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Scripta Materialia 64 (2011) 11211124 www.elsevier.com/locate/scriptamat

Grain rening potency of AlB master alloy on pure aluminum

Tongmin Wang, Zongning Chen, Hongwang Fu, Jun Xu, Ying Fu and Tingju Li
School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, Peoples Republic of China
Received 3 January 2011; accepted 2 March 2011 Available online 8 March 2011

AlB master alloys were ascertained to be ecient grain reners on pure aluminum. Without introducing any stirring during reaction, three experimental Al3B master alloys were prepared via the halide salt route by varying the salt addition temperature, i.e. 750, 850 and 950 C. All of them showed grain rening potency on pure aluminum and that with the 950 C addition temperature was found to be the most ecient. Resistance to fading was also noted during holding after inoculation with this master alloy. Crown Copyright 2011 Published by Elsevier Ltd. on behalf of Acta Materialia Inc. All rights reserved.
Keywords: Casting; Scanning electron microscope (SEM); Aluminum; Grain rening; AlB master alloy

A ne, equiaxed a-Al grain structure imparts high toughness, high yield strength, excellent formability and improved machinability to castings [13]. Commercial aluminum alloys rely mainly on grain rener master alloys to control the grain size of the castings [4,5]. The most popular grain reners are AlTiB master alloys, the use of which for grain renement has been an established practice in aluminum foundries ever since boron addition was shown to remarkably improve the grain renement of aluminum by titanium at hypoperitectic concentrations [6]. The Ti-rich AlTiB reners are known to perform adequately for wrought aluminum alloys and much effort has been made to optimize the processing methods for the production of Al5TiB master alloy with consistent and better performance [714]. In the case of AlSi foundry alloys with a content of Si of >2 wt.%, however, the rening eciency of Al5TiB is poor due to a poisoning eect [15]. It is generally believed that the high content of Si, which forms titanium silicides with Ti and impairs the heterogeneous nucleation potency of TiB2 and TiAl3 particles, is responsible for the poisoning phenomenon in the grain renement of Al Si alloys [1520]. There have been a number of attempts to overcome the poisoning eect. One eective method is to increase the addition level of Al5TiB master alloy, which is a costly solution and thus undesirable in practice [15 17,2123]. Another approach is to develop new reners

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with lower Ti content. AlB master alloys have been reported to possess better grain rening eciency on AlSi alloys than the Al5TiB rener [2426]. In spite of the good performance of the AlB reners, the mechanism for their grain renement is still unclear. It has been reported that the AlB2 particles in the AlB master alloy act as ecient nucleating sites, and the presence of Si enhances their nucleation potency [15]. Zhang et al. [27] predicted, using an edge-to-edge matching crystallographic model, that AlB2 is an eective nucleant similar to TiC and TiB2 but poorer than TiAl3. However, very few experimental proofs have been given to prove the nucleation potency of AlB2 particles when Si is absent. To the contrary, previous studies found that AlB master alloys with AlB2 particles cannot rene the grains of pure aluminum [18,25], and a recent study indicated that they are ecient grain reners of pure aluminum only at a high addition level [28]. These discrepancies cause confusion regarding the nucleation potency of AlB2 for Al grains and obscure the mechanism of grain renement with AlB master alloy. Consequently, it is very desirable to ascertain whether AlB master alloys are ecient grain reners of pure aluminum. Our present work focuses on the grain renement of AlB master alloy on pure aluminum. Three Al3B master alloys with dierent microstructural features were prepared by varying the synthesis temperature. They all showed rening potency on commercial pure aluminum even at a low addition level. It was found that AlB2 particles played an important role in the renement. This is direct evidence proving the nucleation potency of AlB2 itself on Al grains without the enhancement of Si, which could be helpful in understanding the

1359-6462/$ - see front matter Crown Copyright 2011 Published by Elsevier Ltd. on behalf of Acta Materialia Inc. All rights reserved. doi:10.1016/j.scriptamat.2011.03.001

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immanent grain rening mechanism of AlB and B-rich AlTiB master alloys on AlSi alloys. Al3B master alloys were synthesized in the laboratory by reacting KBF4 salt with molten aluminum via the popular halide salt route on a 150 g batch scale. The starting materials were pure aluminum (99.7% Al) and KBF4 powder (commercial purity). Aluminum ingot was rst cut and heated to the required temperature in a graphite crucible using a medium-frequency induction furnace to facilitate rapid melting. The molten metal thus obtained was transferred into a resistance furnace for the subsequent salt addition process. KBF4 salt, weighed to achieve a composition of Al3 wt.% B in the nal alloy, was compacted into a cylindrical block and added to the aluminum melt without stirring. Three experimental Al3B master alloys were produced under the same conditions except for the dierent addition temperatures, which ranged from 750 to 950 C (Table 1). The molten alloy was held at the addition temperature for 10 min. Subsequently, the melt was stirred with a graphite rod for 30 s and cast into a water-cooled copper mold after decanting the by-product KAlF salt from its surface. The microstructures and phases of the nal master alloys were investigated using scanning electron microscopy (SEM) and X-ray diraction (XRD) analysis. For studying the grain renement eciency of each Al3B rener, 400 g of pure aluminum (99.7% Al) was melted in a graphite crucible using the mediumfrequency induction furnace and then transferred into a mini resistance furnace to maintain the temperature of the melt within 710 10 C throughout the whole procedure. A reference sample was taken from the melt with the aim of identifying the grain size before inoculation. A 0.5 g quantity of each experimental master alloy was then inoculated into the melt. This brought the B concentration of the melt to be about 0.005 wt.%. The melt was stirred with a graphite rod for 30 s as soon as the inoculation completed. Samples were taken from the melt 2, 10, 30 and 60 min respectively after the inoculation and cast into a steel mold with a diameter of 25 mm and a height of 45 mm. The samples thus produced were sectioned 20 mm from the bottom and then ground using SiC paper up to 1500 mesh. After a standard polishing procedure, these samples were then etched with Poultons reagent for macrostructure examination. The quantitative analysis of grain size was carried out using the linear intercept method after etching the polished surface of each sample with 0.5% HF solution. The halide salt route, which involves the addition of KBF4 to molten aluminum to prepare the AlB master alloy, is expected to bring about the following reaction: 2KBF4 3Al 2KAlF4 AlB2 1

As shown in Figure 1a, the boride particles in alloy 1, produced with the addition temperature of 750 C, are ne, being smaller than 10 lm. The existence of AlB2 phase was identied by XRD analysis (Fig. 2a). Alloy 1 revealed a few AlB2 particles in its microstructure and is thus claimed to have a low B-pickup in the nal alloy. This is attributed to the lower salt addition temperature, which strongly decreases the reaction rate and thus the B recovery during the production of AlB master alloy. Alloy 2, produced with the salt addition at 850 C, has a dierent microstructural feature and B recovery with respect to alloy 1. A larger fraction of boride particles was found in alloy 2, indicating a higher B-pickup inside it (Fig. 1b). It is evident that the higher addition temperature promoted a more rapid reaction rate, which led to a higher B recovery in the given 10 min holding time. The majority of boride particles are strip-like in alloy 2. This is in accordance with another work, in which AlB master alloy was synthesized by adding AlB2 powder into molten aluminum [29]. AlB2 was conrmed to be the dominant phase in the XRD pattern (Fig. 2b), whereas a slight peak was also noted to be of AlB12.

Figure 1. The microstructure of the experimental Al3B reners produced in the present work: (a) alloy 1, (b) alloy 2 and (c) alloy 3.

Table 1. Processing conditions for the experimental Al3B master alloys. Alloy No. 1 2 3 Addition temperature (C) 750 850 950 Holding time (min) 10 10 10 Stirring No No No

Figure 2. The XRD spectra of (a) alloy 1, (b) alloy 2 and (c) alloy 3.

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The formation of AlB12 during the production of AlB master alloy has been reported previously, and is considered to result from the heat accumulation owing to the highly exothermic salt reaction [30,31] (T.M. Wang, Z.N. Chen, J. Xu, in preparation). The microstructural feature of alloy 3, produced at 950 C, was more complicated, as shown in Figure 1c. The population of boride particles is the highest among the three experimental master alloys. The strip-like AlB2 remained in the microstructure, while some block-like boride particles were also dispersed in the matrix. The XRD spectra of alloy 3, shown in Figure 2c, revealed a large fraction of AlB12 reections. Hence, the dispersed block-like boride particles are suggested to be the AlB12 phase. This is not surprising since alloy 3 was produced at 950 C, around which AlB2 is expected to decompose to yield AlB12 and molten aluminum via a reverse peritectic reaction [32]. Figure 3 clearly shows that the B content in AlB master alloy is vital to the grain rening performance. The experimental master alloys all showed grain rening potency on pure aluminum, though their eciencies were quite dierent. Alloy 1, in which the number of boride particles was rather small, was a poor rener. The performances of alloys 2 and 3 were better; in particular, alloy 3, with the highest B-pickup, exhibited an adequate grain rening eciency on pure aluminum. This is direct evidence proving the heterogeneous nucleation potency of AlB2 in molten aluminum, meeting the theoretical prediction reported in Ref. [27]. It is thus claimed that the AlB master alloys do have grain rening potency on pure aluminum, which is actually in disagreement with previous work [8,25,28]. This discrepancy is likely to be linked to the eect of stirring

Figure 4. Detailed grain size analysis of the grain rened samples.

during the salt reaction. The stirring action, usually employed to promote a more uniform reaction in the halide salt route, was abandoned in the present work because it may cause the coagulation of borides and the entrapment of residual salt, which have been proved to be detrimental to the grain rening eciency of AlTiB master alloys [8,9,11,12]. It has also been reported that AlB2 particles can rene aluminum only at an addition level above the AlB eutectic concentration, i.e. 0.022% [6,33]. The present work, however, proved that even with an addition level of 0.005% (or lower in the cases of alloy 1 and 2), AlB master alloy still has grain rening ecacy. The detailed grain size analysis of these samples is shown in Figure 4. The average grain sizes of the samples without inoculation were all around 800 lm. Alloy 1, with a few AlB2 particles in its matrix, almost lost its grain rening eciency within 60 min after inoculation (637 lm was the average grain size of the sample 60 min after inoculation). However, rejuvenations of grain renement were observed in the samples inoculated by alloy 2 and especially alloy 3 (358 and 320 lm, respectively, at 30 min compared with 263 and 182 lm, respectively, at 60 min after inoculation). This

Figure 3. The response of pure aluminum to grain renement with the experimental master alloys.

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is of great interest since such an Al3B master alloy may nd wide use where a long inoculation time is needed, such as continuous casting. The mechanism for this rejuvenation may be related to the existence of AlB12 in alloys 2 and 3. A slow peritectic transformation of AlB12 to AlB2 prolongs the dissolving time of boride particles and the AlB2 particles thus formed are able to act as new nucleating sites for aluminum nuclei [29,34]. It can be concluded that AlB master alloys do have grain rening potency on pure aluminum, even at an addition concentration below the AlB eutectic. It is believed that the nucleation potency of AlB2 in AlB master alloys mainly accounts for this. The master alloys produced at higher addition temperatures, i.e. 850 and 950 C with a holding time of 10 min, have shown not merely better grain rening performances but also resistance against fading after inoculation. The stirring action is assumed to be responsible for the discrepancy between the present work and others. Further eorts are needed to investigate the fading-resistant capability of AlB master alloys. The authors thank the National Natural Science Foundation of China (Nos. 50601003, 50971032, and 50874022), and New Century Excellent Talents in University (NCET-07-0137), Scientic Research Fund of Liaoning Provincial Education Department.
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