Removal of Vanadium from Molten Aluminum—Part III. Analysis of Industrial Boron Treatment Practice

Transition metal impurities (V, Ti, Zr, and Cr) reduce the electrical conductivity of smelter grade aluminum. These impurities are removed in the form of their borides by reacting with added Al-B master alloys i.e., boron treatment. Although, boron treatment is widely used for the production of high purity aluminum alloys in casthouse the fundamental understanding is lacking and published industrial data are limited. In the current study, industrial trials on the removal of impurities were conducted at one of the high purity aluminum alloys producers in Australasia. Kinetics analysis revealed that the rate of reaction is controlled by the mass transfer of impurities in the bulk melt. The measured mass transfer coefficient (k _m) of V and Ti were 1.1 × 10^?4 and 2.6 × 10^?4 m/s respectively, in the naturally stirred molten aluminum. The rate of V and Ti removal was faster compared to Zr and Cr during the boron treatment of smelter grade aluminum. Mass balance analysis revealed that 70 wt pct of V and Ti combined as borides in the first hour of the total 12 hours of boron treatment process. The calculated amount of un-reacted B was approximately 25.5 wt pct of initial amount added that remained in the final alloy. There was no evidence of boride rings formation, although partially dissolved AlB₁₂ particles were observed under scanning electron microscope. Finally, implications for industrial practice are discussed for the improvement of current boron treatment process that include changing the source of boron, multiple stage addition of boron and better stirring of the molten aluminum.     

Oxidative Removal of Boron from Molten Silicon by CaO-based Flux Treatment with Oxygen Gas Injection

Oxidative removal of boron from molten silicon has been investigated at 1773 K (1500 °C) by CaO-based flux treatment with oxygen gas injection. Since oxygen gas is injected into the silicon melt after adding CaO- or CaCO₃-CaF₂ flux onto the melt, high oxygen partial pressure is maintained at the flux-O₂-Si interface and the removal of boron proceeds under nonequilibrium conditions. The experimental results clarified that the behavior of boron removal from molten silicon depends on the competition between the oxidation reactions of boron and silicon. On the basis of the results obtained, optimum operating conditions for boron removal by the flux treatment were examined from the viewpoints of initial flux composition, reaction time, oxygen gas flow rate, and orifice size of gas injection nozzle. By repeating the batch operation for 120 seconds three times under the optimum conditions determined in the present study, boron concentration in metallurgical-grade silicon could be reduced from 14 to 7.6 mass ppm efficiently.     

Removal of Vanadium from Molten Aluminum—Part II. Kinetic Analysis and Mechanism of VB2 Formation

Transition metal impurities such as vanadium (V), titanium (Ti), zirconium (Zr), and chromium (Cr) reduce the electrical conductivity of smelter grade aluminum. These impurities are removed by the addition of boron-bearing substances (AlB₁₂/AlB₂) and the process is called boron treatment. The quality of the alloy and the economy of boron treatment can be improved by understanding the kinetics and mechanism of VB₂ formation in molten aluminum. Currently, there is limited published information on the heterogeneous kinetics of the boron treatment. In this study, an investigation of the kinetics of V removal from molten Al-1 wt pct V alloys during boron treatment at 1023 K (750 °C) was carried out. The effects of stirring (natural, mechanical, and gas), reaction temperature, and the levels of boron addition were analyzed. The kinetics of the process could be described in two stages. The rate was faster in the early stage of reaction and was halted after 10 minutes. It was concluded that the early stage of reaction was controlled by the mass transfer of V in molten aluminum. In the second stage of reaction, it was concluded that the kinetics was controlled by the diffusion of B through a VB₂ layer formed in the early stage of reaction. It was observed from microscopy analysis that the ring of VB₂ disintegrated during gas stirring of bulk melt and consequently the kinetics of reaction was enhanced.     

The Effect of Melt Conditioning on Segregation of Solute Elements and Nucleation of Aluminum Grains in a Twin Roll Cast Aluminum Alloy

An aluminum alloy was cast by a laboratory scale horizontal twin roll caster with or without melt conditioning by the intensive shearing prior to solidification and then examined by high-resolution electron microscopy. The combined twin roll casting process with solidification formed channels and induced centerline segregation without the conditioning. In comparison, the melt conditioning minimized the severe segregation on the surface as well as at the centerline. Furthermore, large amounts of solute elements were uniformly distributed along grain boundaries or interdendritic regions. Analytical electron microscopy detected a fine oxide particle or a fragmented aluminum particle particularly at the center region of one nucleated aluminum grain. In addition, large oxide particles of about 1 to 5 μm nucleated aluminum grains easily due to low undercooling necessary for the heterogeneous nucleation, whereas small oxides with the size of about 100 to 200 nm requiring large undercooling were pushed along the grain boundaries instead of contributing to the nucleation. The enhanced nucleation of aluminum grains and well-distributed solute atoms in the melt by the melt conditioning resulted in the minimization of macro- and micro-segregations and the formation of a uniform microstructure.     

Study on the Formation and Characterization of the Intermetallics in Friction Stir Welding of Aluminum Alloy to Coated Steel Sheet Lap Joint

Multimaterial fabrication such as joining of steel and aluminum is currently prominent in a variety of industries. Friction stir welding is a novel solid-state welding process that causes good joint strength between steel and aluminum. However, the phenomenon contributing significant strength at the interface is not yet clear. In the present study, the interface of the friction stir lap-welded aluminum and coated steel sheet having joint strength maximum (71.4 pct of steel base metal) and minimum, respectively, under two parameter combinations, i.e., 1000 rpm 50 mm min^?1 and 500 rpm 100 mm min^?1, was exclusively characterized by X-ray diffraction, transmission electron microscopy (TEM), concentration profile, and elemental mapping by electron-probe microanalysis. A TEM-assisted EDS study identifies the morphologies of large size Al₁₃Fe₄ and small size Fe₃Al-type intermetallic compounds at the interface. The diffusion-induced intermetallic growth (thickness) measured from a backscattered image and concentration profile agreed well with the numerically calculated one. The growth of these two phases at 1000 rpm 50 mm min^?1 is attributed to the slower cooling rate (~3.5 K/s) with higher diffusion time (44 seconds) along the interface in comparison to the same for 500 rpm 100 mm min^?1 with faster cooling rate (~10 K/s) and less diffusion time (13.6 seconds). The formation of thermodynamically stable and hard intermetallic phase Al₁₃Fe₄ at 1000 rpm and travel speed 50 mm min^?1 in amounts higher than 500 rpm and a travel speed of 100 mm min^?1 results in better joint strength, i.e., 71.4 pct, of the steel base metal.     

Production of Titanium Powder by Sodiothermic Reduction in CaCl2 Molten Salts

A new sodiothermic reduction process of TiO₂ in CaCl₂ melt was proposed aimed at fine Ti powder preparation. The chemical analysis and direct potentiometric methods were used to investigate the reaction pathway of sodiothermic reduction in CaCl₂ melt. The as-prepared samples were characterized by X-ray diffraction and scanning electron microscopy. It was found that when reductant of Na was added into the CaCl₂ melt, Ca²⁺ was reduced to Ca by Na and Ca dissolved in the CaCl₂ melt. The whole melt would have the reducing power with dissolved Ca. Using this melt as a reaction medium, fine and uniform Ti powder with a purity of around 99 mass pct was successfully produced at 1173 K (900 °C). In addition, as the CaCl₂ melt could dissolve about 20 mol pct CaO, it was found that the molar ratio of TiO₂ and CaCl₂ should be 1:20 to eliminate the by-product CaO from the reaction interface within the experimental period to continue the reduction.     

A Novel Bonding Method of Pure Aluminum and SUS304 Stainless Steel Using Barrel Nitriding

A great deal of research is being carried out on welding or bonding methods between iron and aluminum. However, it is not so easy to make Fe-Al bonding materials with both high strength and light weight. Recently, a new nitriding process has been proposed to produce aluminum nitride on an aluminum surface using a barrel. This study proposes a new concept in the production of a multilayer which has an AlN and Fe-Al intermetallic compound layer between the aluminum and steel using a barrel nitriding process. The bonding process was carried out from 893 K to 913 K (620 °C to 640 °C) for 18, 25.2, and 36 ks with Al₂O₃ powder and Al-Mg alloy powder. After the process, an aluminum nitride (AlN) layer and a Fe-Al intermetallic compound (Fe₂Al_5.4) layer were formed at the interface between the pure aluminum and SUS304 austenitic stainless steel. The thicknesses of the AlN layer and the intermetallic compound layer increased with increasing treatment temperature and time. The maximum hardnesses of the AlN layer and Fe₂Al_5.4 layers were found to be 377HV and 910HV, respectively, after barrel nitriding at 893 K (620 °C) for 18 ks.     

Effect of Bonding Temperature on Interfacial Reaction and Mechanical Properties of Diffusion-Bonded Joint Between Ti-6Al-4V and 304 Stainless Steel Using Nickel as an Intermediate Material

An investigation was carried out on the solid-state diffusion bonding between Ti-6Al-4V (TiA) and 304 stainless steel (SS) using pure nickel (Ni) of 200-μm thickness as an intermediate material prepared in vacuum in the temperature range from 973 K to 1073 K (700 °C to 800 °C) in steps of 298 K (25 °C) using uniaxial compressive pressure of 3 MPa and 60 minutes as bonding time. Scanning electron microscopy images, in backscattered electron mode, had revealed existence of layerwise Ti-Ni-based intermetallics such as either Ni₃Ti or both Ni₃Ti and NiTi at titanium alloy-nickel (TiA/Ni) interface, whereas nickel-stainless steel (Ni/SS) diffusion zone was free from intermetallic phases for all joints processed. Chemical composition of the reaction layers was determined in atomic percentage by energy dispersive spectroscopy and confirmed by X-ray diffraction study. Room-temperature properties of the bonded joints were characterized using microhardness evaluation and tensile testing. The maximum hardness value of ~800 HV was observed at TiA/Ni interface for the bond processed at 1073 K (800 °C). The hardness value at Ni/SS interface for all the bonds was found to be ~330 HV. Maximum tensile strength of ~206 MPa along with ~2.9 pct ductility was obtained for the joint processed at 1023 K (750 °C). It was observed from the activation study that the diffusion rate at TiA/Ni interface is lesser than that at the Ni/SS interface. From microhardness profile, fractured surfaces and fracture path, it was demonstrated that failure of the joints was initiated and propagated apparently at the TiA/Ni interface near Ni₃Ti intermetallic phase.     

Simulation of Magnetohydrodynamic Multiphase Flow Phenomena and Interface Fluctuation in Aluminum Electrolytic Cell with Innovative Cathode

A three-dimensional (3D) transient mathematical model has been developed to understand the effect of innovative cathode on molten cryolite (bath)/molten aluminum (metal) interface fluctuation as well as energy-saving mechanism in aluminum electrolytic cell with innovative cathode. Based on the finite element method, the steady charge conservation law, Ohm’s law, and steady-state Maxwell’s equations were solved in order to investigate electric current field, magnetic field, and electromagnetic force (EMF) field. Then, an inhomogeneous multiphase flow model of three phases including bath, metal, and gas bubbles, based on the finite volume method, was implemented using the Euler/Euler approach to investigate melt motion and bath/metal interface fluctuation. EMF was incorporated into the momentum equations of bath and metal as a source term. Additionally, the interphase drag force was employed to consider different phase interactions. Thus, present work owns three main features: (1) magnetohydrodynamic multiphase flow are demonstrated in detail both in aluminum electrolytic cell with traditional cathode and innovative cathode; (2) bath/metal interface fluctuation due to different driving forces of gas bubbles, EMF, and the combined effect of the two driving forces is investigated, which is critical to the energy saving; and (3) the effect of innovative cathode on melt flow and motion of gas bubbles. A good agreement between the predicated results and measurement is obtained. The velocity difference leading to the melt oscillation decreases due to more uniform flow field. The average velocity of metal in the cell with innovative cathode decreases by approximately 33.98 pct. The gas bubbles in the cell with innovative cathode releases more quickly under the effect of protrusion on the cathode. The average bubble release frequency increases from 1.1 to 1.98 Hz. Hence, the voltage drop caused by gas bubbles would decrease significantly. In addition, the two large vortices are broken into many small vortices due to the protrusion. The final disappearance of the small vortices as a result of viscous dissipation is conducive to the suppression of bath/metal interface fluctuation. The average interface amplitude in the cell with innovative cathode reduces to 75.95 pct of that in the cell with traditional cathode.     

Study on Microstructures of Al-4 wt pct V Master Alloys

Aluminum (Al)-V master alloys have attracted attention, because they can potentially be efficient grain refiners for wrought aluminum alloys. In this paper, the microstructure and factors affecting the microstructure of Al-4 wt pct V master alloys were investigated by means of controlled melting and casting processes followed by structure examination. The results showed that the type and morphology of the V-containing phases in Al-V master alloys were strongly affected by the temperature of the melt, concentration of vanadium in solution in the melt and the cooling conditions. Two main V-containing phases, Al₃V and Al₁₀V, which have different shapes, were found in the alloys prepared by rapid solidification. The Al₃V phase formed when there were both a high temperature (1273 K to 1673 K (1000 °C to 1400 °C)) and a relatively high vanadium content of 3 to 4 wt pct, while the Al₁₀V phase formed at a low temperature (<1373 K (1100 °C)) or a low vanadium content in the range of 1 to 3 wt pct. The results also showed that the type of V-containing phase that formed in the Al-4 wt pct V master alloy was determined by the instantaneous vanadium content.     

Angle of wetting of aluminum oxide with a high-carbon iron melt

The angle of wetting of aluminum oxide with a high-carbon iron melt is studied as a function of temperature and time. It is found that the angle is nearly 94° in the temperature range 1200–1400°C. A preliminary study of the interface is performed using confocal and scanning electron microscopy.     

Coating of 6028 Aluminum Alloy Using Aluminum Piston Alloy and Al-Si Alloy-Based Nanocomposites Produced by the Addition of Al-Ti5-B1 to the Matrix Melt

The Al-12 pctSi alloy and aluminum-based composites reinforced with TiB₂ and Al₃Ti intermetallics exhibit good wear resistance, strength-to-weight ratio, and strength-to-cost ratio when compared to equivalent other commercial Al alloys, which make them good candidates as coating materials. In this study, structural AA 6028 alloy is used as the base material. Four different coating materials were used. The first one is Al-Si alloy that has Si content near eutectic composition. The second, third, and fourth ones are Al-6 pctSi-based reinforced with TiB₂ and Al₃Ti nano-particles produced by addition of Al-Ti5-B1 master alloy with different weight percentages (1, 2, and 3 pct). The coating treatment was carried out with the aid of GTAW process. The microstructures of the base and coated materials were investigated using optical microscope and scanning electron microscope equipped with EDX analyzer. Microhardness of the base material and the coated layer were evaluated using a microhardness tester. GTAW process results in almost sound coated layer on 6028 aluminum alloy with the used four coating materials. The coating materials of Al-12 pct Si alloy resulted in very fine dendritic Al-Si eutectic structure. The interface between the coated layer and the base metal was very clean. The coated layer was almost free from porosities or other defects. The coating materials of Al-6 pct Si-based mixed with Al-Ti5-B1 master alloy with different percentages (1, 2, and 3 pct), results in coated layer consisted of matrix of fine dendrite eutectic morphology structure inside α-Al grains. Many fine in situ TiAl₃ and TiB₂ intermetallics were precipitated almost at the grain boundary of α-Al grains. The amounts of these precipitates are increased by increasing the addition of Al-Ti5-B1 master alloy. The surface hardness of the 6028 aluminum alloy base metal was improved with the entire four used surface coating materials. The improvement reached to about 85 pct by the first type of coating material (Al-12 pctSi alloy), while it reached to 77, 83, and 89 pct by the coating materials of Al-6 pct Si-based mixed with Al-Ti5-B1 master alloy with different percentages 1, 2, and 3 pct, respectively.     

A Comprehensive Study of Diffusion Bonding of Mg AZ31 to Al 5754, Al 6061 and Al 7039 Alloys

In the present study, microstructural and mechanical properties of diffusion bonding of AZ31–Mg with Al 5754, Al 6061, and Al 7039 alloys were compared under same conditions. The vacuum diffusion processes were performed at a temperature of 440 °C, the pressure of 29 MPa, and a vacuum of 1?×?10^?4 torr for 60 min. The microstructural characterizations were investigated using optical microscopy and scanning electron microscopy equipped with EDS analysis and linear scanner. The XRD analysis was performed to study phase figures near the interface zone. The results revealed the formation of brittle intermetallic compounds like Al₁₂Mg₁₇, Al₃Mg₂, and their other combinations at bonding interfaces of all samples. Additionally, the hardness of Al alloys seemed to play a key role in increasing diffusion rate of magnesium atoms toward the aluminum atoms, with Al 6061 alloy having the highest diffusion rate. It consequently led to an increase in diffusion rate and thus formation of a strong diffusion bonding between magnesium and aluminum alloys. The highest strength was about 42 MPa for the diffusion bonding between Mg AZ31 and Al 6061. Further investigations on surfaces indicated that the brittle phases especially Al₃Mg₂ caused brittle fracturing.     

Distribution of aluminum in hot-dip galvanized coatings

Hot-dip galvanized panels of low-carbon (LC) and interstitial-free (IF) steels were produced in a laboratory simulator with an average coating mass of 60 g/m². Three pot aluminum levels were used, viz., 0.10 pct (by wt), 0.15 pct, and 0.18 pct. Metallography, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were used to characterize coating and base steel microstructures. Wet chemical analysis and scanning transmission electron microscopy (STEM) were employed for compositional analyses. The aluminum content of the melt was found to be the predominant factor influencing the distribution of Al in the coating. At 0.18 pct melt aluminum, Al is partitioned between the aluminide inhibition layer at the coating-steel interface (∼80 pct) and the zinc overlay (∼20 pct). At 0.15 pct, it is partitioned among the aluminide layer (∼75 pct to 80 pct), zinc-iron (FeZn₁₃, ζ) intermetallic layer (∼5 pct to 15 pct), and the coating overlay (∼10 pct). At 0.10 pct, the aluminum is divided almost equally between the overlay and the zinc-iron intermetallics. At the two lower aluminum levels is the distribution marginally influenced by the steel grade. The ζ was found to not preferentially nucleate at the ferrite grain boundaries. When both the aluminide and ζ occurred at the coating-steel interface, the ζ particles appeared near discontinuities and thinner regions in the aluminide layer. The coating, relative to the melt, is enriched in aluminum because of its concentration in the aluminide and in the zinc-iron intermetallics. This enrichment increases with melt aluminum through an increase in the aluminum content of the aluminide layer and not of its thickness. In addition, a few tens-of-nanometers-thick layer enriched in aluminum, oxygen, and iron is observed on the outer surface of all coatings. The aluminum content in this layer also increases with an increase in the melt aluminum, but it contributes negligibly to the coatings’s content because of its extreme thinness.     

Interfacial reaction wetting in the boron nitride/molten aluminum system

An improved sessile drop technique which prevented the oxidation of aluminum was used to measure the changes in contact angle between boron nitride and molten aluminum in a purified He-3% H₂ between 1173 and 1373 K. The contact angle progressed through the four wetting phases similar to other ceramics when the results were plotted on a logarithmic time scale. However, at and above 1273 K the equilibrium contact angle was 0° which is much less than those of typical ceramics. Using the value in phase II, the original contact angle between boron nitride and aluminum (contact angle between non-reacted boron nitride and aluminum) was estimated to be 133° at 1373 K. The wetting progressed by producing another non-wetting material, AIN, in this non-wetting system. The detailed mechanism of the solid/liquid/vapor interfacial advance during wetting in such a system was also explained using Cassie's equation.     

The interfacial tension between aluminum and cryolite melts saturated with alumina

A Method was developed for measuring the capillary depression of Met.allic aluminum in an alumina tube in a cryolite melt. As the tube was progressively lowered through the melt into the Met.al the volume of gas expelled was measured by the movement of a meniscus of liquid in a horizontal glass tube. No movement occurred after the tube entered the aluminum until it was far enough down that the Met.al could enter it. A correction was applied for the finite radius of the crucible holding the melt, the necessary theory being derived. The contact angle between Met.al, alumina, and cryolite was determined from the shape of the Met.al frozen in the crucible. It was found that the contact angle of the Metal on alumina is very close to 180 deg, and that the interfacial tension at 1000°C is 460 ± 27 mN · m^-1 (standard deviation). Interfacial tension decreases with increasing NaF/AlF₃ ratio, and increases with addition of MgF₂ or Li₃AlF₆. CaF₂ has no significant effect. The hypothesis is advanced that the effect of ratio is due to adsorption of Na atoms, generated by the reaction 3 NaF + Al ⇌ A1F₃ + 3Na, at the interface. Application of the Gibbs adsorption isotherm suggests that at molar ratios NaF/AlF₃ above 2.8 the interface is covered with a monolayer of sodium atoms.     

Effect of Heat Treatment on Microstructure and Properties of High Boron-High Speed Steel

A new type of high boron-high speed steel (HB-HSS) with different boron content was selected for oil quenching at 1050 °C, and different temperature of tempering treatment was chosen. By using optical microscopy, scanning electron microscopy, X-ray diffraction, Rockwell hardness tester, red hard treatment and wear test, the effects of heat treatment on microstructure and properties of HB-HSS were investigated. The experimental results indicate that the quenching microstructure of HB-HSS consists of α-Fe, M₂(B, C), M₇(B, C)₃ and a few of M₂₃(C, B)₆. When the tempering temperature is lower than 500 °C, the shape of carboborides will change from discontinuous sheet to continuous net, and the uniformity in microstructure is improved, and the hardness is not changed during the process. When the tempering temperature is higher than 500 °C, the continuous net of M₂(B, C) is recovered. When the tempering temperature is higher than 600 °C, the microstructure of HB-HSS get thickened because of overheating, and the hardness get significantly reduced. With the increase of tempering temperature, the weight loss of the sample is decreased, and the wear resistance of the sample is increased. When tempering temperature exceeds 500 °C, the weight loss of the sample has an obvious increase and its wear resistance decreases. The wear resistance of the sample decreases after the red-hardness treatment. The wear loss is about 8.4 mg when the boron content is 2.0% and the tempering temperature is 500 °C, which is the best of test samples.     

Electrically Enhanced Boron Removal from Silicon Using Slag

An approach to enhance silicon refining using slag has been developed. The enhancement of the process was carried out by applying electrical potential difference across the slag and the silicon phase. This resulted in a shift in the apparent equilibrium in favor of higher partition ratio for the impurities. The application of electrical potential difference also enhanced the mass transfer rate increasing the overall kinetics of the process. This has been demonstrated in laboratory experimentations for the removal of boron from silicon-boron melts using slag. A CaO-SiO₂-Al₂O₃ slag was reacted with Si-B melt at 1823 K (1550 °C). Electrical potential differences were applied through graphite rods immersed in each of the liquid phase. The results showed that the apparent B-partition ratio and the apparent slag mass transfer coefficient were increased by a factor of 1.2 and 1.4, respectively, when a potential difference of 3 V was applied to the phases. The technique has the potential to be used for improving the existing slag refining process by increasing the overall kinetics and the slag capacity to absorb the impurities.     

TEM Studies of Boron-Modified 17Cr-7Ni Precipitation-Hardenable Stainless Steel via Rapid Solidification Route

Commercial grade 17Cr-7Ni precipitation-hardenable stainless steel has been modified by adding boron in the range 0.45 to 1.8 wt pct and using the chill block melt-spinning technique of rapid solidification (RS). Application of RS has been found to increase the solid solubility of boron and hardness of 17Cr-7Ni precipitation-hardenable stainless steel. The hardness of the boron-modified rapidly solidified alloys has been found to increase up to ~280 pct after isochronal aging to peak hardness. A TEM study has been carried out to understand the aging behavior. The presence of M₂₃(B,C)₆ and M₂(B,C) borocarbides and epsilon-carbide in the matrix of austenite and ferrite with a change in heat treatment temperature has been observed. A new equation for Creq is also developed which includes the boron factor on ferrite phase stability. The study also emphasizes that aluminum only takes part in ferrite phase stabilization and remains in the solution.     

The Influence of Surface Anisotropy Crystalline Structure on Wetting of Sapphire by Molten Aluminum

The wetting of sapphire by molten aluminum was investigated by the sessile drop technique from 1073 K to 1473 K (800 °C to 1200 °C) at PO₂ <10^?15 Pa under Ar atmosphere. This study focuses on sapphire crystalline structure and its principle to the interface. The planes “a” and “b” are oxygen terminated structures and wet more by Al, whereas the “c” plane is an aluminum terminated structure. A wetting transition at 1273 K (1000 °C) was obtained and a solid surface tension proves the capillarity trends of the couple.