Removal of B from Si by solidification refining with Si-Al melts

To discuss the removal of B by solidification refining of Si with a Si-Al melt, the segregation of B between solid Si and the Si-Al melt was investigated by use of the temperature-gradient-zone melting (TGZM) method. The segregation ratio of B at its infinite dilution was determined to be 0.49 (1473 K), 0.32 (1373 K), and 0.22 (1273 K), respectively. With the obtained segregation ratio, the activity coefficient of B in solid Si at its infinite dilution relative to pure solid B was determined by the following equation:

Removal of Boron from Silicon-Tin Solvent by Slag Treatment

To eliminate B effectively from Si for its use in a solar cell, a novel process involving the slag refining of molten Si with Sn addition was investigated. The partition ratio of B between CaO-SiO₂-24 mol pct CaF₂ slag and Si-Sn alloy at 1673 K (1400 °C) was determined by the chemical equilibrium technique. It was found that the partition ratio of B was remarkably increased with the increase in Sn content of alloy, which attributes to the increase in activity coefficient of B as well as the oxygen partial pressure. The partition function was accounted as much as 200 when the alloy composition was Si-82.4 mol pct Sn, which was much higher than the reported values in the range of 1 to 3. The required amounts of slag used for B removal from Si-30, 50, and 70 mol pct Sn melts were only 15.6 pct, 6.5 pct, and 1.2 pct of that used for the removal of B directly from MG-Si without Sn addition in a single slag treatment.     

Evolution of boride morphologies in TiAl-B alloys

The solidification of γ-TiAl alloys with relatively low (<2 at. pct) additions of boron is discussed. Binary Ti-Al alloys containing 49 to 52 at. pct Al form primary α-(Ti) dendrites from the melt, which are subsequently surrounded by γ segregate as the system goes through the peritectic reactionL + α →γ. Alloys between 45 and 49 at. pct Al go through a double peritectic cascade, forming primary β-(Ti) surrounded by α-(Ti) and eventually by γ in the interdendritic spaces. Boron additions to these binary alloys do not change the basic solidifi-cation sequence of the matrix but introduce the refractory compound TiB₂ in a variety of mor-phologies. The boride develops as highly convoluted flakes in the leaner alloys, but needles, plates, and equiaxed particles gradually appear as the B content increases above ∼1 at. pct. Increasing the solidification rate initially promotes the formation of flakes over plates/needles and ultimately gives way to very fine equiaxed TiB₂ particles in the interdendritic spaces of the metallic matrix. Furthermore, the primary phase selection in the 49 to 52 at. pct Al range changes from α-(Ti) to β-(Ti) at supercoolings of the order of 200 K. The different boride morphologies are fully characterized, and their evolution is rationalized in terms of differences in their nucleation and growth behavior and their relationship to the solidification of the inter-metallic matrix. Formerly Research Assistant, University of California-Santa Barbara (UCSB) Formerly Professor of Materials and Dean of the College of Engineering at UCSB     

Effect of Hot Rolling on Grain Refining Performance of Al–5Ti–1B Master Alloy on Hot Tearing on Al–7Si–3Cu Alloy

It has been known experimentally that TiAl₃ acts as a powerful nucleant for the solidification of aluminum from the melt; however, a full microscopic understanding is still lacking. To improve microscopic understanding, hot rolling technique has been performed to the Al–5Ti–1B alloy and the effect of shape and size of the particles on grain refinement has been studied. The effect of hot rolling of Al–5Ti–1B master alloy on its grain refining performance and hot tearing have been studied by OM, XRD, and SEM. Hot rolling improves the grain refining performance of this master alloy, which is required to reduce hot tearing in Al–7Si–3Cu alloy. The improvement in grain refining performance of Al–5Ti–1B master alloy on rolling is due to the fracture of larger TiAl₃ particles into fine particles during rolling. The presented results illustrate that the morphology of TiAl₃ particles alter from the plate-like structure in the as-cast condition Al–5Ti–1B master alloy to the blocky type after rolling due to the fragmentation of plate-like structures. The grain refining response and effect on hot tearing of Al–7Si–3Cu alloy have been studied with as-cast and rolled Al–5Ti–1B master alloys. The results display hot-rolled master alloys revealing enhanced grain refining performance and minimizing hot tear tendency of the alloy at much lower addition level as compared to as-cast master alloys.     

Effect of Compositional Variation on the Microstructural Evolution and the Castability of Al–Mg–Si Ternary Alloys

This study examined the microstructural evolution and castability of Al–Mg–Si ternary alloys with varying Si contents. Al–6Mg–xSi alloys (where x = 0, 1, 3, 5, and 7; all compositions in mass pct) were examined, with Al–6 mass pct Mg as a base alloy. The results showed that in the ternary alloys with Si ≤ 3 pct, the solidification process ended with the formation of eutectic α-Al–Mg₂Si phases generated by a univariant reaction. However, in the case of ternary alloys with Si > 3 pct, solidification was completed with the formation of α-Al–Mg₂Si–Si ternary eutectic phases generated by a three-phase invariant reaction. In addition to the eutectic Mg₂Si phases, the primary Mg₂Si phases formed in each of the ternary alloys, and the size of both sets of phases increased with increasing Si content. The two-phase eutectic α-Al–Mg₂Si nucleated from the primary Mg₂Si phases. The inoculated Al–6Mg–1Si alloy had the smallest grain size. Moreover, the grain-refining efficacy of the Al–5Ti–B master alloy in the ternary alloys decreased with increasing Si content in the alloys. Despite the poisoning effect of Si on the potency of TiB₂ compounds in the inoculated Al–6Mg–1Si alloy, the grain size of the alloy was slightly smaller than that of the Al–6Mg binary alloy. This resulted from the increasing growth restriction factor (induced by Si addition) of the Al–6Mg–1Si alloy. In terms of the castability, the examined alloys showed different levels of susceptibility to hot tearing. Among the alloys, the ternary Al–6Mg–5Si alloy exhibited the highest susceptibility to hot tearing, whereas the Al–6Mg–7Si exhibited the lowest. The severity of hot tearing initiated by the unraveling of the bifilm was determined by the freezing range, grain size, and the amount of eutectic phases at the end of the solidification process.

     

A metallographic study of porosity and fracture behavior in relation to the tensile properties in 319.2 end chill castings

A metallographic study of the porosity and fracture behavior in unidirectionally solidified end chill castings of 319.2 aluminum alloy (Al-6.2 pct Si-3.8 pct Cu-0.5 pct Fe-0.14 pct Mn-0.06 pct Mg-0.073 pct Ti) was carried out using optical microscopy and scanning electron microscopy (SEM) to determine their relationship with the tensile properties. The parameters varied in the production of these castings were the hydrogen (∼0.1 and ∼0.37 mL/100 g Al), modifier (0 and 300 ppm Sr), and grain refiner (0 and 0.02 wt pct Ti) concentrations, as well as the solidification time, which increased with increasing distance from the end chill bottom of the casting, giving dendrite arm spacings (DASs) ranging from ∼15 to ∼95 /im. Image analysis and energy dispersive X-ray (EDX) analysis were employed for quantification of porosity/microstructural constituents and fracture surface analysis (phase identification), respectively. The results showed that the local solidification time(viz. DAS) significantly influences the ductility at low hydrogen levels; at higher levels, however, hydro-gen has a more pronounced effect (porosity related) on the drop in ductility. Porosity is mainly observed in the form of elongated pores along the grain boundaries, with Sr increasing the porosity volume percent and grain refining increasing the probability for pore branching. The beneficial effect of Sr modification, however, improves the alloy ductility. Fracture of the Si, β-Al₅FeSi, α- Al₁₅(Fe,Mn)₃Si₂, and Al₂Cu phases takes place within the phase particles rather than at the particle/Al matrix interface. Sensitivity of tensile properties to DAS allows for the use of the latter as an indicator of the expected properties of the alloy.     

Fabrication of Al-3.7?Pct Si-0.18?Pct Mg Foam Strengthened by AlN Particle Dispersion and its Compressive Properties

Al-3.7 pct Si-0.18 pct Mg foams strengthened by AlN particle dispersion were prepared by a melt foaming method, and the effect of foaming temperature on the foaming behavior was investigated. Al-3.7 pct Si-0.18 pct Mg alloy containing AlN particles was prepared by noncompressive infiltration of Al powder compacts with molten Al alloy in nitrogen atmosphere, and it was foamed at different foaming temperatures ranging from 1023 to 1173 K. The porosity of prepared foam decreases and the pore structure becomes homogeneous with increasing foaming temperature. When the foaming temperature is higher than 1123 K, homogeneous pores are formed in the prepared ingot without using oxide particles and metallic calcium granules, which are usually used for stabilizing a foaming process. This stabilization of the foaming at high temperatures is possibly caused by Al₃Ti intermetallic compounds formed at high temperature and AlN particles. Compression tests for the prepared foams revealed that the absorbed energy per unit mass of prepared Al-3.7 pct Si-0.18 pct Mg foam is higher than those of aluminum foams strengthened by alloying or dispersion of reinforcements. It is remarkable that the oscillation in stress, which usually appears in strengthened aluminum foams, does not appear in the plateau stress region of the present Al-3.7 pct Si-0.18 pct Mg foam. The homogeneity in cell walls and pore morphology due to the stabilization of pore formation and growth by AlN and Al₃Ti particles is a possible cause of this smooth plateau stress region.     

The constitution of the system Al-Ti-B with reference to aluminum-base alloys

Direct and differential thermal analyses have been used to determine the liquidus temperatures and isothermals in the aluminum-base corner of the Al-Ti-B system, and with microscopical information and electron microprobe analyses provide results on which is based a provisional phase diagram. The TiB₂ liquidus rises very steeply from the aluminum corner of the diagram and is bounded on either side by monovariant reactions which almost coincide with the binary Al-B and Al-Ti liquidus curves. If the Ti:B ratio exceeds 7∶3 wt pct (1∶2 at. pct), TiB₂ precipitates on cooling until there occurs a monovariant reaction involving Al₃Ti, while at lower Ti:B ratios there occurs a monovariant reaction which involves AlB₂. The grain refining action of ternary alloys is discussed with reference to the form of the phase diagram.     

Behavior of Boron in Molten Aluminum and its Grain Refinement Mechanism

The mechanism of heterogeneous grain refining of aluminum by ultrafine elemental boron particles was investigated. In order to facilitate the observation of the boron-aluminum interface, a boron filament was introduced in a melt at 1013 K (740 °C) containing different levels of Ti. The Al/B interface was studied using transmission electron microscopy and different phases were identified using the electron diffraction method. The experimental results showed that boron is dissolved in pure aluminum while its dissolution is inhibited in presence of titanium solute. A thin layer of TiB₂ formed at the surface of boron thickens with residence time in the melt. The mechanisms by which aluminum is crystallized on boron are discussed.     

Impurities Removal from Metallurgical-Grade Silicon by Combined Sn-Si and Al-Si Refining Processes

The purification of metallurgical-grade silicon (MG-Si) by combined solvent refining processes has been studied. The final high-purity silicon was recovered through Sn-Si refining and Al-Si refining processes in sequence after acid leaching, and the removal mechanism of impurities was explored. Inductively coupled plasma (ICP) chemical analysis revealed the concentrations of main impurities including B and P, and typical metallic impurities except for solvents Sn and Al were reduced to below 1 ppmw. The final removal efficiencies of B and P were 97.7 pct and 99.8 pct, respectively, and those of most metallic impurities were above 99.9 pct. SEM analysis showed that P-containing phases (Al-Ca-Mg-Si-P and Al-Si-P) formed on the surface of refined Si after Sn-Si refining and Al-Si refining, which was confirmed to be the main approach for P removal. It was also found that the formation of binary silicide such as Fe₃Si₇ and Mn₁₁Si₁₉ or multicomponent phases such as Ca-Mg-Si phase occurred during the solvent refining process, and they segregated on the grain boundaries in Si or attached to the surface of Si, which led to high removal efficiency of metallic impurities by the solvent refining process.     

Solid-Liquid Interface Energy between Silicon Crystal and Silicon-Aluminum Melt

By examining the surface morphologies of undercooled Si-20 at. pct Al alloy during and after the solidification process, it is determined that the critical undercooling for silicon to grow from lateral mode to intermediary mode ΔT* and that from intermediary mode to continuous mode ΔT** are 131 and 239 K, respectively. A method that predicts the solid-liquid interface energy of binary lateral growth materials on the basis of ΔT* and ΔT** has been developed. Formulas between the physical parameters and the solid-liquid interface energy have been obtained. The interface energy between silicon crystal and Si-Al melt predicted from ΔT* is almost equal to that from ΔT**. The present results of the solid-liquid interface energy predicted according to ΔT* and ΔT** obtained in Si-20 at. pct Al alloy are in very good agreement with the reported results of the grain-boundary method and the critical undercooling method from ΔT* and ΔT** obtained in pure silicon.     

Influence of Reaction Temperature and Reaction Time for the Manufacturing of Al–Ti–B (Ti:B?=?5:1, 1:3) Master Alloys and Their Grain Refining Efficiency on Al–7Si Alloys

In the present work, ternary Al?CTi?CB master alloys have been prepared in an induction furnace by the reaction between preheated halide salts (K₂TiF₆ and KBF₄) and liquid molten Al. A number of process parameters such as reaction temperature (800, 900, 1,000?°C), reaction time (45, 60, 75?min.) and compositions (Ti/B ratio: 5/1, 1/3) have been studied. The indigenously prepared master alloys were characterised by chemical analysis, particles size analysis, XRD and SEM/EDX microanalysis. Results of particle size analysis suggest that the sizes of the intermetallic particles [Al₃Ti and TiB₂ in Al?C5Ti?C1B and (Al, Ti)B₂ in Al?C1Ti?C3B] present in various Al?CTi?CB master alloys increases with increase in reaction temperature (800?C1,000?°C) and reaction time (45?C75?min.). The population of the particles decreases with increase in reaction time and temperature. Further, SEM/EDX studies revealed that different morphologies of the intermetallic particles were observed at different reaction temperatures and reaction times. Further, the performances of the above-prepared master alloys were assessed for their grain refining efficiency on Al?C7Si alloy by macroscopy, DAS analysis. Grain refinement studies suggest that, B-rich Al?C1Ti?C3B master alloy shows better grain refinement performance on Al?C7Si alloy when compared to Ti-rich Al?C5Ti?C1B master alloy.     

Functionally Graded Al Alloy Matrix <Emphasis Type="Italic">In-Situ</Emphasis> Composites

In the present work, functionally graded (FG) aluminum alloy matrix in-situ composites (FG-AMCs) with TiB₂ and TiC reinforcements were synthesized using the horizontal centrifugal casting process. A commercial Al-Si alloy (A356) and an Al-Cu alloy were used as matrices in the present study. The material parameters (such as matrix and reinforcement type) and process parameters (such as mold temperature, mold speed, and melt stirring) were found to influence the gradient in the FG-AMCs. Detailed microstructural analysis of the composites in different processing conditions revealed that the gradients in the reinforcement modify the microstructure and hardness of the Al alloy. The segregated in-situ formed TiB₂ and TiC particles change the morphology of Si particles during the solidification of Al-Si alloy. A maximum of 20 vol pct of reinforcement at the surface was achieved by this process in the Al-4Cu-TiB₂ system. The stirring of the melt before pouring causes the reinforcement particles to segregate at the periphery of the casting, while in the absence of such stirring, the particles are segregated at the interior of the casting.     

The effect of molybdenum addition on properties of iron aluminides

The effect of the addition of up to 10 pct molybdenum on several metallurgical properties of Fe-28Al (at. pct) to which 1 pct TiB₂ was added for grain refinement has been studied. It was determined that the addition of molybdenum results in a decrease in grain size, an increase in the recrystallization temperature, and an increase in the DO₃ to B2 ordering transformation temperature. The solubility limit of molybdenum in the matrix of the base alloy was found to be about 6 pct. At this concentration, another 1 pct is dissolved in the TiB₂ precipitates. Tensile strengths were increased slightly by adding up to 2 pct Mo, but ductility decreased, even though grain sizes were reduced. The fracture mode in tension did not change with addition of molybdenum up to 2 pct.     

Microstructure evolution in tial alloys with b additions: Conventional solidification

Solidification microstructures of arc-melted, near-equiatomic TiAl alloys containing boron additions are analyzed and compared with those of binary Ti-Al and Ti-B alloys processed in a similar fashion. With the exception of the boride phase, the matrix of the ternary alloy consists of the same α₂ (DO₁₉) and γ (Ll₀) intermetallic phases found in the binary Ti-50 at. pct Al alloy. On the other hand, the boride phase, which is TiB (B27) in the binary Ti-B alloys, changes to TiB₂ (C32) with the addition of Al. The solidification path of the ternary alloys starts with the formation of primary α (A3) for an alloy lean in boron (∼1 at. pct) and with primary TiB₂ for a higher boron concentration (∼5 at. pct). In both cases, the system follows the liquidus surface down to a monovariant line, where both α and TiB₂ are solidified concurrently. In the final stage, the α phase gives way to γ, presumably by a peritectic-type reaction similar to the one in the binary Ti-Al system. Upon cooling, the α dendrites order to α₂ and later decompose to a lath structure consisting of alternating layers of γ and α₂.     

Solidification paths and carbide morphologies in melt-processed MoSi2-SiC In Situ composites

The present investigation was undertaken to elucidate the microstructural evolution of MoSi₂-SiC in situ composites produced by melt processing. An assessment of the existing liquidus projection was performed by a combination of thermodynamic modeling, analysis of solidification microstructures, and measurements of the thermal history during solidification. Results show that the quasibinary MoSi₂-SiC eutectic occurs at ∼2 at. pct C and 2283 K, rather than 8 at. pct C and 2173 K, as previously reported. The ensuing L+MoSi₂+SiC monovariant line runs almost parallel to the SiMoSi₂ binary and terminates at a ternary L ↔ Si+MoSi₂+SiC eutectic calculated at 1.5Mo-0.84C (at. pct) and ∼1670 K. The maximum amount of SiC that may be produced by solidification along the quasibinary isopleth is ∼37 vol pct, of which ∼35 vol pct grows as primary. Analysis of solidification microstructures shows SiC grows with the cubic β polytype structure (B3), while MoSi₂ grows with the tetragonal C11 _b structure. Primary SiC may grow as equiaxed particles, platelets, and hopper crystals. Coupled growth with MoSi₂ leads to SiC in the shape of thin ribbons, sheets, and needles. The facets of the SiC crystals were identified to be of the {111} and {002} type, in agreement with the periodic bond chain analysis. The predominant platelike morphology was shown to develop due to a re-entrant twin mechanism similar to that observed in Si and Ge.     

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.     

Grain refinement in aluminum alloyed with titanium and boron

The aluminum corner of the ternary Al-B-Ti diagram was explored. A eutectic: Liq — Al + TiAl₃ + (Al, Ti)B₂ was found at approximately 0.05 wt pct Ti, 0.01 wt pct B; 659.5‡C. TiB₂ and A1B₂ form a continuous series of solid solutions, but no distinct ternary phase was found. The addition of boron to aluminum-titanium alloys expands the field of primary crystallization of TiAl₃ toward lower titanium contents and steepens the liquidus. In equilibrium conditions, pronounced grain refinement is found only in alloys in which TiAl₃ is primary and nucleates the aluminum solid solution before any other impurity can act. The peritectic reaction facilitates this priority but it is not necessary for grain refinement. Because of the low diffusivity of titanium and boron in aluminum, equilibrium is seldom attained and in commercial practice grain refinement by TiAl₃ is found also outside its equilibrium field of primary crystallization.     

Development of Al-Ti-C grain refiners containing TiC

Cast Al-Ti-C grain refiners were synthesized by reacting up to 2 pct graphite particles of 20 micron average size with stirred Al-(5 to 10) pct Ti alloy melts, which generated submicron-sized TiC particles within the melts, and their solidified structures showed preferential segregation of the carbide phase in the grain or cell boundary regions and occasional presence of free carbon whose amount exceeded equilibrium values. At the usual melt temperatures of below 1273 K, though, TiC formed first, but was subsequently found to react with the melt forming a sheathing of A1₄C₃ and Ti₃AlC which resulted into poisoning of the TiC particles. However, it was possible to reverse these reactions in order to regain the virgin TiC particles by superheating the melts in the temperature region where TiC particles are thermodynamically stable. Grain refining tests using the TiC master alloys produced fine equiaxed grains of cast aluminum whose sizes were comparable to that obtainable with the standard TiB₂ commercial grain refiner. TiC particles introducedvia the master alloys were found to occur in the grain centers, thereby confirming that they nucleated aluminum crystals. On leave from Regional Research Laboratory (CSIR), Bhopal, is Research Associate.     

Co-deformation processing and modeling of <Emphasis Type="Italic">In-Situ</Emphasis> multiphase composites

A series of in-situ, deformation-processed metal matrix composites were produced by direct powder extrusion of blended constituents. The resulting composites are comprised of a metallic Ti-6Al-4V matrix containing dispersed and co-deformed discontinuously reinforced-intermetallic matrix composite (DR-IMC) reinforcements. The DR-IMCs are comprised of discontinuous TiB₂ particulate within a titanium trialuminide or near-γ Ti-47Al matrix. Thus, an example of a resulting composite would be Ti-6Al-4V+40 vol pct (Al₃Ti+30 vol pct TiB₂) or Ti-6Al-4V+40 vol pct (Ti-47Al+40 vol pct TiB₂), with the DR-IMCs having an aligned, high aspect ratio morphology as a consequence of deformation processing. The degree to which both constituents deform during extrusion has been examined using systematic variations in the percentage of TiB₂ within the DR-IMC, and by varying the percentage of DR-IMC within the metal matrix. In the former instance, variation of the TiB₂ percentage effects variations in relative flow behavior; while in the latter, varying the percentage of DR-IMC within the metallic matrix effects changes in strain distribution among components. The results indicate that successful co-deformation processing can occur within certain ranges of relative flow stress; however, the extent of commensurate flow will be limited by the constituents’ inherent capacity to plastically deform.