Trans Indian Inst Met (December 2012) 65(6):553557 DOI 10.

1007/s12666-012-0221-y

TECHNICAL PAPER

TP 2589

Fe Bearing Intermetallic Phase Formation in a Wrought AlMgSi Alloy

S. Kumar P. S. Grant K. A. Q. OReilly

Received: 6 July 2012 / Accepted: 16 September 2012 / Published online: 10 October 2012 Indian Institute of Metals 2012

Abstract This paper investigates the two dimensional (2D) and three dimensional (3D) morphologies of the Fe bearing intermetallics that forms during the direct chill casting of an AA6063 Al alloy. An intermetallic phase extraction technique was used to facilitate 3D interconnectivity, morphology and fraction of intermetallics. Metallographic 2D analyses suggest the presence of Chinese-script-type and needle-type morphology Fe bearing intermetallics typically at the primary Al grain boundaries, whereas 3D analyse of the extracted intermetallics suggests those particles have dendrite-type and platelet-type morphologies. In-addition, globular shaped intermetallics which were observed in 2D within the primary Al grains where observed to have sphere shaped rosette-type morphology in 3D. ac-AlFeSi and b-AlFeSi were the two dominant intermetallic phases observed in the as-cast billet. Clusters of Ti rich particles were observed at the point from which growth appears to have started suggesting a possible nucleating site for the Fe intermetallics to form during solidication. Keywords AA6063 Al alloy DC casting Intermetallics Extraction

1 Introduction Due to superior strength, good formability and heat-treatability, AlMgSi (6xxx series) alloys have found potential
S. Kumar (&) P. S. Grant K. A. Q. OReilly Department of Materials, The EPSRC Centre for Innovative Manufacturing in Liquid Metal Engineering, University of Oxford, Oxford OX1 3PH, UK e-mail: kumar.sundaram@materials.ox.ac.uk

applications as structural materials in the automotive and building industries. Most commercial wrought Al alloys are cast using the direct chill (DC) casting process [1]. During solidication, the solid solubility of the minor alloying elements (Fe, Si, Mn and Mg) in the primary Al decreases, as a result they tend to segregate to the liquid that is the lost to solidify. Hence, this results in the formation of complex intermetallics at the cell and grain boundaries. Since the solidication conditions in DC casting are non-equilibrium, the type of intermetallic that forms may vary [2]. In-order to modify the as-cast Fe bearing intermetallics into more favourable forms for downstream processing, the cast billet is usually subjected to heat treatment. The necessity to increase the use of recycled aluminium pushes casting technologies to tolerate higher impurity content, particularly Fe [3]. Therefore, in-order to develop advanced casting technologies and heat treatment processing routes for recycled alloys it is essential to understand the nature of the intermetallics that form during DC casting. There is considerable literature available to understand the type of Fe bearing intermetallic in DC cast 6xxx series Al alloys billet specically focused on two dimensional (2D) metallographic analysis [4, 5], but very few investigations are available concerning 3D morphological analysis [6]. Therefore in this study, the 3D morphological nature of the Fe bearing intermetallic particles that form during DC casting is investigated. A phase extraction technique is used to facilitate observation of the 3D nature of the intermetallic particles by dissolving the Al matrix [7]. In-addition inclusions in liquid metals are inevitable. They either enter through inoculant additions or form in situ during liquid metal handling. This paper also highlights the possible role of inclusions on the intermetallic phase formation during solidication.

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2 Experimental Details The elemental composition of the AA6063 Al alloy used in this study is 0.45Mg, 0.41Si, 0.19Fe, 0.07Mn, 0.01Cu, 0.01Ti and balance Al (all in wt%). The alloy was DC cast into a 190 mm billet. The billet was analysed across its cross-section. The mounted samples were grounded and mechanically polished with a colloidal silica suspension having a grain size of 0.04 lm for 2D microstructural analysis. For grain size analysis the samples were anodised using Barkers reagent (7 ml HBF4 [48 %], 93 ml H2O) at 20 V for 60 s. Grain size and dendrite arm spacing (DAS) were measured using the mean liner intercept method on the polarised images taken using a Zeiss Axiophot2 optical microscope. Intermetallic particles were extracted by dissolving the Al matrix using anhydrous boiling butan-1-ol (butanol) while keeping the intermetallics intact. The intermetallics were then collected on a polytetrauoroethylene lter paper with pore size of 2 lm. A Philips 1700 X-ray diffractometer (XRD) was used for the phase identication. A JEOL 840A scanning electron microscope (SEM) equipped with secondary electron and back-scattered electron (BSE) detectors and an energy-dispersive X-ray spectrometer (EDS) was used to analyse the intermetallic phases. A JEOL 840F eld emission gun (FEG) SEM was used for high resolution images.

grains. The average grain size and DAS of the primary Al at the centre of the cast billet is 102 13 and 30 7 lm, respectively. It is interesting to note that the large aspect ratio containing discrete particles are decorated along the primary Al grain boundaries (Fig. 1). In-addition to these grain boundary particles, ne spherical shaped particles were observed within the primary Al grains. SEM 2D metallographic analysis reveals that those large aspect ratio intermetallic particles were either in the form of Chinesescript-type (Fig. 2a) or needle-type (Fig. 2b) morphologies. Further, the spherical shaped particles were observed to have rosette-type (Fig. 2c) morphology. The EDS analysis of the metallographic samples revealed a narrow range of Fe:Si ratio within these intermetallics. Among these intermetallics, the Chinese-script-type particles have higher (4.3) Fe:Si ratios than the needle-type (2.4) ones. 3.2 3D Analysis In-order to understand the 3D nature of these intermetallics it is essential to remove the Al matrix and analyses the extracted particles. It is very interesting to note that these extracted intermetallics were well interconnected (Fig. 3) and they are typically more than two hundred of microns in length, which could not be ascertained from the 2D observations made of the metallographic samples. Therefore it may not be appropriate to characterise the Fe bearing intermetallic using only 2D metallographic samples. Such lengthy and well interconnected intermetallics have been observed to usually form along the grain boundaries. It is also interesting to note that the intermetallics which were observed with the Chinese-script-type and needle-type morphologies seen in 2D were observed to have dendrite-type (Fig. 4a) and platelet-type (Fig. 4b) morphologies in 3D analysis, respectively. In-addition, the intermetallics which were observed within the primary Al grains have a very different rosette-type 3D morphology (Fig. 4c). XRD analysis of the extracted particles revealed that ac-AlFeSi and b-AlFeSi are the two dominant as-cast Fe bearing intermetallic phases observed in this alloy (Fig. 5).

3 Results 3.1 2D Analysis Anodised microstructures of the sample from the centre (Fig. 1) of the cast billet suggest ne equiaxed primary Al

4 Discussion 4.1 Solidication and Phase Selection Due to non-equilibrium solidication conditions in DC casting and the low solid solubility of solute elements (Fe, Si) in Al, excess solute tends to segregate into the liquid at solidliquid interface. This solute rich liquid will be the last to solidify and results in the formation of various

Fig. 1 Optical micrograph shows the primary Al grains, where the label A denotes the location of large aspect ratio particles and label S denotes the location of ne spherical particles

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Fig. 3 FEG-SEM image of an extracted intermetallic showing a well interconnected intermetallic network

Fig. 2 BSE-SEM images showing 2D morphology of the different Fe bearing intermetallics observed in the metallographic sample. Where a Chinese-script-type, b needle-type and c rosette-type particles, respectively

intermetallic phases. The anodised microstructure clearly reveals that these intermetallic phases mostly form at the grain and cell boundaries. Thermodynamic calculation using PandaT simulation [8] suggest that the primary Al is the rst phase to form during solidication and followed by Al13Fe4, ac-AlFeSi, b-AlFeSi and Mg2Si as temperature lowers. These intermetallic phases form as the result of various eutectic and peritecitc solidication reactions. The absence of Al13Fe4 in the present billet suggests that the

corresponding reaction might be suppressed or allowed to transform to different phase. The absence of Mg2Si in the XRD pattern is not unusual for as-cast alloy and is likely to be due to Mg2Si being present below the detection limit of the XRD. For a given local composition, intermetallic phase selection is determined by two criteria: competitive nucleation and competitive growth [2]. Competitive nucleation favours the intermetallics which have high nucleation temperatures or low under-cooling for nucleation, whereas competitive growth favours the phase having the higher growth temperature or higher growth rate. The nucleation of Fe bearing intermetallic phases may be enhanced by the presence of potent nucleating substrates such as preformed primary Al or pre-solidied reaction products or inclusions. Interestingly in the present study, Ti rich particle and oxide particle clusters were frequently observed to be associated with ac-AlFeSi and b-AlFeSi. Figure 6a shows a cluster of TiB particles associated with a b-AlFeSi platelet, suggesting TiB acted as a nucleating substrate. The higher magnication of this cluster shows (Fig. 6b) typical hexagonal morphology of TiB2 particles. TEM analysis [9] showed the existence of good lattice matching between TiB2 and b-AlFeSi. Such Fe bearing intermetallics nucleated in this way have been observed to have distinct points of origin. Figure 4a shows a petal-like dendrite-type ac-AlFeSi particle growing from a central point. EDS analysis revealed the presence of Ti rich particles at this location and suggests it as the point of origin for the petals. Inclusions such as TiB2 and oxides may nucleate the Fe bearing intermetallics either directly or through forming an intermediate compound. Thus inclusions can trigger intermetallic phase selection.

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c-AlFeSi -AlFeSi

Intensity (A.U)
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Fig. 5 XRD pattern from the extracted particles

a higher Fe:Si than b-AlFeSi. Therefore it is the combination of competitive nucleation, competitive growth and local composition which ultimately governs the phase selection. 4.2 Intermetallic Morphology Both ac-AlFeSi and b-AlFeSi have been observed at grain boundaries. Usually grain boundary ac-AlFeSi has petallike dendrite-type morphology with smooth and ripple surfaces. The side edges of these particles as either faceted or dendrite-like in nature. The multiple growth nature of this ac-AlFeSi is due to its cubic crystal structure, which helps to adopt different growth shapes according to the local solute or thermal uctuations. b-AlFeSi has usually been observed to have faceted platelet-type morphology (note that literature usually says needles) with rough surface. The side edges of these platelets have large growth steps and ridge lines. The faceted platelet nature of b-AlFeSi is due to monoclinic crystal structure. It was interesting to note the branching ability of these platelets which is contrary to reports in the literature that claim that b change its growth direction and hence only grows in one direction. Re-entrant twin edge growth and step growth is seems to be the main growth mechanisms for b-AlFeSi. In-addition to these large aspect ratio intermetallics it was very interesting to note the ne globular intermetallics within grains. The 3D metallographic analysis revealed these to spherical rosette-type morphologies. These spheres-like particles are made up of clusters of nano-sized ne particles. TEM analysis [11] of similar particles revealed that they are ne polycrystalline ac-AlFeSi particles. Such ne sized particles would only be able to form at high cooling rates. During solidication, as the primary Al dendritic arms grow, it is possible for the dendrite tips to

Fig. 4 FEG-SEM images of extracted Fe bearing intermetallic particles showing a dendrite-type ac-AlFeSi, b platelet-type b-AlFeSi and c rosette-type ac-AlFeSi

Though the inclusion helps the nucleation criteria on the intermetallic phase selection, the growth criteria must also play a further role. For a given growth velocity, the phases having the higher growth temperature will be thermodynamically favourable for growth. Though the inclusions nucleate a particular phase, if the growth criteria is not favourable than it is possible that later in the solidication process a different intermetallic will dominate. In-addition the local chemical composition plays a signicant role in the solidication reaction, especially Si [10]. Of the two phases that have been observed in this study, ac-AlFeSi has

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Trans Indian Inst Met (December 2012) 65(6):553557 Fig. 6 FEG-SEM images showing Ti rich particles associated with platelet-type b-AlFeSi. Where b is the higher magnication image of the arrow make in a indicates the location of Ti rich particles cluster

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split and engulf small pockets of solute rich liquid or such pockets also can form between secondary dendrite arms. These pockets of entrapped solute rich liquid may not contain active nuclei and therefore may under cool well below the ac-AlFeSi and Al eutectic reaction temperature. Thus there may be copious nucleation in this super cooled liquid resulting in rapid freezing and the formation of clusters of ne nano-sized ac-AlFeSi particles, as observed. It is important to note that most of these spherical type particles were found separate without interconnectivity, this further supports that these intermetallics form from isolated liquid. Intermetallics morphology inuences the physical properties of the nal product. It has been reported that needle/platelet-type morphology containing intermetallic is detrimental to mechanical properties [12].

wrought Al alloys. Therefore it is essential to develop processing routes which can reduce this intermetallic interconnectivity.
Acknowledgments The authors would like to acknowledge the nancial support of SAPA and EPSRC Centre for Innovative Manufacturing in Liquid Metal Engineering and Feng Yan, of the Brunel University, UK, for providing the PandaT data.

References
1. Eskin D G, Physical Metallurgy of Direct Chill Casting of Aluminum Alloys, Taylor and Francis Group, Oxford (2008), p 8. 2. Allen C M, OReilly K A Q, Cantor B, and Evans P V, Prog Mater Sci 43 (1998) 89. 3. Kumar S, Hari Babu N, Scamans G M, Eskin D G, and Fan Z, Int J Mater Res. http://www.ijmr.de/MK110760 4. Onurlu S, and Tekin A, J Mater Sci 29 (1994) 1652. 5. Tanihata H, Sugawara T, Matsuda K, and Ikeno S, J Mater Sci 34 (1999) 1205. 6. Sweet L, Zhi S M, Gao S X, Taiylor J A, and Easton M A, Metall Mater Trans A 42 (2011) 1737. 7. Verma A, Kumar S, Grant P S, and OReilly K A Q, in Proceedings of the International Conference of Aluminium Alloys, (eds) Weiland H, Rollett A D, and Cassada W A, Pittsburgh (2012), p 1413. 8. http://www.computherm.com/pandat.html. Accessed 5 July 2012 9. Sha G, Intermetallic Phase Selection in 6xxx Series Al Alloys, D. Phil. Thesis, University of Oxford (2001). 10. Langsrud Y, Key Eng Mater 44&45 (1990) 95. 11. Hsu C, OReilly K A Q, Cantor B, and Hamerton B, Mater Sci Eng A 304306 (2001) 119. 12. Zajac S, Hutchinson B, Johansson A, and Gullman L O, Mater Sci Technol 10 (1994) 323.

5 Conclusions In this AA6063 alloy DC cast billet, ac-AlFeSi and b-AlFeSi were the two dominant Fe bearing intermetallic phases. Grain boundary ac-AlFeSi has a dendrite-type morphology whereas b-AlFeSi has a platelet-type morphology. ac-AlFeSi which was observed within the Al grains can have a sphere like rosette-type morphology. Other than this spherical type particle, most of the Fe bearing intermetallic that were observed at the grain boundaries and cell boundaries of the primary Al where well interconnected. Interconnectivity plays a crucial role in the downstream, secondary deformation processing of

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