Research Summary

Aluminum Alloys

The Grain Renement of 6063 Aluminum Using Al-5Ti-1B and Al-3Ti-0.15C Grain Reners
P. Moldovan and Gabriela Popescu
The Al-Ti-B grain reners containing boride nucleant particles are used to promote a uniform microstructure throughout aluminum ingots and to suppress the growth of columnar grains. In addition, for the last eight years a new generation of Al-Ti-C grain reners has been used commercially in a wide range of alloy systems. This paper will compare the potency of the commercially available Al-5Ti-1B grain rener with that of the Al-3Ti-0.15C grain rener for the 6063 cast alloy. INTRODUCTION It is well known that the size of aluminum alloy grains depends on the state of the melt before casting.1 Alloy crystals grow starting from the nucleus of crystallization. For grain renement of aluminum alloys, treatment of the melt is necessary before casting to improve mechanical and casting properties. This grain renement also increases the alloys density, uniformity of response to heat treatment, extrusion, and improvement of surface nishing. The principal approach to grain renement is inoculation in the melt with a nucleating agent. In the grain renement of aluminum alloys, commercial ternary Al-Ti-B master alloys are added to suppress the growth of columnar grains and to promote the formation of equiaxed ne-grain structures throughout the casting. The common commercially available AlTi-B master alloys for wrought alloys are: Al-5Ti-1B, Al-5Ti-0.6B, Al-5Ti0.2B, Al-3Ti-1B, and Al-3Ti-0.2B.2 All of these grain reners have a Ti:B ratio greater than the value for stoichiometric TiB2 (%Ti/%B = 2.22), so they contain TiB2 particles and TiAl3 particles. TiAl3 particles go into solution after contact with liquid aluminum, and TiB2 insoluble
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particles act as good nucleation sites for aluminum grains. For an efficient nucleant, the interface between the nucleant and melt must be of higher energy than that between the nucleant and the solid crystal (NL > NS). Unfortunately, large clusters of TiB2 can cause quality problems such as porosity in foils for packaging, surface defects in lithographic sheets, and

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reduced mechanical properties of plates for structural applications in the aircraft industry.3,4 In the early 1980s, Alcoa initiated a program with its grain rener suppliers to develop a boron-free grain rener that would provide consistent as-cast grain size control in a variety of alloys.5 As a result, a commercial grain rener based on the Al-Ti-C system was introduced by Anglo-Blackwells in 1986. The alloy had a nominal composition of Al-6Ti-0.02C. Alloys such as Al-6Ti-0.02C had a high Ti:C ratio and consequently required substantial titanium additions to provide sufcient nucleant particles for effective grain renement. A lower Ti:C ratio was desired to reduce the addition rates; the Al-3Ti-0.15C grain rener was introduced commercially to meet this demand.5 A cooperative research program under the E.U. BriteEuram Program has been carried out to develop an improved Al-Ti-C grain rener of 5% titanium and 0.25% carbon. Al-3Ti-0.15C and Al-5Ti0.25C alloys have been tested in a wide range of alloy systems and under different casting conditions.28 The objective of this paper is to compare the potency of the commercially available grain rener Al-3Ti-0.15C with that of Al-5Ti-1B in a 6063 wrought alloy casting. See the sidebar for experimental procedures. CHARACTERISTICS OF COMMERCIAL GRAIN REFINERS Commercially available Al-Ti-B and Al-Ti-C grain reners in the form of 9-mm-diameter rods were used in these experiments. The chemical analysis results for the grain reners are summarized in Table A in the sidebar. For the purposes of optical examina59

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Figure 1. Backscattered electron and EDS quantitative results of (a) TiAl3 platelet, with 62.37 wt.% aluminum, 0.05 wt.% silicon, and 37.58 wt.% titanium, and (b) boride particles in an Al-5Ti-1B grain rener, with 63.61 wt.% boron, 28.93 wt.% aluminum, and 7.46 wt.% titanium.

EXPERIMENTAL PROCEDURES In order to evaluate the performance of the grain reners, samples of a 6063 alloy were prepared from commercial 99.7%Al, AlSi50, and AlMg10 master alloys. Aluminum was melted and superheated to a temperature between 720C and 750C under Fluxal 2 protection. After the addition of AlSi50 and AlMg10, the melt was stirred with a graphite rod for homogenization. The metallic bath was degassed with pure argon gas at a ow rate of 1.5L/min. for 10 min. The alloy was cast in the form of rods with a diameter of 30 mm. Disk samples were taken from the 6063 alloy for quantometer analysis. The results of the chemical analysis are, in weight percent, Si-0.427, Mg-0.466, Ni-0.002, Cu-0.001, Mn-0.025, Zn-0.002, Fe-0.183, and balance Al. The alloy was cut in pieces, cleaned, dried, and melted in an electrical furnace with Kanthal resistance into a Diamant crucible with a 2 kg capacity. Melt temperature was measured and automatically adjusted to hold at 700C throughout the experiment. A grain-rener addition of Al-Ti-B or Al-Ti-C was done once this temperature was established. The Al-3Ti-0.15C and Al-5Ti-1B grain reners (Table A) were inoculated into the melt and stirred about 2 min. The cast structures were microscopically studied. A quantitative microscopic analysis was performed on an Olympus BX60M microscope with a Hitachi KP-M1 video camera, using the Omnimet Express 4.0 analysis program. Also, the microstructural analysis was conducted using an XL30 ESEM electron microscope equipped with an energy dispersive system.
Table A. Chemical Analysis of the Grain Reners (wt.%) Grain Rener Al-Ti-B Al-Ti-C Ti 4.95 3.13 B 1.08 C 0.18 Fe 0.10 0.09 Si 0.04 0.06 V 0.09 0.12 Zn 0.01 0.01 Cu 0.01 0.01 Al Bal. Bal.

mean size being about 123 m. The sample rened with 2 g/kg Al3Ti-0.15C had a grain size of 42 m to 150 m with a mean size of about 94 m. DISCUSSION The Al-Ti-B grain reners are preferred over Al-Ti-C grain refiners to control the grain size of wrought aluminum alloys. Al-Ti-C grain reners have been developed mainly in response to aluminum industry requirements for reduced defects in foil and lithographic sheet alloys (1xxx and 8xxx), bright trim alloys (5xxx and 6xxx), and can stock alloys (3xxx and 5xxx).7 Al-3Ti-0.15C became commercially available in 19962 and has been most widely applied by the aluminum industry. It has been reported that the main reason for reduced agglomeration in the aluminum melt rened with Al-Ti-C grain rener compared with that treated with Al-Ti-B is that salts are not used in the manufacture of Al-Ti-C grain rener.6 With the 2 g/kg Al-3Ti-0.15C addition, the cast bars were better in terms of surface appearance than those

tion, transversal sections were cut from the rods and nished using standard metallographic techniques. Polished samples were deep etched in a dilute NaOH solution for examination using a scanning-electron microscope. The Al-Ti-B grain reners contain TiAl3 platelets and small TiB2 particles. From the quantitative analysis of the detected image, one can observe that the TiAl3 platelets are distributed relatively uniformly, with a maximum length of 120 m. From the energy-dispersive system (EDS) analysis (Figure 1), it can be noted that the blocky type of TiAl3 platelets contain aluminum, titanium, and silicon (as impurities). Small boride particles, no larger than 0.5 m, have been observed in the Al-5Ti-1B grain rener. Figure 2 shows the microstructure of Al-3Ti-0.15C. It can be observed that the grain rener contains platelets of TiAl 3 with a maximum length of 135 m and TiC particles with a maximum size of 1 m. GRAIN REFINERS: A PERFORMANCE EVALUATION Alcoa cold nger tests (ACF) were conducted to investigate the grainrening efciency of the Al-5Ti-1B and Al-3Ti-0.15C. Experience has
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shown that the Alcoa method is a good predictor of grain rener performance in commercial ingot-casting processes3,5 and is a good measure of the propensity for twinned columnar growth.6 The ACF test comprises a ceramic mold, preheated in a furnace at 730C prior to testing, into which the molten 6063 alloy is introduced before being solidied with a water-cooled copper cone. Solidication proceeds vertically from the top to the bottom of the mold. The samples were sectioned longitudinally and the sawed face of one half was surface-machined. This surface was macro-etched with Tuckers reagent (in volume percent, HCl-45, HF-15, HNO3-15, and H2O-25). To measure the grain size, a sample was cut from a location 25.4 mm below the copper chill. The sample was polished, microetched with 1% HF reagent, and the grain size was determined with quantitative microscopic analysis. Macrostructures produced by the ACF test are shown in Figure 3. Figure 4 shows the grain sizes measured as a function of addition rate. A ner grain size and almost fully equiaxed structure was achieved with Al-3Ti-0.15C. The sample rened using 2 g/kg Al-5Ti-1B had a grain size varying between 37 m and 208 m, the

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Figure 2. (a) Backscattered electron and EDS quantitative results of TiAl3 platelet, with 76.97 wt.% aluminum and 23.03 wt.% titanium, and (b) TiC particles distribution in an Al-3Ti-0.15C grain rener, with 22.49 wt.% carbon and 77.51 wt.% titanium.

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produced with Al-5Ti-1B. The Alcoa test samples have shown to be a good predictor for the onset of twinned columnar growth. The nal as-cast grain size in wrought alloys is dictated by the population of potent nuclei and constitution effects.2 As grain-rener additions, TiB2 and TiC particles provide potent substances for nucleation, according to the theory of heterogeneous nucleation. The effectiveness of an inoculant (TiB2 or TiC) depends on the wetting angle and the surface roughness. The titanium excess gained through the rapid dissolution of blocky TiAl3 particles contributes to the constitutional effect on growth of aluminum grains. The most important factors to stimulate borides and carbides in the nucleation of -Al are growth restriction and undercooling. Titanium greatly affects the growth restriction factor: GRF = m.C0.(k1) where m is the slope of the liquidus line (m = 35), C0 is the bulk solute (titanium) concentration, and k is the equilibrium partition coefcient between the melt and primary aluminum grains (k = 7). Titanium, therefore, provides a ne grain size as long as potential nuclei

300 Average Grain Size (m) 250 200 150 100 50 0

Al-5Ti-1B Al-3Ti-0.15C

0.5 1 1.5 2 2.5 Grain Refiner Addition Rate (g/kg)

Figure 4. Alcoa cold nger test data for 6063 alloy grain rened with Al-5Ti-1B and Al-3Ti-0.15C.

The efciency of Al-Ti-B and Al-Ti-C grain reners is inuenced by factors in the casting process: casting method, casting speed, metal treatment system, and ingot geometry. The casting speed and ingot geometry determine the solidication rate. An increased solidification rate provides an increased undercooling of the melt (i.e., it stimulates the nucleation of solid-phase grains). The casting technology affects the temperature gradients at the ingot surface.9 High-temperature gradients will facilitate the growth of columnar grains if there are enough potent nuclei (TiB2 or TiC) available, and there will also be larger differences between surface regions and the rest of the ingot.
References
1. P. Moldovan, Treatment of Molten Metals (Bucharest, Hungary, V.I.S. Print, 2001) pp. 309330. 2. Men G. Chu, Grain Refining of Commercial Aluminum Wrought Alloys, Light Metals 2002, ed. Wolfgang Schneider (Warrendale, PA: TMS, 2002), pp. 899907. 3. Hoefs et al., Development of an Improved AlTiC Master Alloy for the Grain Renement of Aluminum, Light Metals 1997, ed. R. Huglen (Warrendale, PA: TMS, 1997), pp. 777784. 4. M. Yun et al., A Study of TiCAl 315TM Grain Renement in a Roll Cast AA8111 Aluminum Alloys, Light Metals 2000, ed. R.D. Peterson (Warrendale, PA: TMS, 2000), pp. 857862. 5. A.J. Whitehead, S.A. Danilak, and D.A. Granger, The Development of a Commercial Al-3%Ti-0.15%C Grain Rening Master Alloy, Light Metals 1997, ed. R. Huglen (Warrendale, PA: TMS, 1997), pp. 785793. 6. Angela Hardman and David Young, The Grain Rening Performance of TICAR Master Alloy in Various Aluminum Alloy Systems, Light Metals 1998, ed. B.J. Welch (Warrendale, PA: TMS, 1998), pp. 983988. 7. W. Schneiner et al., A Comparison of the Behaviour of AlTiB and AlTiC Grain Reners, Light Metals 1998, ed. B.J. Welch (Warrendale, PA: TMS, 1998), pp. 953961. 8. A.J. Whitehead, P.S. Cooper, and R.W. McCarthy, An Evaluation of Metal Cleanliness and Grain Renement of 5182 Aluminum Alloy DC Cast Ingot Using Al3%Ti-0.15%C and Al-3%Ti-1%B Grain Refiners (Paper presented at the 128th TMS Annual Meeting & Exhibition, San Diego, California, 13 March 1999). P. Moldovan and Gabriela Popescu are with the Material Science and Engineering Faculty at the University Politehnica of Bucharest in Romania. For more information, contact Gabriela Popescu, University Politehnica of Bucharest, Material Science and Engineering Faculty, Splaiuil Independentei 313, Bucharest, 77206 Romania. gabriella81us@yahoo.com.

are available and will be the key parameter for casthouses to activate as many particles (borides or carbides) as possible. An improved uniformity of grain size with Al-3Ti-0.15C compared to Al-5Ti-1B has been observed in the experiments. This could be advantageous in reducing homogenizing times, giving a more uniform response on working, and producing more uniform properties in nished sections.

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Figure 3. The macrostructure of samples produced with the Alcoa test (a) poured from melt with no grain rener added; (b) melt grain rened with 2 g/kg addition of Al-5Ti-1B; (c) melt grain rened with 2 g/kg addition of Al-3Ti-0.15C.

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