Iron-Rich Intermetallic Phases and Their Role in Casting Defect Formation in Hypoeutectic Al-Si Alloys

L. LU and A.K. DAHLE Iron is the most common and detrimental impurity in aluminum casting alloys and has long been associated with an increase in casting defects. While the negative effects of iron are clear, the mechanism involved is not fully understood. It is generally believed to be associated with the formation of Fe-rich intermetallic phases. Many factors, including alloy composition, melt superheating, Sr modification, cooling rate, and oxide bifilms, could play a role. In the present investigation, the interactions between iron and each individual element commonly present in aluminum casting alloys, were investigated using a combination of thermal analysis and interrupted quenching tests. The Fe-rich intermetallic phases were characterized using optical microscope, scanning electron microscope, and electron probe microanalysis (EPMA), and the results were compared with the predictions by Thermocalc. It was found that increasing the iron content changes the precipitation sequence of the phase, leading to the precipitation of coarse binary platelets at a higher temperature. In contrast, manganese, silicon, and strontium appear to suppress the coarse binary platelets, and Mn further promotes the formation of a more compact and less harmful phase. They are therefore expected to reduce the negative effects of the phase. While reported in the literature, no effect of P on the amount of platelets was observed. Finally, attempts are made to correlate the Fe-rich intermetallic phases to the formation of casting defects. The role of the phase as a nucleation site for eutectic Si and the role of the oxide bifilms and AlP as a heterogeneous substrate of Fe intermetallics are also discussed.

I. INTRODUCTION

IRON is the most common and detrimental impurity present in aluminum casting alloys and has long been associated with an increase in casting porosity. After examining the effect of iron on casting porosity, Taylor et al.[1,2,3] found that porosity in Al-5Si-1Cu and Al-10Si-1Cu alloys starts to increase at intermediate iron contents. By using the same techniques, Otte[4] examined the effect of iron on porosity formation in an Al-9Si-3Cu alloy. He found that the total level of porosity increased slightly with iron content and that a large region of interconnected sponge-like porosity formed at high iron contents. Iwahori et al.[5] also studied the relationship between porosity and melt iron level. They suggested that feeding decreased dramatically at iron contents above a critical value. In addition to its negative effect on casting porosity, iron was also reported to reduce the castability, the mechanical properties (particularly ductility), the corrosion resistance, and the machinability of Al-Si casting alloys.[6,7] While the negative effects of iron are clear, the mechanism involved is not fully understood. It is generally believed to be associated with the formation of Fe-rich intermetallic phases during solidification. A number of Fe-rich intermetallic phases, including (Al8Fe2Si or Al15(Fe,Mn)3Si2), (Al5FeSi), (Al8Mg3FeSi6), and (Al4FeSi2), have been identified in Al-Si casting alloys.[610] Among them, the phase was reported to be particularly deleterious to the castability and mechanical properties.[6,7,8] The platelet-like mor-

L. LU, Research Fellow, and A.K. DAHLE, Associate Professor, are with the CRC for Cast Metals Manufacturing (CAST), Division of Materials Engineering, The University of Queensland, Brisbane, QLD 4072, Australia. Contact e-mail: l.lu@minmet.uq.edu.au Manuscript submitted December 7, 2003.
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phology of this phase is expected to cause severe feeding difficulties during solidification, and eventually to increase the tendency to porosity formation. It has been suggested that the formation of porosity at high iron contents is due to the precipitation of coarse platelets, which block the interdendritic flow channels.[15,11,12] Taylor et al.[1,2,3] further suggested that the formation of large platelets at high iron contents facilitates the nucleation of eutectic Si, therefore leading to a rapid deterioration of the interdendritic permeability. The nucleation of eutectic Si on platelets has been proposed in the literature.[12,13] However, no direct evidence has been presented yet. It has also been suggested that the platelets are effective pore nucleation sites and therefore likely increase gas porosity in castings.[11] Since iron is inevitable and cannot be economically removed from the molten aluminum, strategies have to be developed to neutralize its negative effects. It is well known that addition of such elements as Mn, Cr, Be, and Ni can neutralize the embrittling effect of iron by modifying the platelet-like morphology to a less harmful, more compact form.[6,8,14] However, some technical problems associated with addition of these elements to iron-containing melts exist.[6,15,16] More recently, it was found that the volume fraction, size, and morphology of the Fe-rich intermetallic phases are strongly influenced by the iron content,[13] Mn content,[17,18] Mg content,[19] P content,[20,21] cooling rate,[18,22,23] Sr modification,[17,19,2224] and melt superheating.[18] Table I summarizes various measures reported to be effective in modifying the Fe-rich intermetallics. While much effort has been made with the aim of neutralizing the negative effects of Ferich intermetallic phases, almost all the work was conducted for specific commercial casting alloys containing many other elements, which might interact with the element of interest. Due to the complexity of commercial alloys, it is sometime difficult to generalize the results from one alloy to another.
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Table I. Various Measures Reported to Modify the Fe-Rich Intermetallics[13,1724] Parameters Fe Mn, Cr, Be, Ni, etc. Mg P Sr Cooling rate Melt superheating Possible Effects change precipitation sequence of transform into , but increase the total amount of Fe-rich intermetallics transform into promote the nucleation of dissolution, fragmentation, and even decomposition (at extremely high levels) of low cooling rate generally favors the formation of refine and reduce the Fe-rich intermetallics including and avoid sludge formation
Fig. 1External defects found upon inspection of the elbow castings[28].

While considerable studies have been reported on the morphologies of Fe-rich intermetallics, the nucleation of such intermetallics has been somehow overlooked. Recent work by Campbell and co-workers[17,25,26] has proposed that the Fe-rich intermetallics nucleate and grow on the externally wetted surfaces of the oxide films, which are entrained into the melts during the pouring operation. This is in contrast to the suggestion by Sigworth[20] that P present in the melts (probably AlP) has a role in nucleating the Fe-rich intermetallics. Campbell et al. have further applied this nucleation mechanism to explain the cracks often observed along the central axis of Fe-rich intermetallics. This theory is still in its early stage and somewhat speculative. Nevertheless, it may open up new avenues for engineering the nucleation and growth of Fe-rich intermetallics. The present investigation was hence aimed at determining the interactions between iron and each individual element commonly present in Al-Si casting alloys in order to clarify the effects of these elements on the formation of Fe-rich intermetallic phases. Attempts are also made to correlate Fe-rich intermetallic phases to the formation of casting defects. The role of the phase as a nucleation site for eutectic Si and the role of the oxide bifilms and AlP as a heterogeneous substrate for Fe-rich intermetallics are also discussed. II. EXPERIMENTAL A. Melt Preparation An Al-7 pct Si-0.4 pct Mg ternary alloy was selected as a base alloy and prepared from commercial purity aluminum, silicon, and magnesium in an induction furnace. After being homogenized at 750 C for 10 minutes, the melt was alloyed according to a predetermined scheme. Iron addition was made at approximately 750 C using ALTAB Fe compact (75 pct Fe, 15 pct Al, and 10 pct nonhygroscopic Na-free flux) to achieve nominal levels of 0.3 pct and 0.7 pct, in order to study the effect of iron content on the formation, size, and amount of Fe-rich intermetallic phases. For the melts with 0.7 pct Fe, further additions of individual elements such as Mn, P, Sr, and Si were made using ALTAB Mn compact (75 pct Mn, 15 pct Al, and 10 pct nonhygroscopic Na-free Flux), AlCuP rod (1.4 pct P and 19 pct Cu), Al10Sr rod (10 pct Sr), and silicon, respectively, to achieve nominal levels of 0.3 pct Mn, 100 ppm P, 250 ppm Sr, and 10 pct Si. This enables us to
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examine the interactions between iron and each individual element. Combined additions of selected elements were also made in some circumstances. All master alloys used in the present investigation were supplied by London & Scandinavian Metallurgical Company in U.K. Following alloying, degassing was then carried out using high-purity N2 gas at a flow rate of 5 L/min. This was conducted at about 750 C for 10 minutes through a graphite lance with a porous plug. The degassed melt was then skimmed and transferred to an electrical resistance furnace, which was held at 750 C. B. Thermal Analysis and Interrupted Quenching Test Thermal analysis was performed using a preheated graphite crucible and a centrally located, stainless steelsheathed type N thermocouple to monitor the sequence of phase precipitation and to develop a strategy for the following quenching trials. Three interrupted quenching trials, corresponding to different stages of the solidification process, were then carried out using a special stainless steel quenching cup. The cooling rate for thermal analysis was about 1 C/sec just prior to nucleation of the first solid. This technique, in combination with electron probe microanalysis (EPMA), is expected to establish information about the type and the precipitation sequence of Fe-rich intermetallics during solidification. C. Elbow Castings An elbow mold arrangement developed to simulate a section of a casting[27,28] was used to examine the shrinkage defects formed in the alloys. Figure 1 shows the locations where visible external defects usually form on the castings. For each of these positions, a number between 0 and 3 was assigned to describe the severity of the casting defect. A rating of 0 was given when there was no externally discernable casting defect and a rating of 3 was given to the most severe casting defect observed. Intermediate defects were given a rating between 0 and 3 depending on their severity. In elbow castings, hot tearing and surface slumping are two major external defects observed. Positions A, B, C, and D in Figure 1 are indicators of surface slumping (or shrinkage). The sum of these positions provides an overall rating
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for the amount of surface slumping of the casting. Position E, located at the junction between the vertical plate and the runner, is the location where hot tearing would occur. Elbow castings were made immediately after TA and quenching trials. The elbow molds were preheated at 300 C for 3 hours prior to casting and the melts were cast at about 740 C for 7 pct Si and 720 C for 10 pct Si, respectively. D. Sample Characterization Samples for chemical analysis were collected and prepared according to Australian Standard (AS 2612) and analyzed using a bench top spark optical emission spectrometer. While good recovery was achieved for most elements, the Sr level is lower than the nominal level likely due to the degassing operation after Sr addition. Therefore, the analytical value from the OES spectrometer was quoted for Sr in the article. For microstructural observation, fully solidified and quenched samples were sectioned vertically along the thermocouple line and mounted in resin. Metallographic samples were prepared using a standard procedure with a final polishing stage of 0.05 m colloidal silica suspension. While all polished samples were evaluated using an optical microscope, selected samples were examined using a PHILIPS*
*PHILIPS is a trademark of Philips Electron Optics Corp., Acht, The Netherland.

content of 29 wt pct, although the polyhedral blocky precipitates contain slightly more Mn compared to the Chinese scriptlike phase. It is therefore believed that the Chinese scriptlike and the blocky precipitates are both phases with slightly different Fe/Mn atomic ratios. Thermal analysis was conducted for all experimental alloys of varying additions. Figure 3 shows an example of the cooling curve and its temperature derivative obtained from the melt with nominal 0.7 pct Fe. The derivative curve clearly reveals five peaks (inflection points in the cooling curve) during the solidification, marked 1 to 5. Based on the microstructural observation of the quenched and fully solidified samples, the possible reactions corresponding to each individual peak were identified and summarized in Table III. This is generally in agreement with our understanding of the Al-Si-Fe-Mn quaternary phase diagram.[10] It is clear in Table III that needles can precipitate at different temperatures via two different reactions. This explains our earlier observation of different sizes of needles. While Reaction 6 is not detected by thermal analysis, most likely due to the limited amount of liquid as well as the slow solid-state diffusion, the phase is clearly evident in the final microstructure across the samples. However, as shown in Figure 4(a), phase is usually limited only to the surface of needles since Reaction 6 is unlikely completed. Also shown in Figure 4 are the typical microstructures observed in the samples as a result of Reactions 4 (Figure 4(b)) and 5 (Figure 4(c)), respectively. B. Effect of Iron Content on the Formation of Iron-Rich Intermetallic Phases In Figure 5, the microstructures of the quenched and fully solidified samples with 0.7 pct Fe are compared to those of the corresponding samples with 0.3 pct Fe. As shown in Figure 5(a), a small needle-like phase was observed in the fully solidified sample; however, no phase formed prior to the eutectic Si at 0.3 pct Fe. Since it is closely related to the Si phase spatially, this phase is believed to form along with Si in a ternary eutectic reaction (4 in Table III). This was further confirmed by the thermal analysis. At 0.7 pct Fe, the majority of phase precipitates prior to the eutectic Si, as shown in Figure 5(b). Since it was usually found to coexist with Al dendrites with its tips projecting into the remaining liquid, this phase is believed to grow via a binary eutectic reaction prior to the eutectic Si (2 in Table III). Based on their precipitation sequence, the needles are hereafter classified as the binary and ternary , corresponding to the pre-eutectic and co-eutectic in the literature.[13] It was concluded that increasing the iron content not only increases the total amount of phase, but also shifts the precipitation sequence of the phase toward a higher temperature. The binary observed in the sample with 0.7 pct Fe forms earlier at a higher temperature; therefore, it is extremely coarse. It is expected to bridge the interdendritic network and block its feeding channels. This is clearly evidenced in the quenched sample in Figure 5(b). C. Effect of Mn, Si, and P additions on the Formation of Iron-Rich Intermetallic Phases 1. Mn addition As shown in Figure 5, the Fe-rich intermetallic phase precipitates almost entirely as phase in the absence of Mn.
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XL30 scanning electron microscope. The chemical compositions of Fe-rich intermetallics were determined using an electron probe (JEOL 8800). For EPMA analysis, pure eleJEOL is a trademark of Japan Electron Optics Ltd., Tokyo.

ment standards were used. These standards including highpurity aluminum (99.97 pct) and high-purity magnesium (99.97 pct) were freshly polished prior to calibration. III. FORMATION OF IRON-RICH INTERMETALLIC PHASES A. Iron-Rich Intermetallic Phases Present in the Samples Figure 2 shows typical phases present in the sample fully solidified from the melt with 0.7 pct Fe and 0.3 pct Mn. Apart from Al (A), eutectic Si (B), and Mg2Si (C), three other phases with different morphologies including needle-like (D, E), blocky (F), and Chinese scriptlike (G) were identified across the sample. The needle-like phase observed was further categorized into two size groups, coarse (D) and fine (E). The average compositions of these phases observed in the selected samples are listed in Table II. Based on the EPMA analysis, the needle-like phase contains about 15 wt pct Si and 26 wt pct Fe when no manganese is added. Therefore, it is not difficult to conclude that this precipitate is actually the phase with its formula close to Al5FeSi. With the presence of Mn in the sample, a small amount of Fe in the phase (D, E in Figure 2) is substituted by Mn, or Al5(Fe,Mn)Si. However, the combined Fe and Mn content in Table II showed only negligible change. It is also clear from Table II that the Chinese scriptlike (G in Figure 2) and the blocky precipitates (F in Figure 2) have a similar Si content of 9 wt pct and a similar combined Fe and Mn
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Fig. 2Backscattered electron images of the sample fully solidified from the melt of 0.7 pct Fe and 0.3% Mn (A: Al, B: eutectic Si, C: Mg2Si, D: coarse , E: fine , F: blocky , G: Chinese script-like ).

Figure 6 presents the microstructures of the samples quenched at the temperature immediately after Peak 2 in Figure 3 and fully solidified, respectively, from the melt with 0.7 pct Fe and 0.3 pct Mn. It is clear that, with the addition of Mn, both the amount and the size of the binary decrease
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considerably. However, the total amount of Fe-rich precipitates is increased. This is because part of the Fe in the melt precipitates as a new Chinese scriptlike (or polyhedral) phase, , prior to the eutectic Si. As a result, the amount of the binary phase decreases. This is clearly observed in
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Table II. Average Compositions of Major Fe-Rich Intermetallic Phases Measured by EPMA Al Alloys 0.7 pct Fe 0.7 pct Fe 0.3 pct Mn 0.7 pct Fe 0.3 pct Mn 200 ppm Sr 10 pct Si 0.7 pct Fe 0.3 pct Mn Phase Morphology needle needle Chinese script blocky Chinese script needle Chinese script Wt Pct 59.09 58.08 62.05 61.90 61.67 59.87 60.61 Si Wt Pct 15.39 17.54 8.93 9.57 9.13 18.16 9.90 Mn Wt Pct 0.01 3.88 8.36 11.85 8.49 3.36 10.18 Fe Wt Pct 26.01 20.76 21.20 17.43 21.10 20.58 19.37 Fe/Mn Atomic 4.70 2.23 1.29 2.18 5.38 1.67 Fe Mn 26.0 24.6 29.6 29.3 29.6 24.0 29.6 Total* Wt Pct 100.59 100.47 100.59 100.83 100.44 102.06 100.11

Wt Pct

*The total concentration in the table includes the Mg and Cu concentrations, which are not listed due to their negligible amount.

Therefore, Mn is expected to suppress the formation of the coarse binary phase and promote the more compact, less harmful phase. This further confirms the findings previously reported in the literature[6,8,14,17,18] that Mn is very effective in inhibiting the formation of the platelets. However, it is worthwhile to mention that while adding a small amount of Mn plays a positive role in combining with Fe to form the Chinese scriptlike phase instead of the coarse platelet morphology, excessive Mn addition will cause severe sludge problems. It will also significantly increase the total amount of brittle Fe-rich intermetallic phases in the microstructure. 2. Si addition Figure 7 shows the microstructures of the quenched and fully solidified samples with 10 pct Si. In Figure 7(a), increasing Si from 7 to 10 pct suppresses the binary phase as expected. This agrees with the thermal analysis in which Peak 2 has disappeared. While not shown in Figure 7(a), a few platelets were observed in the quenched sample. However, the majority of phase observed in the final microstructure in Figure 7(b) is ternary . Therefore Si, like Mn, is expected to suppress the coarse binary . But unlike Mn, it will not increase the total amount of intermetallics in the structure. With further addition of 0.3 pct Mn, both and phases were observed to precipitate prior to the eutectic Si; however, the Chinese scriptlike precipitates are more predominant. This, again, demonstrates that Mn facilitates the formation of the compact phase. 3. P addition It has been suggested that AlP particles in the melt could act as nucleation sites for the platelets.[20,21,23] Therefore, addition of P likely leads to an increased amount of the latter in the structure. Figures 8(a) and (b) show the microstructures of quenched and fully solidified samples containing 100 ppm P. No increase in the amount of platelets was observed either in the quenched structure or in the final structure. Nor were AlP particles found along the sides of the platelets, as reported in the literature. The structural observation has been further demonstrated by the thermal analysis in Figure 8(c), where P has a negligible effect on the thermal event related to the precipitation. However, P addition appears
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Fig. 3Cooling curve and its temperature derivative of the melt with nominal 0.70 pct Fe.

Table III. Possible Reactions Identified in the Experimental Alloys Peaks 1 2 Possible Reactions L S Al depending on the melt composition L S Al b L S Al a b L S Al a L S Al Si L S Al Si b L S Al Si Mg2Si L b S Al Si p Approximate Temperatures,* C 611 581

3 4 5 6

567 565 548 not detected

*The temperatures listed in Table III were obtained from the melt of 0.7 pct Fe.

the quenched sample in Figure 6(a). The effect of Mn was also observed in the thermal analysis where Peak 2 becomes less significant and occurs at a lower temperature compared to the melt without Mn addition.
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(a)

(b)

(c)
Fig. 4Typical microstructures observed in the fully solidified sample with 0.3 pct Fe (a) and (c) quaternary eutectic by Reaction [5].
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phase by Reaction [6], (b) ternary eutectic by Reaction [4],

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(a)

(b)

Fig. 5Microstructures of the samples quenched at temperature immediately after Peak 2 (top) and fully solidified (bottom), from the melts with (a) 0.3 pct and (b) 0.7 pct Fe, respectively.
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(a)

(a)

(b)
Fig. 6Microstructures of the samples (a) quenched at the temperature immediately after Peak 2 and (b) fully solidified from the melt with 0.7 pct Fe and 0.3 pct Mn.
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(b)
Fig. 7Microstructures of samples (a) quenched at the temperature around Peak 2 and (b) fully solidified from the melt containing 0.7 pct Fe and 10 pct Si.
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(a)

(b)

(c)
Fig. 8Microstructures of samples (a) quenched at the temperature immediately after Peak 2 and (b) fully solidified from the melt containing 100 ppm P. (c) Temperature derivatives measured from the melts with and without P addition.

to suppress Peak 5, which is responsible for the quaternary reaction. Since P addition was made using the AlCuP rod, which contains about 19 pct Cu, addition of 100 ppm P will inevitably introduce about 0.14 pct Cu into the melt. Part of this amount of Cu is expected to remain in the liquid until the end of solidification, leading to a depressed Peak 5. D. Effect of Sr Addition on the Formation of Iron-Rich Intermetallic Phases The Sr has been extensively reported to be very effective in refining the platelets, particularly at low coolMETALLURGICAL AND MATERIALS TRANSACTIONS A

ing rates.[17,19,2224] Different mechanisms, including fragmentation, dissolution, and decomposition of the platelets, have been proposed in the literature[23] in order to explain the refining phenomena of Sr. In the fragmentation/ dissolution mechanism, it was suggested that Sr could play an important role in breaking up or partially dissolving the platelets, therefore reducing the length of platelets. However, this seems to be confused. As mentioned earlier, the binary platelets form via the following eutectic reaction: L S Al b [1]

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It is expected that is the leading phase during the eutectic solidification and will be gradually covered by the Al dendrites. Due to the irregularity of the (Al ) eutectic, when the sample is sectioned, it is likely that some segments of a single platelet are exposed while the other segments are somehow covered by the Al dendrites. Therefore it may appear as if it is fragmented or dissolved. This is clearly shown in Figure 9. These platelets arrowed in Figure 9 are believed to belong to the same continuous pieces, which are so bent and covered by the Al dendrites as if they were fragmented or dissolved. Therefore, the length of platelets measured assuming the fragmentation/dissolution effect may not be reliable. Furthermore, the decomposition mechanism of the platelets suggested in the literature[23] at high Sr levels is believed to take place via L b S Al Si p [2]

feeding channels of the interdendritic network earlier. In Figure 10(c), addition of Mn caused no discernable change in casting porosity level compared with Figure 10(b), and all sponge-like pores are seemingly concentrated in the center of the casting thanks to its role in suppressing the coarse binary and promoting the more compact . In Figure 10(d), increasing Si content suppresses the harmful binary and increases the volume fraction of the eutectic Si, therefore improving the castability as expected. In Figures 10(e) and (f), it is clear that Sr addition decreases and redistributes casting porosity. The observed benefit of Sr addition is attributed to the facts that Sr changes the eutectic nucleation mode[29] and refines the phase slightly. All pores formed at the boundary between the eutectic grains. It appears in Figure 10 that the effect of Sr on the casting porosity could completely mask the effects resulting from the formation of Fe-rich intermetallics. B. Shrinkage Defects Table IV summarizes the ratings of casting defects observed upon inspection of the elbow castings of selected compositions. Different degrees of surface slumping were clearly observed depending on alloy composition. Two mechanisms may contribute to the overall surface slumping of the elbow casting. First of all, the Fe-rich intermetallic phases are very dense, and the formation of such dense phases is expected to consume a considerable amount of Si. This in turn reduces the amount of eutectic Si formed in the final structure, consequently leading to an increase in the overall slumping of the alloy during solidification. Increasing Fe and Mn contents is expected to increase the total amount of Fe-rich intermetallic phases in the structure, therefore increasing the surface slumping. The reduced surface slumping by increasing Si content can be explained by the facts that Si increases the volume fraction of the eutectic and it suppresses the formation of Fe-rich intermetallics. Second, Sr modification can reduce the overall surface slumping since it dramatically changes the eutectic nucleation mode and therefore enables a massive eutectic growth front from the surface, combined with independent nucleation of large eutectic grains in the interior. Hot tearing occurs at the junction between the vertical plate and the runner in all elbow castings of selected compositions, as summarized in Table IV. It appears that Mn addition increases the solidification shrinkage and degrades interdendritic feeding, and therefore increases the hot tearing susceptibility. In contrast, however, increasing Fe reduces the hot tearing susceptibility, although it increases the surface slumping of the casting. This may be due to the formation of coarse binary phase, which acts as bridges of the isolated primary Al dendrites and therefore strengthens the matrix enough to resist the shrinkage it induces. As indicated in Table IV, Si reduces the hot tearing susceptibility while Sr has a negligible effect on hot tearing under the present conditions. V. DISCUSSION A. Comparison between Observations Made in the Present Study and Thermocalc Predictions Since Thermocalc was developed based on the equilibrium assumption, it cannot predict any effect of Sr addition. Therefore, the effect of Sr will not be included in the folMETALLURGICAL AND MATERIALS TRANSACTIONS A

As a result, phase is converted into phase by rejecting Si ahead of the platelets. However, as demonstrated earlier, this reaction takes place across the samples irrespective of the Sr level in the sample. Figure 9 compares the microstructures of the samples without and with Sr addition. While the platelets in the samples with Sr added were slightly refined compared to those in the sample with a similar Fe level but without Sr addition, the effect of Sr on the platelets is less significant than that reported in the literature.[21,23] This may be attributed to a much lower Sr level employed here. The Sr was also found to slightly depress the precipitation temperature of the binary phase according to the thermal analysis. The reason for the depression of precipitation temperature due to Sr addition is not yet understood. It may be related to the effect of Sr on the surface tension of the melts, which may negatively change the nucleation and growth of the phase. A further mechanism could involve entrained oxides, which have recently been suggested to nucleate the phase. Strontium is known to be a surface-active element, thereby potentially altering the characteristics of the oxide films.[17,25,26] Furthermore, strontium could form intermetallics on the surface of the potential nucleants for the phase. IV. EFFECT OF IRON-RICH INTERMETALLIC PHASES ON THE FORMATION OF CASTING DEFECTS A. Casting Porosity Figure 10 illustrates the macrographs of sectioned surfaces, taken under indirect illumination conditions, of the castings solidified at a cooling rate of about 1 C/sec from the melts of selected compositions. Porosity was observed to different extents in all castings. At a low iron content of 0.3 pct in Figure 10(a), sponge-like pores were observed in the center of the casting, which probably solidifies last when feeding becomes difficult. The formation of ternary platelets during the eutectic solidification is believed to be responsible for the formation of such sponge-like pores. Increasing Fe content from 0.3 to 0.7 pct, the casting in Figure 10(b) shows a similar level of porosity, but distributed across a wider area. This is likely due to the precipitation of coarse binary platelets prior to the eutectic solidification, which block the
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(a)

(b)

(c)
Fig. 9Microstructures of the samples quenched at the temperature immediately after Peak 2 in Figure 3 from the melts with and without Sr addition (a) 0.7 pct Fe, (b) 0.7 pct Fe 135 ppm Sr, and (c) 0.7 pct Fe 0.3 pct Mn 200 ppm Sr.
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(a)

(b)

(c)

(d )

(e)

(f)

Fig. 10Sectioned surface of the castings of selected compositions, indicating different degrees of casting porosity: (a) 0.3 pct Fe, (b) 0.7 pct Fe, (c) 0.7 pct Fe 0.3 pct Mn, (d) 0.7 pct Fe 10 pct Si, (e) 0.7 pct Fe 135ppm Sr, and (f ) 0.7 pct Fe 0.3 pct Mn 200ppm Sr.
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Table IV. Ratings of Casting Defects Observed in the Elbow Castings with Selected Compositions Alloys 0.3 pct Fe 0.7 pct Fe 0.7 pct Fe 135 ppm Sr 0.7 pct Fe 0.3 pct Mn 0.7 pct Fe 10 pct Si 0.7 pct Fe 0.3 pct Mn 10 pct Si Overall Surface Slumping A B C D 3 6 4 9 4 8 Hot Tearing 3 2 2 3 1 2

phase can precipitate prior to the eutectic Si. The total amount of phase increases with the amount of Fe added. In Figure 11(a), both manganese and silicon were found to strongly depress the precipitation of the coarse binary . However, Si will not reduce the total amount of phases present in the structure as Mn does. While suppressing the phase, Mn is predicted to promote the precipitation of phase, as shown in Figure 11(b). Overall, Mn increases the total amount of Fe-rich intermetallic phases despite the significant decrease in the amount of phase formed. Furthermore, addition of Si will not change the total amount of Fe-rich intermetallic phases. Unlike our observations, no phase was expected to precipitate prior to the eutectic Si at 10 pct Si and 0.3 pct Mn from Thermocalcs prediction. The reason for the discrepancy between the Thermocalc predictions and our experimental observations can be attributed to the equilibrium assumption on which Thermocalc is based. It is worthwhile mentioning that, according to the Thermocalc prediction in Figure 11(b), phase can precipitate across a wide temperature range and even prior to the primary Al in case of 10 pct Si, 0.7 pct Fe, and 0.3 pct Mn, causing sludge problems. It is also worthwhile mentioning that Thermocalc has predicted the presence of the quaternary eutectic reaction (Reaction 5 in Table III), which involves the formation of phase. However, it cannot predict the phase formed via the peritectic reaction (Reaction 6 in Table III). This is because the Thermocalc model is based on the Scheil equation, which neglects any solid-state diffusion. B. Possibility of for Eutectic Si Phase as a Nucleation Site

(a)

(b)
Fig. 11Precipitation of (a) and (b) phases predicted using Thermocalc.

lowing discussion. As shown in Figure 11, the weight fractions of both and phases predicted using Thermocalc (version 2.00) agree qualitatively with the experimental observations made earlier. Based on the Thermocalc predictions, two major Fe-rich intermetallic phases, i.e., and , may be present in the structure, depending on the melt composition. No phase was predicted to form if only Fe was added to the melt. Generally, at low Fe contents, phase is expected to form at a lower temperature through a ternary eutectic reaction. At higher iron contents, a considerable amount of
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As mentioned in Section I, phase has been suggested as a possible nucleant for eutectic Si. This argument was mainly based on the observation that phase was often found to coexist or occur in close contact with eutectic Si. However, no direct evidence has yet been produced to demonstrate that eutectic Si actually nucleates on and grows from the phase. Our earlier observations have revealed two types of phase in the microstructure: one precipitates prior to the eutectic Si while the other forms via a ternary eutectic reaction. Figure 12 shows the microstructures of samples quenched during the eutectic arrest from the melts with additions of about 0.3 pct Fe, 0.7 pct Fe, and 0.7 pct Fe 0.3 pct Mn, respectively. In addition to the primary Al, , and formed prior to the quenching test, the growing eutectic grains are also observed. If the phase is a potent nucleant for eutectic Si, one would expect that it will dictate the spatial distribution of eutectic grains and significantly increase the number of eutectic grains in the last two cases due to the presence of needles in the melts. However, Figure 12 shows only negligible changes both in the spatial distribution and the number of eutectic grains, although there are a large amount of needles available in the structure in the last two cases. The eutectic grains were observed across the entire area as expected and were not necessarily related to the needles spatially. Therefore, it is believed that the eutectic grains are nucleated independently of the phase. The microstructures in Figure 13 were taken from the samples solidified without interruptions from the melts with the compositions of 0.3 pct Fe, 0.7 pct Fe, and 0.7 pct Fe
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(a)

(b)

(c)
Fig. 12Microstructures of samples quenched at 100 sec after the beginning of the eutectic arrest from the melts with varying additions of Fe and Mn: (a) 0.3 pct Fe, (b) 0.7 pct Fe, and (c) 0.7 pct Fe 0.3 pct Mn. Letter A represents the growing eutectic grains.
832VOLUME 36A, MARCH 2005 METALLURGICAL AND MATERIALS TRANSACTIONS A

(a)

(b)

(c)
Fig. 13Microstructures of samples fully solidified from the melts with varying additions of Fe and Mn: (a) 0.3 pct Fe, (b) 0.7 pct Fe, and (c) 0.7 pct Fe 0.3 pct Mn.
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Table V. Crystal Structural Parameters of Si and Crystal Structure C C M M Lattice Parameters(A) a 5.43088 5.451 6.12 5.792 b 6.12 12.273 c 41.5 4.313 d Spacing between Two Densest Planes(A) 3.1355 3.14 1.943 1.946 (1,1,1) (1,1,1) (1,1,19) (1,5,1)

Phase* d Spacing between Two Second Densest Planes(A) 1.9201 1.93 5.200 4.250 (2,2,0) (2,2,0) (0,0,8) (0,0,1) d Spacing between TwoThird Densest Planes(A) 1.6375 1.64 4.270 2.047 (3,1,1) (3,1,1) (0,1,7) ( 1,5,1)

Phase Si AlP -Al5FeSi (200031) -Al5FeSi (491499)

*X-ray powder data files are retrieved from the database PCPDFWIN (version 2.02), which was complied under auspices of JCPDSInternational Centre for Diffraction Data (ICDD) in 1999.

0.3 pct Mn, respectively. All samples shown in Figure 13 have displayed a similar ternary eutectic (Al Si ), which formed via L S Al Si b [3]

Since the phase and Si are two of three phases in the suggested ternary eutectic reaction, they are expected to be closely related spatially. Since Si and are both faceted phases, they tend to form an irregular eutectic structure, as observed in Figure 13. There is no evidence suggesting that the phase has acted as a nucleation site for the eutectic Si. It appears that these two phases intercept each other during growth and grow in a coupled mode. It has also been argued that phase may be a potent nucleant for Si due to the similarity in their crystal structure. Table V compares the crystal structural parameters of synthetic Si to those of two types of phase. It is clear that despite certain similarities in d spacing among some of the three densest planes huge difference exists in the unit cell structure between Si and phase. This alone is not enough to demonstrate its potency as a nucleant for eutectic Si. C. Nucleation of Fe-Rich Intermetallic Phases Based on the observations that the formation of a coarse brittle Fe-rich intermetallic phase can be completely suppressed in a well-modified alloy, Sigworth[20] suggested that P present in the melts (probably as AlP) has a role in nucleating such intermetallics. By combining with P, Sr is expected to deactivate the AlP particles in the melts, and therefore to depress the Fe-rich intermetallics. After observing the particles located along the long sides of the platelets, Samuel and co-workers[21,23] further suggested that these are AlP particles, which act as nucleation sites for the platelets. However, no evidence was provided in the article to support their suggestion that these particles are actually AlP. In fact, it is very difficult to keep the AlP particles intact during the normal procedure of metallographic sample preparation due to its strong tendency to react with water. The crystal structural parameters of AlP are also listed in Table V. While a good lattice match exists between AlP and Si, there is only a limited similarity between AlP and . A melt with a nominal level of 100 ppm P and 0.7 pct Fe was therefore prepared in this investigation to study the possible role of AlP in nucleating the platelets. A higher than normal P level was used to ensure the formation of AlP in the melt. Unfortunately, no particles were observed sit834VOLUME 36A, MARCH 2005

ting along the platelets as suggested in the literature. The Sr has been demonstrated to deactivate the AlP particles. If AlP indeed acts as a nucleation site for the platelets, then further addition of Sr is expected to decrease the number of the platelets. However, a negligible effect of Sr addition was observed in the present investigation. More recently, after assessing the structure mismatch between typical oxides usually found in aluminum casting alloys and the -Fe intermetallic phase using the planar disregistry, Campbell and co-workers[17,26] and Penners et al.[21] proposed that the Fe-rich intermetallics nucleate and grow on the external, wetted surfaces of the oxide bifilms, which are entrained into the melts during the pouring operation. They have applied this mechanism to explain the commonly observed central cracks in and around some intermetallics and the aluminum matrix. It was believed that the gap between the two inner, dry sides of a bifilm in aluminum casting alloys constitutes a crack. Bearing this theory in mind, the authors have carefully examined all the samples from this study in order to confirm the presence of the central cracks and oxide bifilms in and around the Fe-rich intermetallic precipitates. However, as evidenced in all the micrographs in the previous sections, no cracks were observed. This may be because Cao and Campbell employed a special entrainment process in their investigation to incorporate oxide film into the melts.[26] This process permits formation of the folded oxides and precipitation of the Fe-rich intermetallics in the melts under a convection-free environment. However, in the present investigation, the liquid sample was taken by submerging a preheated stainless steel ladle into the carefully skimmed melt and was allowed to solidify immediately at a cooling rate of 1 C/sec. This sampling procedure and cooling condition may not facilitate the formation of oxide bifilms in the samples, on which the Fe-rich intermetallics nucleate and grow.

VI. CONCLUSIONS 1. Three different types of Fe-rich intermetallic phases including , , and have been identified across the samples based on the phase composition and morphology. The experimental observations generally agree with the Thermocalc predictions. 2. Increasing the Fe content changes the precipitation sequence of the phase. At low iron contents, the phase is expected to form at a lower temperature through a ternary eutectic reaction. At higher iron contents, the majority of phase precipitates prior to the eutectic Si, leading to the formation of coarse, binary platelets. This coarse phase may
METALLURGICAL AND MATERIALS TRANSACTIONS A

3.

4.

5.

6. 7.

block feeding channels earlier, and cause feeding problems and casting porosity. In addition, increasing Fe content reduces the hot tearing susceptibility, although it increases the overall surface slumping of the castings. Strontium slightly depresses the precipitation temperature of phase and produces a little finer phase. It was also found that addition of Sr to the melt has changed the mode of the eutectic nucleation. As a result, it reduces the overall surface slumping and redistributes casting porosity. The Sr addition has a negligible impact on hot tearing susceptibility under the present conditions. Manganese suppresses the formation of coarse binary phase and replaces it with a more compact and less harmful phase. Despite its benefit in modifying the Fe-rich intermetallics, it increases the total amount of iron-rich intermetallic phases. The Mn addition increases the overall surface slumping and the hot tearing susceptibility. Addition of Mn caused no significant change in casting porosity level and all sponge-like pores are seemingly concentrated in the center of the casting. Increasing silicon helps suppress the coarse binary phase. However, it will not increase the total amount of iron-rich intermetallic phases present in the microstructure as Mn does. Therefore, increasing Si content is expected to reduce overall surface slumping and hot tearing susceptibility as well as casting porosity. No increase in the number of platelets was observed with the addition of P, nor were AlP particles found along the sides of the platelets. No evidence was found to suggest that needles nucleate the eutectic Si. The role of the oxide bifilms as a heterogeneous substrate of Fe-intermetallics was also discussed. No central cracks were found to be present in and around the Fe-rich intermetallic precipitates in the present investigation. ACKNOWLEDGMENTS

REFERENCES
1. J.A. Taylor, G.B. Schaffer, and D.H. StJohn: Metall. Mater. Trans. A, 1999, vol. 30A, pp. 1643-50. 2. J.A. Taylor, G.B. Schaffer, and D.H. StJohn: Metall. Mater. Trans. A, 1999, vol. 30A, pp. 1657-62. 3. J.A. Taylor, G.B. Schaffer, and D.H. StJohn: Metall. Mater. Trans. A, 1999, vol. 30A, pp. 1651-55. 4. M.O. Otte: PhD. Thesis, University of Queensland, Brisbane, 2000. 5. H. Iwahori, H. Takamiya, K. Yonekura ,Y. Yamamoto, and M. Nakamura: Imono, 1988, vol. 60, pp. 590-95. 6. P.N. Crepeau: AFS Trans., 1995, vol. 103, pp. 361-66. 7. T.O. Mbuya, B.O. Odera, and S.P. Nganga: Int. J. Cast Met. Res., 2003, vol. 16 (5), pp. 451-65. 8. A. Couture: Int. J. Cast Met. Res., 1981, vol. 6 (4), pp. 9-17. 9. W. Khalifa, F.H. Samuel, and J.E. Gruzleski: Metall. Mater. Trans. A, 2003, vol. 34A, pp. 807-25. 10. L. Backerud, G. Chai, and J. Tamminen: Solidification of Characteristics of Aluminium Alloys: Volume 2Foundry Alloys, AFS/Skanalumium, Des Plaines, IL, 1990, pp. 1-255. 11. N. Roy, A.M. Samuel, and F.H. Samuel: Metall. Mater. Trans. A, 1996, vol. 27A, pp. 415-29. 12. L.A. Narayanan and F.H. Samuel: AFS Trans., 1992, vol. 100, pp. 383-91. 13. L. Liu, A.M. Samuel, F.H. Samuel, H.W. Doty, and S. Valtierra: Int. J. Cast Met., 2003, vol. 16 (4), pp. 397-408. 14. L.F. Mondolfo: Manganese in Aluminium Alloys, The Manganese Centre, Neuilly sur Seine, France, 1978. 15. G.K. Sigworth, S. Shivkumar, and D. Apelian: Trans. Am. Foundrymens Soc., 1989, vol. 97, p. 811. 16. S.G. Shabestari and J.E. Gruzleski: Cast Met., 1994, vol. 6 (4), pp. 217-24. 17. S.G. Shabestari, M. Mahmudi, M. Emamy, and J. Campbell: Int. J. Cast Met. Res., 2002, vol. 15 (1), pp. 17-24. 18. A.N. Lakshmanan, S.G. Shabestari, and J.E. Gruzleski: Z. Metallkd., 1995, vol. 86 (7), pp. 457-64. 19. F.H. Samuel and A.M. Samuel: Int. J. Cast Met. Res., 1997, vol. 10 (3), pp. 147-57. 20. G.K. Sigworth: Modern Casting, 1987, vol. 77 (7), pp. 23-25. 21. A. Pennors, A.M. Samuel, F.H. Samuel, and H.W. Doty: Trans. Am., Foundrymens Soc., 1998, vol. 106, pp. 251-64. 22. F.H. Samuel, G. Pucella, C. Villeneuve, A.M. Samuel, H.W. Doty, and S. Valtierra: Int. J. Cast Met. Res., 1999, vol. 12 (3), pp. 197-210. 23. A.M. Samuel, A. Pennors, C. Villeneuve, F.H. Samuel, H.W. Doty, and S. Valtierra: Int. J. Cast Met. Res., 2000, vol. 13 (4), pp. 231-53. 24. S.G. Shabestari and J.E. Gruzleski: Trans. Am. Foundrymens Soc., 1995, vol. 103, pp. 285-93. 25. J. Campbell: Castings, Butterworth Heinemann, Oxford, United Kingdom, 2003, p. 335. 26. X. Cao and J. Campbell: Metall. Mater. Trans. A, 2003, vol. 34A, pp. 1409-20. 27. A.K. Dahle, J.A. Taylor, and D.A. Graham: Alum. Trans., 2000, vol. 3 (1), pp. 17-30. 28. M.A. Easton and D.H. StJohn: Int. J. Cast Met., 2000, vol. 12, pp. 393-408. 29. A.K. Dahle, K. Nogita, J.W. Zindel, S.D. McDonald, and L.M. Hogan: Metall. Mater. Trans. A, 2001, vol. 32A, pp. 949-59.

The authors acknowledge the financial support of the Cooperative Research Centre for Cast Metals Manufacturing (CAST). CAST was established and is supported by the Australian Governments Cooperative Research Centres Program. LSM and Comalco are acknowledged for supplying the master alloys and the commercial purity aluminum ingot, respectively, and Elkem Silicon for supplying the silicon used in this research.

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