Effect of the salt addition practice on the grain refining efficiency of Al–Ti–B master alloys

The impact of the salt addition practice on the microstructure and grain refining efficiency of Al–Ti–B alloys produced by the “halide salt” route was investigated. The grain refining performance of an experimental Al–5Ti–1B master alloy was optimized when the halide salts were pre-mixed before addition to aluminium melt at 800 °C during the production of the grain refiner. The stirring action provided during salt addition was found to degrade, while a high rate of addition was found to improve, the grain refining efficiency. In view of the above, an improved salt addition practice to ensure an exceptional grain refining performance is claimed to comprise the following steps: melting commercial purity aluminium ingot; addition of pre-mixed salts to molten aluminium at 800 °C, at once to facilitate a rapid salt reaction, gently mixing the salts with the aluminium melt without introducing any stirring. The grain refiner master alloy thus produced gives an average grain size of 102 μm 2 min after inoculation.     

Production of Al–Ti–B master alloys from Ti sponge and KBF4

It is of great interest to replace the K₂TiF₆ salt so as to reduce the volume of fluoride-bearing particulate material to be added to the aluminium melt in the popular “halide salt” process. Ti sponge was used in the present work as the source of Ti in the production of an Al–5Ti–1B grain refiner. Addition of Ti granules into molten aluminium, either premixed with or before KBF₄ salt, has produced Al–5Ti–1B alloys where the boride particles were relatively few and predominantly of the AlB₂ type. The grain refining efficiency of these alloys were far from satisfactory. TiB₂ was the dominant boride phase with sufficient number of blocky aluminide particles when Ti, in excess of the TiB₂ stoichiometry was supplied before hand and the balance was reserved for co-addition with KBF₄. Al₃Ti particles were generated soon after the Ti solubility limit was exceeded in the first step while the boride particles were subsequently produced by the reaction between molten aluminium, KBF₄ and K₂TiF₆. The Al–5Ti–1B master alloy thus produced provided an adequate grain refining performance while the amount of particulate material to be added to the aluminium melt was reduced by nearly 30%.     

Production of Al–Ti–B grain refining master alloys from Na2B4O7 and K2TiF6

It is very desirable to replace the KBF₄ salt in the popular “halide salt” process to reduce the volume of fluoride salts to be added to molten aluminium in the production of Al–Ti–B grain refiners. Being over 2 times richer in B, Na₂B₄O₇ is a promising replacement for KBF₄, and is used in the present work to produce Al–Ti–B grain refiner master alloys. A fraction of the aluminide particles were entrapped in the spent salt giving a relatively lower Ti recovery when KBF₄ was replaced by Na₂B₄O₇. The grain refining performance of the Al–Ti–B grain refiner alloy thus produced was nevertheless acceptable. The spent salt became too viscous with the oxides, aluminides and borides to be removed by decanting when Na₂B₄O₇·5H₂O was used to supply boron. The viscous spent salt, entrained in the grain refiner alloy, did not only impair its performance, but also hurt the fluidity of the molten alloy and made pouring difficult.     

A novel Al–Ti–B alloy for grain refining Al–Si foundry alloys

Al–Ti–B refiners with excess-Ti (Ti:B > 2.2) perform adequately for wrought aluminium alloys but they are not as efficient in the case of foundry alloys. Silicon, which is abundant in the latter, forms silicides with Ti and severely impairs the potency of TiB₂ and Al₃Ti particles. Hence, Al–Ti–B alloys with excess-B (Ti:B < 2.2) and binary Al–B alloys are favored to grain refine hypoeutectic Al–Si alloys. These grain refiners rely on the insoluble (Al,Ti)B₂ or AlB₂ particles for grain refinement, and thus do not enjoy the growth restriction provided by solute Ti. It would be very attractive to produce excess-B Al–Ti–B alloys which additionally contain Al₃Ti particles to maximize their grain refining efficiency for aluminium foundry alloys. A powder metallurgy process was employed to produce an experimental Al–3Ti–3B grain refiner which contains both the insoluble AlB₂ and the soluble Al₃Ti particles. Inoculation of a hypoeutectic Al–Si foundry alloy with this grain refiner has produced a fine equiaxed grain structure across the entire section of the test sample which was more or less retained for holding times up to 15 min.     

The performance of Al–Ti–C grain refiners in twin-roll casting of aluminium foilstock

The master alloys based on the Al–Ti–B system have been used extensively for refining the grain structure of aluminum alloys. The quality-related problems linked with the TiB₂ particles, however, have generated an interest in the Al–Ti–C grain refiners as an acceptable replacement for Al–Ti–B master alloys. TiC particles are smaller than the TiB₂ particles and are less prone to agglomeration. Al–3Ti–0.15C grain refiners have been in use for some time in several alloy systems. Much of the work reported on this alloy, however, has been from DC casting while performance data in strip casting is not available. In the present work, a commercial Al–3Ti–0.15C grain refiner was employed in the twin-roll casting of AA8111 foilstock. Its grain refining efficiency was compared with that of the Al–5Ti–0.2B master alloy, the standard grain refiner in aluminium industry for the manufacture of aluminium foil products.     

Microstructure and grain refining performance of a new Al–Ti–C–B master alloy

A kind of Al–Ti–C–B master alloy with a uniform microstructure is prepared using a melt reaction method. It is found that the average grain size of α-Al can be reduced from 3500 to 170 μm by the addition of 0.2 wt.% of the prepared Al–5Ti–0.3C–0.2B and the refining efficiency does not fade obviously within 60 min. It is considered that the TiC_xB_y and TiB_2−mC_n particles found at the grain center are the effective and stable nucleating substrates for α-Al during solidification, which accounts for the good grain refining performance.     

Laser treatment and PVD TiN coating of Ti–6Al–4V alloy

Laser gas assisted processing can be used to modify the surface properties of Ti–6Al–4V alloy through the use of gaseous interaction with the laser melted surface. Laser surface melting of titanium and its alloys in nitrogen to form a layer of TiN embedded in a metallic matrix which is enriched in alloying elements has attracted considerable interest. The surface roughness of the laser-treated surface is poor, therefore, a secondary processing becomes essential. In the present study, duplex treatment of Ti–6Al–4V alloy was carried out. The alloy surface was melted initially under a controlled nitrogen atmosphere, which in turn resulted in a laser-induced nitrided surface. The resulting workpiece surface, then, was PVD TiN coated. In order to assess the wear properties of the resulting surface, friction tests were carried out. SEM, XRD and microhardness were carried out for microstructural analysis and material characterization. It was found that the adhesion of the TiN coating to the base alloy improved considerably in the case of laser-treated workpieces and smooth transition in plastic shearing resistance between the TiN coating and the base alloy enhanced the wear properties of the laser-treated surface.     

A novel fading-resistant Al-3Ti-3B grain refiner for Al-Si alloys

Al-Ti-B refiners with excess-Ti perform adequately for wrought aluminum alloys but inefficiently in the case of foundry alloys. The high content of silicon in the latter, which forms silicides with Ti and severely impairs the refining potency of the nuclei, is known to be responsible for the poor performance. Hence, new grain refiners, such as Al-3B and Al-3Ti-3B master alloys with excess-B have been developed with well documented advantages for Al-Si alloys. It is very desirable to involve TiAl₃ particles in the Al-3Ti-3B master alloy to maximize its grain refining efficiency. However, fading phenomenon is a key drawback for application of the TiAl₃-containing refiners in aluminum foundry. In the present work, new Al-3Ti-3B grain refiners, containing TiB₂, AlB₁₂ and TiAl₃ particles were developed with an aim to prolong the acting time after inoculation. The results showed that inoculation of Al-7Si alloy with thus meliorated Al-3Ti-3B grain refiner has produced a fine grain structure which was approximately maintained up to 30 min.     

Characterisation of oxide films produced by plasma electrolytic oxidation of a Ti–6Al–4V alloy

The paper discusses processing and property aspects of oxide films formed on a Ti–6Al–4V alloy by AC plasma electrolytic oxidation (PEO) in aqueous solutions containing aluminate, phosphate, silicate and sulfate anions and some of their combinations. Structure, composition, mechanical tribological and corrosion resistant characteristics of the films formed are studied by SEM, XRD and microhardness analyses, and by scratch, impact, pin-on-disc friction and potentiodynamic corrosion testing. It is found that the films produced from the aluminate–phosphate electrolyte are dense and uniform and are composed mainly of Al₂TiO₅ and TiO₂ phases of the rutile form. The films possess a beneficial combination of 50–60 μm thickness, 575 kg/mm² hardness and high adhesion and provide a low wear rate (3.4×10⁻⁸ mm³/Nm) but a relatively high friction coefficient of μ=0.6–0.7 against steel, caused by material transfer from the counterface. A minimum friction coefficient of μ=0.18 is recorded during the testing of softer rutile–anatase films, 7 μm thick, produced from a phosphate electrolyte. Both of these types of film show good corrosion resistance in NaCl and physiological solutions, where the corrosion current is approximately 1.5 orders of magnitude lower than that of the uncoated substrate. SiO₂/TiO₂-based films with 70–90 μm thickness and high bulk porosity produced from silicate and silicate–aluminate electrolytes demonstrate better corrosion behaviour in H₂SO₄ solution, due to the greater chemical stability of the film phase components in this environment.     

The impact characteristics of Ti–6Al–4V plates hardfacing by laser alloying NiAl+ZrO2 powder

This investigation considers the alloying of NiAl powders, with 0, 10, 20, 30, and 40 wt.% of ZrO₂ added, by the CO₂ laser upon Ti–6Al–4V base metals. Trial experiments are performed to obtain the optimum thickness of the powder, 0.1 mm, and the transverse speed, 1 mm/s, upon which the hardfacing process was based. The microstructures of the alloying layers were analyzed by OM, X-ray spectroscopy and SEM/EDS. The mechanical properties of the alloying layers were analyzed by micro-hardness and impact tests. The results indicated that the microstructure of the hardfacing layer was finer and its micro-hardness was higher than those of the base material. During the hardfacing process, NiAl and ZrO₂ powder were dissolved in a molten pool, reacted with other elements, and new phases were then formed. Impact tests revealed that the absorption of the vibration increased as the ZrO₂ added.     

Al–Ti–B grain refiners via powder metallurgy processing of Al/K2TiF6/KBF4 powder blends

The response to thermal exposure of ball-milled Al/K₂TiF₆/KBF₄ powder blends was investigated to explore the potential of PM processing for the manufacture of Al–Ti–B alloys. K₂TiF₆ starts to be reduced by aluminium as early as 220 °C when ball-milled Al/K₂TiF₆/KBF₄ powder blends are heated. The reaction of KBF₄ with aluminium follows soon after. The Ti and B thus produced are both solutionized in aluminium before precipitating out as Al₃Ti and TiB₂. All these reactions take place below the melting point of aluminium. The ball-milled Al/K₂TiF₆/KBF₄ powder blends heat treated at approximately 525 °C can be compacted to produce Al–Ti–B pellets with in situ formed Al₃Ti and TiB₂ particles. These pellets are shown to be adequate grain refiners for aluminium alloys.     

Theory of the nonlinear internal friction associated with bulk diffusion of solute atoms around dislocations in Al–Mg alloys

In this paper the nonlinear (amplitude-dependent) internal friction (P₃ peak) in cold-worked Al–Mg alloys is theoretically studied by solving the bulk diffusion equations of the solute atoms (Mg atoms) under the action of dislocation drag. The results in the case of a constant external stress show that the bow-out distance of the dislocation has an exponential relation with time, which can be well described by an exponential creep function with a Gaussian distribution in τ. With the increasing strain amplitude, the relaxation strength Δ and relaxation time τ decrease, while the distribution parameter increases. Both activation energy H and pre-exponential factor τ₀ deduced from τ through Arrhenius relation are dependent on strain amplitude.     

Activity measurements of Al and Cu in Si–Al–Cu melt at 1273 and 1373 K by the equilibration with molten Pb

For the effective control of Al introduction to solidified Si during the solidification refining of Si with the Si–Al-based melt for the solar cell material or the LPE Si film growth processes from the Si–Cu–Al solvent, thermodynamic properties of the Si–Al–Cu melt were investigated at 1273 and 1373 K. Activities of Al and Cu in the Si–Al–Cu melt were measured by the equilibration with molten Pb. Also, the excess Gibbs energy of the melt was studied by the ternary regular solution model.

The evaluated thermodynamic properties of the Si–Al–Cu melt indicated that Cu addition to the Si–Al melt brings the smaller activity coefficient of Al and is effective for reducing the Al content of solidified Si from the melt more effectively than its dilution effect for Al.