Scripta mater. 43 (2000) 881 886 www.elsevier.

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VISUALISATION OF OXIDE FILM DEFECTS DURING SOLIDIFICATION OF ALUMINIUM ALLOYS

S. Fox and J. Campbell
Cast Metals Research Group, IRC in Materials for High Performance Applications, University of Birmingham, Birmingham B15 2TT, UK (Received June 19, 2000) (Accepted June 21, 2000) Keywords: Casting; Aluminium alloy; X-ray radiography; Theory and modelling defects; Oxide films Introduction Aluminium alloy castings are now becoming commonplace in highly demanding safety critical applications in the automotive and aerospace industries. It is, therefore, imperative that internal defect structures and potential failure mechanisms are fully understood if reliable castings are to be produced consistently by the foundry. Traditionally, porosity has been held responsible for the majority of casting defects. However, few workers have considered the extreme difficulty and physical implications of the direct nucleation of voids within a casting. In the present study, we are proposing a novel test and a radically new mechanism for the development of macroscopic defects from pre-existing or processrelated metal damage within aluminium alloys. At present, the test gives a qualitative snapshot of liquid metal quality but work is underway to develop this into a fully quantitative real-time analysis system for use in the primary and secondary aluminium industries. Background The two most important interactions that occur between liquid aluminium and its environment are the dissolution of hydrogen and the formation of oxide films. Hydrogen dissolves readily in liquid aluminium but is much less soluble in the solid metal [1]. The free energy of formation of alumina is such that it is practically impossible to prevent film formation at exposed surfaces [2]. The potential for introducing defects into castings, therefore, begins at primary alloy production, where hydrogen gas and oxide films become incorporated into the melt. Most foundries, therefore, use some form of degassing and fluxing operation to minimise these pre-existing problems. Unfortunately, this is now often the stage where real damage is done to the liquid metal. The clean, degassed metal is transferred from the holding furnace to the mould via a pump, launder or ladle. Unless this operation is carried out quiescently, new oxide films are incorporated into the melt during transfer and mould filling. It is crucial to understand what happens when oxide films are enveloped by liquid metal. Figure 1 shows a schematic diagram of the entrainment of an oxide film due to splashing at the surface of an aluminium alloy melt. It is essential to note that the surface entrains as a double oxide, folded dry side to dry side. This is the only way in which oxide films can be introduced into the liquid metal. Even if a thick oxide film is pushed into the melt, in an effort to create a single immersed inclusion, it will be surrounded by two new, non-wetting surface films. The microscopic surface roughness of these solid
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Figure 1. Formation of folded double oxide films [2].

films results in point contact at asperties in the surface and, therefore, gas entrapment between the contacting films. The defect constitutes a crack in the liquid. The existence of shear-type forces due to bulk turbulence or stirring within the melt may then distort or compact double films into highly contorted structures but still retaining the characteristics of convoluted cracks. Having described the possible mechanisms of film entrapment, the presence of damaging oxide films is often only detected when a casting leaks or fractures at such inclusions. Until now, the ubiquitous presence of these very thin double films has not been widely accepted because no single metal quality test has been able to resolve such thin but extensive defects. We have developed a novel reduced pressure test that allows a detailed assessment of metal quality through the simultaneous visualisation of double oxide films and hydrogen content. Experimental The method that has been used to visualise film defects in this work is based on the existing Reduced Pressure Test (U.S.A), which is also known, with slight variations in operating procedure, as the Straube Pfeiffer (Germany), Foseco Porotec (UK) and IDECO test (Germany). In these tests, two small samples of melt are solidified in thin-walled steel moulds in air and under a partial vacuum respectively. Hydrogen content may then assessed by inspection of the melt surface during solidification under vacuum. Melt quality, which is a combined measure of film and gas content, can also be determined from density measurements of the two samples, the percentage difference giving the density index. In the present work, a novel reduced pressure test machine was constructed so that tests could also be carried out using chemically-bonded sand moulds. The machine consists of a vacuum chamber, a filtration system, a precision pressure regulator, a pressure transmitter and a rotary vacuum pump, see Figure 2(a). The vacuum system is semi-automatic in operation and tests can be carried out at absolute pressures ranging from 5 mbar to 250 mbar (one two-hundredth to one quarter of an atmosphere). Wooden patternwork was constructed to produce pairs of either conical or flat plate sand moulds using the Ashland Cold Box Isocure or No Bake Pepset processes. The novelty of the technique is in the x-ray radiographic examination of the test castings. The plate castings have overall dimensions of 35 to 45 mm across (bottom to top) are approximately 50 mm high and are 15 mm thick. The design of the plate castings is such that the larger faces are parallel, the samples are, therefore, ready for x-ray examination without further preparation. Samples of Al-7Si-0.4Mg type alloy were taken from small-scale laboratory melts and from large-scale melts in a commercial foundry. In each test, the two sand moulds were filled using a small pre-heated ladle and while one casting is allowed to solidify in air, the other is quickly transferred to

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Figure 2. Reduced Pressure Test machine and filled plate mould.

the vacuum chamber using the carrier shown in Figure 2(b). The solidified samples were removed from the moulds and cleaned with a wire brush before density index testing and x-ray radiographic examination. Results Figure 3 shows radiographs of plate castings from a series of tests that were carried out on metal from a large gas-fired melting furnace in a commercial foundry. The sample that was solidified in air, Figure 3(a), shows evidence of fine scale shrinkage porosity in the form of approximately equi-axed specks, which are of the order of one millimetre in diameter, appearing in dark contrast. At a test pressure of 200 mbar, Figure 3(b), the specks have become elongated into thin streaks of several millimetres in length. At 100 mbar, Figure 3(c), these streaks have undergone a further increase in length and, now, also in thickness. The three further reductions in pressure (50, 25 and 12.5 mbar, Figures 3(d-e) respectively) result in corresponding increases in defect dimensions. Identical behaviour was observed in radiographs that were obtained from the central section of the larger truncated cone shaped castings. The results from density index tests on the plate and cone castings are shown in Table 1 above. It is interesting to note that although the radiographs showed a clear trend in the enlargement of defect morphology with reducing test pressure, there is no corresponding relationship between test pressure and density index. It should be noted that melt sampling for these tests took place over a period of two hours and that intermittent firing of the gas burners during this time resulted in instantaneous metal temperatures ranging from 780 to 790C. Figure 4 shows a pair of reduced pressure tests that were carried out on samples of laboratory melt with a hydrogen content of around 0.07 cm3/100 g (as measured by the Severn Science Hyscan test). The internal defect structure appears to be more finely dispersed and is not as sharply defined as that of the previous samples but it still retains an irregular film-like appearance. Increasing the hydrogen content of the laboratory melt still further, to around 0.32 cm3/100 g, resulted in the growth of spherical pores in the reduced pressure test. Figure 5 shows corresponding radiographs for this gassy melt. Figure 5(b) clearly shows that any evidence of pore nucleation sites has disappeared. Discussion of Results The sequence of radiographs in Figure 3 graphically demonstrates a previously unknown phenomenonthat of unfolding double oxide films, in this case under a negative externally applied hydrostatic

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Figure 3. X-ray radiographs showing development of internal defect structure with decreasing test pressure in reduced pressure test plate castings (1000 12.5 mbar absolute pressure).

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TABLE 1 Variation of Density Index with Test Pressure

Test Pressure (mbar) 200 100 50 25 12.5 Plate Casting Density Index (%) 1.26 1.78 3.65 2.30 2.86 Cone Casting Density Index (%) 1.55 1.39 5.02 1.71 4.37

pressure. It is proposed that the small grey specks in the samples that were solidified under ambient pressure are actually double oxide films that have been crumpled into discrete packets, under the influence of shear-type forces within the melt. The specks have acted as potent nucleation sites for

Figure 4. X-ray radiographs showing centre of plate castings with intermediate hydrogen content.

Figure 5. X-ray radiographs showing centre of plate castings with high hydrogen content.

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internal porosity and have begun to open-up during the final stages of solidification in order to accommodate the internal strains that arise from shrinkage. If this negative internal stress is artificially increased by the application of a vacuum whilst the metal is still liquid, the double oxide film packets begin to unravel. This is clearly shown by the transformation from a compact morphology to thin elongating streaks, to expanded film-like defects as the test pressure is reduced (Figure 3(a) to (f)). The streak-like appearance of the porosity is due to an edge-on view of an essentially planar defect. The fact that these defects are shown in such high contrast at the lowest test pressure suggests that they almost completely penetrate the 15 mm casting thickness. The more extensive areas of porosity, shown at lower contrast in Figure 3(f) are a result of defects lying at different angles to the major plane of the casting. The larger defects, of 10 to 15 mm in diameter may, therefore, have dimensions that are only limited by the thickness of the sand mould that was used for these tests. The absence of a correlation between density index and the radiographic images in Figure 3 demonstrates the unreliable nature of the density index test as an indicator of melt quality. Small variations in the size and distribution of film defects can have a large effect on the relative density measurements. Increasing the hydrogen content of the melt results in the inflation of the original double oxide film nuclei in the reduced pressure test samples. Figure 4 showed an intermediate situation, in which the original double oxide films are becoming unfurled and slightly expanded by the effective internal pressure of hydrogen gas. The high level of hydrogen in the samples in Figure 5 has resulted in the complete transformation of the defects into expanded spheres. Further Work At present the test technique that has been described gives only a qualitative assessment of the existence of entrained double oxide films and an indication of hydrogen content. The test will, therefore, be further refined by the use of image analysis. Measurements of the overall image density will be used to determine hydrogen content, and, analysis of the size, aspect ratio and distribution of defects will enable quantification of the oxide film content. The test could also be further developed into a powerful on-line analytical technique, for the assessment of metal quality, by the use of dedicated real-time radiography. Conclusions 1. This reduced pressure test is capable of revealing the presence of double oxide film defects, and, predicting the potential for the formation of hydrogen porosity in aluminium alloy castings. 2. The mechanism for the creation of extended oxide film defects, by unfolding under reduced pressure, may also apply to defects subjected to internal gas pressure and/or shrinkage. Acknowledgments The authors are grateful to the Ashland Chemical Company who funded this work as part of a joint research programme to investigate the occurrence of mould metal interactions in castings. References
1. 2. E. A. Brandes, ed., Smithells Metals Reference Book, p. 122, Butterworths, London (1983). J. Campbell, Castings, p. 11, Butterworth-Heinemann, Oxford (1997).