial master alloys. In Table 1, while the atomic ratio of Cr to B for CrBx-bearing master alloy is very close to the stoichiometric value for CrB2, the compositions of both the TiSix and the MnCx-bearing master alloys are far away from the theoretical values for the targeted particles. Therefore, no targeted particles are expected to be present in these alloys.
Phosphorous is a common trace impurity element in commercial aluminium. It originates from impurities in the alumina so that the potline Al contains somewhere around 5-20 ppm P. Phosphorous can also arise from the refractory furnace lining in melting and holding furnaces. It is well established that AlP is a good nucleus for silicon, and this is used commercially to grain refine primary silicon crystals in hypereutectic Al—Si alloys which contain silicon contents above about 12 wt %, and 18 wt % is common. In hypoeutectic alloys, it is suggested that the modifiers (such as Sr) neutralise the AlP particles, thereby reducing the eutectic nucleation frequency, although the effect has not received significant attention. It is therefore of interest to investigate whether it is possible to tailor specific combinations of P and Sr to achieve a high nucleation frequency together with a refined and fibrous Si morphology.
A phosphorus containing master alloy Al CuP having 19 wt % Cu, 79.6 wt %, 1.4 wt % was used as the nucleating agent after Sr modification.
a), (b), (c), (d) shows the macrographs of samples quenched at halfway through the eutectic reaction and the micrographs of fully solidified samples with different levels of P in Sr-modified Al-10% Si alloys.
Samples of the aluminium-silicon melts with varying additions of Sr and P were subjected to Tatur test casting. The melts were cast as unmodified Al—Si, 150 ppm Sr modified Al—Si alloy with zero, 8 ppm and 30 ppm additions of phosphorus.
As can be seen from
The exact balance of P and Sr addition for optimising the porosity performance of alloys, while maintaining a well modified eutectic depends on the casting conditions and local cooling rate of the casting.
From the work with additions of Ti-bearing master alloys into Sr-modified melts, it is understood that aluminium boride may be a potent nucleus for the eutectic colonies. Therefore experiments have been conducted with addition of Al-3% B master alloy into Sr-modified melts. One repetitive run was conducted and the results appear very promising. The Ti and B containing master alloys used as the Al B producing nucleating agent were commercially available alloys Tibor and Tibloy having the composition set out in Table 3.
The impurity level of Ti in the liquid alloys did not affect the effectiveness of the nucleating particles for this invention. For some of tests where Tibloy was used, the Ti concentration in the melt can reach up to about 1000 ppm.
a)-(d) and 7(a)-(d) show the macrographs of samples quenched halfway through the eutectic reaction and the micrographs of fully solidified samples, respectively.
Among the three trial master alloys, the CrBx-bearing alloy is effective in promoting the eutectic nucleation, while TiSix- and MnCx bearing master alloys have only negligible effect. Absence of the potent nucleating particles with a right size distribution in the master alloys is suspected of being responsible for the weak effects observed for these trial master alloys.
The applicants have concluded that it is possible to refine eutectic colonies while keeping a well-modified eutectic structure by additions of an appropriate amount of AlP, CrBx and AlBx into Sr-modified melts. Given the right size distribution, TiSix and MnCx could also be used effectively. Melts modified by other eutectic modifying elements such as sodium, antimony, barium, calcium, yttrium, lithium, potassium, and rare earth elements such as ytterbium, europium and mischmetal, such as lanthanum, cerium, praseodynium and neodynium used for eutectic modification are also able to benefit from the addition of these nucleant particles.
The schematic illustration in
Number | Date | Country | Kind |
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2004906910 | Dec 2004 | AU | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/AU2005/001826 | 12/2/2005 | WO | 00 | 8/18/2009 |
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WO2006/058388 | 6/8/2008 | WO | A |
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