Kinetics of Sulphation of Nickel and Cobalt Ferrites with Na$O, Melt Containing F'e3+ Ions

It has been experimentally established that nickel and cobalt can be extracted from their ferrites with sodium sulphate melt containing femc ions. The kinetics of extraction from synthetic ferrites using a melt of sodium and ferric sulphates of eutectic composition has been studied as a function of the particle size of the ferrite and temperature in the range 900 to 1073 K. The divalent ions in the ferrite exchange with the ferric ion in the melt, leaving a residue of hematite.The rate of reaction conforms to the Crank-Ginstling-Brounshtein diffusion model. The reaction rate is governed by the counter-diffusion of ~ e an~d ~+i ' +(or co2+) ions in the hematite lattice. Analytical expressions for the rate constants have been derived from the experimental data as a function of particle size and temperature. The activation energy for the extraction of nickel from nickel ferrite is 154(+10) kJ mol-' and the corresponding value for cobalt is 142(+10)kJ mol;'. In sulphation roasting of minerals containing nickel, the yield of nickel is generally limited to 75% due to the formation of insoluble ferrites. The use of melts based on sodium sulphate provides a possible route for enhancing the recovery of nickel to approximately 98%.

Microstructure and texture evolution during beta extrusion of boron modified Ti-6A1-4V alloy

Boron addition to conventional titanium alloys below the eutectic limit refines the cast microstructure and improves mechanical properties. The present work explores the influence of hypoeutectic boron addition on the microstructure and texture evolution in Ti-6Al-4V alloy under beta extrusion. The beta extruded microstructure of Ti-6Al-4V is characterized by shear bands parallel to the extrusion direction. In contrast, the extruded Ti-6Al-4V-0.1B alloy shows a regular beta worked microstructure consisting of fine prior beta grains and acicular alpha-lamellae with no signs of the microstructural instability. Crystallographic texture after extrusion was almost identical for the two alloys indicating the similarity in their transformation behavior, which is attributed to complete dynamic recrystallization during beta processing. Microstructural features as well as crystallographic texture indicate dominant grain boundary related deformation processes for the boron modified alloy that leads to homogeneous deformation without instability formation. The absence of shear bands has significant technological importance as far as the secondary processing of boron added alloys in (alpha + beta)-phase field are concerned. (C) 2012 Elsevier B.V. All rights reserved.

Microstructure and mechanical properties of oxidation resistant suction cast Nb-Si-Al alloy

In this paper, we report a significant improvement in mechanical and oxidation properties of near eutectic Nb-Si alloys by the addition of aluminum (Al) and control of microstructural length scale. A comparative study of two alloys Nb-18.79at%Si and Nb-12.3at%Si-9at%Al were carried out. The processing for microstructure refinements were carried out by vacuum suction casting in water cooled thick copper mould. It is shown that addition of Al suppresses Nb3Si phase and promotes beta Nb5Si3 phase under nonequilibrium solidification condition. The microstructural length scale and in particular eutectic spacing reduces significantly to 50-100 nm in suction cast ternary alloy. A detailed TEM study shows the presence of delta-Nb11Si4 phase in Nb matrix. The hardness of Nb solid solution can be increased as a consequence to a level observed in Nb3Si intermetallic due to the well oriented precipitates. Compression test yields the ultimate strength of 1.8 +/- 0.1 GPa and engineering strain of 2.3 +/- 0.03%. In comparison, the binary Nb-18.79 at% Si alloy possesses an ultimate strength of 1.35 +/- 0.1 GPa and strain of 0.2 +/- 0.01% when processed under identical conditions. The latter exhibits coarser microstructural length scale (300-400 nm) and a brittle behavior. The indentation fracture toughness of Al containing suction cast alloy shows a value of 20.2 +/- 0.5 MPa root m which represents a major improvement over bulk Nb-Si eutectic alloy. The detailed thermal studies confirm a multifold improvement in oxidation resistance up to 1000 degrees C. (C) 2012 Elsevier B.V. All rights reserved.

Microstructural Evolution and Some Unusual Effects During Thermo-Mechanical Cycling of Sn-Ag-Cu Alloys

Sn-Ag-Cu (SAC) solders are susceptible to appreciable microstructural coarsening during storage or service. This results in evolution of joint properties over time, and thereby influences the long-term reliability of microelectronic packages. Accurate prediction of this aging behavior is therefore critical for joint reliability predictions. Here, we study the precipitate coarsening behavior in two Sn-Ag-Cu (SAC) alloys, namely Sn-3.0Ag-0.5Cu and Sn-1.0Cu-0.5Cu, under different thermo-mechanical excursions, including isothermal aging at 150 degrees C for various lengths of time and thermo-mechanical cycling between -25 degrees C and 125 degrees C, with an imposed shear strain of similar to 19.6% per cycle, for different number of cycles. During isothermal aging and the thermo-mechanical cycling up to 200 cycles, Ag3Sn precipitates undergo rapid, monotonous coarsening. However, high number of thermo-mechanical cycling, usually between 200 and 600 cycles, causes dissolution and re-precipitation of precipitates, resulting in a fine and even distribution. Also, recrystallization of Sn-grains near precipitate clusters was observed during severe isothermal aging. Such responses are quite unusual for SAC solder alloys. In the regime of usual precipitate coarsening in these SAC alloys, an explicit parameter, which captures the thermo-mechanical history dependence of Ag3Sn particle size, was defined. Brief mechanistic description for the recrystallization of Sn grains during isothermal aging and reprecipitation of the Ag3Sn due to high number of thermo-mechanical cycles are also presented.

Microstructural and mechanical behavior study of suction cast Nb-Si binary alloys

The solidification pathways of Nb rich Nb-Si alloys when processed under non-equilibrium conditions require understanding. Continuing with our earlier work on alloying additions in single eutectic composition 1,2], we report a detailed characterization of the microstructures of Nb-Si binary alloys with wide composition range (10-25 at% Si). The alloys are processed using chilled copper mould suction casting. This has allowed us to correlate the evolution of microstructure and phases with different possible solidification pathways. Finally these are correlated with mechanical properties through studies on deformation using mechanical testing under indentation and compressive loads. It is shown that microstructure modification can significantly influence the plasticity of these alloys.

Role of convection in microstructure evolution during solidification

In this study, we present a new computational approach for studying the effect of melt convection on solidification at the micro-scale level. Models for dendritic and eutectic growth are developed on the basis of the enthalpy technique and incorporate the presence of flow in the domain. Simulation results show the growth and motion of dendrites and evolution of eutectic lamellae and their interaction with melt flow. The present study provides the foundation for development of an efficient generalized micro-scale solidification model, which can potentially be coupled with system-scale models based on the same framework.

Melting and solidification behavior of Pb-Sn embedded alloy nano-particles

Nano-sized bimetallic dispersoids consisting of (Pb) and beta-(Sn) phases of eutectic composition (Pb26.1Sn73.9) embedded in aluminum and Al-Cu-Fe quasicrystalline matrices have been prepared by rapid solidification processing. The two phases, face centered cubic (Pb) and body center tetragonal, beta-(Sn) solid solution co-exist in all the embedded nanoparticles at room temperature. The phases bear crystallographic orientation relationship with the matrix. In situ TEM study has been carried out for the alloy particles to study the melting and the solidification behavior. The detailed microscopic observations indicate formation of a single-phase metastable fcc (Pb) in the nano-particles prior to the melting during heating. Solidification of these particles begins with nucleation of fcc (Pb), which phase separates into fcc (Pb) and beta-(Sn) lamellae in the solid state. In situ X-ray diffraction study is carried out to obtain lattice parameter of metastable fcc (Pb) and thereby an estimate of amount of Sn dissolved in the metastable (Pb) prior to the melting. The results are discussed in terms of a metastable phase diagram between fcc Pb and fcc Sn and invoking the size effect on the metastable phase diagram. The size factor is found to play a critical role in deciding the pathway of phase transformation as well as the extension of solid solubility of Sn in fcc (Pb) in the nano-particles.

Semisolid Processing of A380 Al Alloy Using Cooling Slope

This study is aimed toward obtaining near spherical microstructural features of Rheocast A380 aluminum alloy. Cooling slope (CS) technique has been used to generate semisolid slurry from the superheated alloy melt. Spherodization of primary grains is the heart of semisolid processing which improves mechanical properties significantly in the parts cast from semisolid state compared to the conventional casting processes. Keeping in view of the desired microstructural morphology, i.e., rosette or spherical shape of primary alpha-Al phase, successive slurry samples have been collected during melt flow and oil quenched to investigate the microstructure evolution mechanism. Conventionally cast A380 Al alloy sample shows dendritic grains surrounded by large eutectic phase whereas finer, near spherical grains have been observed within the cooling slope processed slurry and also in the solidified castings which confirms the effectiveness of semisolid processing of the alloy following cooling slope technique. Grain refiner addition into the alloy melt is found to have favorable effect which leads to the generation of finer primary grains within the slurry with higher degree of sphericity.

Comprehending the Formation of Eutectics and Cocrystals in Terms of Design and Their Structural Interrelationships

The phenomenon of cocrystallization, which encompasses the art of making multicomponent organic solids such as cocrystals, solid solutions, eutectics, etc. for novel applications, has been less studied in terms of reliably and specifically obtaining a desired cocrystallization product and the issues that govern their formation. Further, the design, structural, and functional aspects of organic eutectics have been relatively unexplored as compared to solid solutions and cocrystals well-established by crystal engineering principles. Recently, eutectics were proposed to be designable materials on par with cocrystals, and herein we have devised a systematic approach, based on the same crystal engineering principles, to specifically and desirably make both eutectics and cocrystals for a given system. The propensity for strong homomolecular synthons over weak heteromolecular synthons and vice versa during supramolecular growth was successfully utilized to selectively obtain eutectics and cocrystals, respectively, in two model systems and in two drug systems. A molecular level understanding of the formation of eutectics and cocrystals and their structural interrelationships which is significant from both fundamental and application viewpoints is discussed. On the other hand, the obscurity in establishing a low melting combination as a eutectic or a cocrystal is resolved through phase diagrams.

Effects of Microstructure and Loading on Fracture of Sn-3.8Ag-0.7Cu Joints on Cu Substrates with ENIG Surface Finish

When dropped, electronic packages often undergo failure by propagation of an interfacial crack in solder joints under a combination of tensile and shear loading. Hence, it is crucial to understand and predict the fracture behavior of solder joints under mixed-mode high-rate loading conditions. In this work, the effects of the loading conditions (strain rate and loading angle) and microstructure interfacial intermetallic compound (IMC) morphology and solder yield strength] on the mixed-mode fracture toughness of Sn-3.8 wt.%Ag-0.7 wt.%Cu solder joints sandwiched between two Cu substrates with electroless nickel immersion gold (ENIG) metallization have been studied, and compared with the fracture behavior of joints attached to bare Cu. Irrespective of the surface finish, the fracture toughness of the solder joints decreased monotonically with strain rate and mode-mixity, both resulting in increased fracture proportion through the interfacial IMC layer. Furthermore, the proportion of crack propagation through the interfacial IMC layer increased with increase in the thickness and the roughness of the interfacial IMC layer and the yield strength of the solder, resulting in a decrease in the fracture toughness of the joint. However, under most conditions, solder joints with ENIG finish showed higher resistance to fracture than joints attached directly to Cu substrates without ENIG metallization. Based on the experimental observations, a fracture mechanism map is constructed correlating the yield strength of the solder, the morphology and thickness of the interfacial IMC, and the fracture mechanisms as well as the fracture toughness values for different solder joints under mode I loading.

Differential Cocrystallization Behavior of Isomeric Pyridine Carboxamides toward Antitubercular Drug Pyrazinoic Acid

Pyrazinoic acid, the active form of the antitubercular pro-drug Pyrazinamide, is an amphiprotic molecule containing carboxylic acid and pyridine groups and therefore can form both salts and cocrystals with relevant partner molecules. Cocrystallization of pyrazinoic acid with isomeric pyridine carboxamide series resulted in a dimorphic mixed-ionic complex with isonicotinamide and in eutectics with nicotinamide and picolinamide, respectively. It is observed that with alteration of the carboxamide position, steric and electrostatic compatibility issues between molecules of the combination emerge and affect intermolecular interactions and supramolecular growth, thus leading to either cocrystal or eutectic for different pyrazinoic acid-pyridine carboxamide combinations. Intermolecular interaction energy calculations have been performed to understand the role of underlying energetics on the formation of cocrystal/eutectic in different combinations. On the other hand, two molecular salts with piperazine and cytosine and a gallic acid cocrystal of the drug were obtained, and their X-ray crystal structures were also determined in this work.

Compressive flow behavior of Al-Si based alloy: Role of heat treatment

The flow characteristics of a near eutectic Al-Si based cast alloy have been examined in compression at strain rates varying from 3 x 10(-4) to 10(2) s(-1) and at three different temperatures, i.e., room temperature (RT), 100 degrees C and 200 degrees C. The dependence of the flow behavior on heat treatment is studied by testing the alloy in non-heat treated (NHT) and heat treated (HT) conditions. The heat treatment has strong influence on strain rate sensitivity (SRS), strength and work hardening behavior of the alloy. It is observed that the strength of the alloy increases with increase in strain rate and it increases more rapidly above the strain rate of 10(-1) s(-1) in HT condition at all the temperatures, and at 100 degrees C and 200 degrees C in NHT condition. The thermally dependent process taking place in the HT matrix is responsible for the observed greater SRS in HT condition. The alloy in HT condition exhibits a larger work hardening rate than in NHT condition during initial stages of straining. However, the hardening rate decreases more sharply at higher strains in HT condition due to precipitate shearing and higher rate of Si particle fracture. Thermal hardening is observed at 200 degrees C in NHT condition due to precipitate formation, which results in increased SRS at higher temperatures. Thermal softening is observed in HT condition at 200 C due to precipitate coarsening, which leads to a decrease in SRS at higher temperatures. Stress simulations by a finite element method support the experimentally observed particle and matrix fracture behavior. A negative SRS and serrated flow are observed in the lower strain rate regime (3 x 10(-4)-10(-2) s(-1)) at RT and 100 degrees C, in both NHT and HT conditions. The observations show that both dynamic strain aging (DSA) and precipitate shearing play a role in serrated flow. (C) 2015 Elsevier B.V. All rights reserved.

Deformation behaviour of Rheocast A356 Al alloy at microlevel considering approximated RVEs

A micromechanical approach is considered here to predict the deformation behaviour of Rheocast A356 (Al-Si-Mg) alloy. Two representative volume elements (RVEs) are modelled in the finite element (FE) framework. Two dimensional approximated microstructures are generated assuming elliptic grains, based on the grain size, shape factor and area fraction of the primary Al phase of the said alloy at different processing condition. Plastic instability is shown using stress and strain distribution between the Al rich primary and Si rich eutectic phases under different boundary conditions. Boundary conditions are applied on the approximated RVEs in such a manner, so that they represent the real life situation depending on their position on a cylindrical tensile test sample. FE analysis is carried out using commercial finite element code ABAQUS without specifying any damage or failure criteria. Micro-level in-homogeneity leads to incompatible deformation between the constituent phases of the rheocast alloy and steers plastic strain localisation. Plastic stain localised regions within the RVEs are predicted as the favourable sites for void nucleation. Subsequent growth of nucleated voids leads to final failure of the materials under investigation.

Correlation of microstructure and creep behaviour of MRI230D Mg alloy developed by two different casting technologies

The relationship between the as-cast microstructure and creep behaviour of the heat-resistant MRI230D Mg alloy produced by two different casting technologies is investigated. The alloy in both ingot-casting (IC) and high pressure die-casting (HPDC) conditions consists of alpha-Mg, 06 ((Mg,AI)(2)Ca), Al-Mn and Sn-Mg-Ca rich phases. However, the HPDC alloy resulted in relatively finer grain size and higher volume fraction of finer, denser network of eutectic C36 phase in the as-cast microstructure as compared to that of the IC alloy. The superior creep resistance exhibited by the HPDC alloy at all the stress levels and temperatures employed in the present investigation was attributed to the more effective dispersion strengthening effect caused by the presence of finer and denser network of the C36 phase. The increased amount of the eutectic C36 phase was the only change observed in the microstructures of both alloys following creep tests. (C) 2015 Elsevier B.V. All rights reserved.

Effect of processing route on phase stability in equiatomic multicomponent Ti20Fe20Ni20Co20Cu20 high entropy alloy

The evolution of microstructure and phase formation in equiatomic Ti20Fe20Ni20Co20Cu20 high entropy alloy synthesised by conventional arc melting followed with suction casting and ball milling with spark plasma sintering route is distinctly different. The cast microstructure exhibits one body centre cubic and two face centre cubic high entropy phases based on titanium, cobalt and copper respectively along with a eutectic containing Ti2Ni type Laves phase. On the contrary, spinodal decomposed microstructure consisting of cobalt and copper solid solution is obtained in the sintered sample. However, long term annealing of cast sample at 950 degrees C reveals a eutectoid transformation with different phases than the cast sample. The aforementioned observations are discussed using CALPHAD thermodynamical approach and available literature.