Synthesis of nanodispersed phases during rapid solidification and crystallization of glasses in Ti75Ni25 alloys

The formation of the metallic glass and crystalline phases and related microstructures and the decomposition behavior of rapidly solidified Ti75Ni25 alloys obtained under different processing conditions have been investigated in detail. The competition between glass transition and nucleation of beta-Ti during rapid solidification leads to the possibility of synthesizing the nanocomposites of beta-Ti and glass. Additionally, it is shown that the presence of a small amount of Si also promotes simultaneous nucleation of fine Ti2Ni intermetallic compound. Thermodynamic calculation of the metastable phase diagram indicates the presence of a metastable eutectic reaction between alpha-Ti and Ti2Ni. Evidence of this reaction at lower cooling rates has been presented. On heating, the glass decomposes through this reaction. Finally, on the basis of understanding of the microstructural evolution during decomposition, a new approach has been adopted to synthesize a nanodispersed composite of alpha-Ti in the crystalline Ti2Ni matrix with a narrow size distribution by controlling the devitrification heat treatment of the metallic glass.

The effect of SiC particles on the size and morphology of eutectic silicon in cast A356/SiCp composites

Properties of cast aluminium matrix composites are greatly influenced by the nature of distribution of reinforcing phase in the matrix and matrix microstructural length scales, such as grain size, dendrite arm spacing, size and morphology of secondary matrix phases, etc. Earlier workers have shown that SIC reinforcements can act as heterogeneous nucleation sites for Si during solidification of Al-Si-SiC composites. The present study aims at a quantitative understanding of the effect of SiC reinforcements on secondary matrix phases, namely eutectic Si, during solidification of A356 Al-SiC composites. Effect of volume fraction of SiC particulate on size and shape of eutectic Si has been studied at different cooling rates. Results indicate that an increase in SiC volume fraction leads to a reduction in the size of eutectic Si and also changes its morphology from needle-like to equiaxed. This is attributed to the heterogeneous nucleation of eutectic Si on SiC particles. However, SiC particles are found to have negligible influence on DAS. Under all the solidification conditions studied in the present investigation, SiC particles are found to be rejected by the growing dendrites. (C) 1999 Elsevier Science Ltd. All rights reserved.

Grain Floatation During Equiaxed Solidification of an Al-Cu Alloy in a Side-Cooled Cavity: Part II-Numerical Studies

In this article, a single-phase, one-domain macroscopic model is developed for studying binary alloy solidification with moving equiaxed solid phase, along with the associated transport phenomena. In this model, issues such as thermosolutal convection, motion of solid phase relative to liquid and viscosity variations of the solid-liquid mixture with solid fraction in the mobile zone are taken into account. Using the model, the associated transport phenomena during solidification of Al-Cu alloys in a rectangular cavity are predicted. The results for temperature variation, segregation patterns, and eutectic fraction distribution are compared with data from in-house experiments. The model predictions compare well with the experimental results. To highlight the influence of solid phase movement on convection and final macrosegregation, the results of the current model are also compared with those obtained from the conventional solidification model with stationary solid phase. By including the independent movement of the solid phase into the fluid transport model, better predictions of macrosegregation, microstructure, and even shrinkage locations were obtained. Mechanical property prediction models based on microstructure will benefit from the improved accuracy of this model.

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.

Laser assisted directional solidification of zirconia-based eutectics

Directionally solidified zirconia-based eutectic (DSE) fibres were obtained using the laser floating zone (LFZ) method. Two systems were investigated: zirconia-barium zirconate and zirconia-mullite. The purpose was to take advantage of zirconia properties, particularly as an ionic conductor and a mechanical rein-forcement phase. The influence of processing conditions in the structural and microstructural characteristics and their consequences on the electrical and mechanical behaviour were the focus of this thesis. The novel zirconia-barium zirconate eutectic materials were developed in order to combine oxygen ionic conduction through zirconia with protonic conduction from barium zirconate, promoting mixed ionic conduction behaviour. The mi-crostructure of the fibres comprises two alternated regions: bands having coarser zirconia-rich microstructure; and inter-band regions changing from a homogeneous coupled eutectic, at the lowest pulling rate, to columnar colony microstructure, for the faster grown fibres. The bands inter-distance increases with the growth rate and, at 300 mm/h, zirconia dendrites develop enclosed in a fine-interpenetrated network of 50 vol.% ZrO2-50 vol.% BaZrO3. Both phases display contiguity without interphase boundaries, according to impedance spec-troscopy data. Yttria-rich compositions were considered in order to promote the yttrium incorporation in both phases, as revealed by Raman spectroscopy and corroborated by the elemental chemical analysis in energy dispersive spectros-copy. This is a mandatory condition to attain simultaneous contribution to the mixed ionic conduction. Such results are supported by impedance spectrosco-py measurements, which clearly disclose an increase of total ionic conduction for lower temperatures in wet/reduction atmospheres (activation energies of 35 kJ/mol in N2+H2 and 48 kJ/mol in air, in the range of 320-500 ºC) compared to the dry/oxidizing conditions (attaining values close to 90 kJ/mol, above 500 ºC). At high temperatures, the proton incorporation into the barium zirconate is un-favourable, so oxygen ion conduction through zirconia prevails, in dry and oxi-dizing environments, reaching a maximum of 1.3x10-2 S/cm in dry air, at ~1000 ºC. The ionic conduction of zirconia was alternatively combined with another high temperature oxygen ion conductor, as mullite, in order to obtain a broad elec-trolytic domain. The growth rate has a huge influence in the amount of phases and microstructure of the directionally solidified zirconia-mullite fibres. Their microstructure changes from planar coupled eutectic to dendritic eutectic mor-phology, when the growth rate rises from 1 to 500 mm/h, along with an incre-ment of tetragonal zirconia content. Furthermore, high growth rates lead to the development of Al-Si-Y glassy phase, and thus less mullite amount, which is found to considerably reduce the total ionic conduction of as-grown fibres. The reduction of the glassy phase content after annealing (10h; 1400 ºC) promotes an increase of the total ionic conduction (≥0.01 S/cm at 1370 °C), raising the mullite and tetragonal zirconia contents and leading to microstructural differ-ences, namely the distribution and size of the zirconia constituent. This has important consequences in conductivity by improving the percolation pathways. A notable increase in hardness is observed from 11.3 GPa for the 10 mm/h pulled fibre to 21.2 GPa for the fibre grown at 500 mm/h. The ultra-fine eutectic morphology of the 500 mm/h fibres results in a maximum value of 534 MPa for room temperature bending strength, which decreases to about one-fourth of this value at high temperature testing (1400 ºC) due to the soft nature of the glassy-matrix.

Microstructural and mechanical study of AL2O3/Er3Al5O12 eutectic rods grown by the laser floating zone method

Eutectic rods of Al2O3–Er3Al5O12 were grown by directional solidification using the laser-heated floating zone method at rates in the range 25–1500 mm/h. Their microstructure and mechanical properties (hardness, toughness and strength) were investigated as a function of the growth rate. A homogeneous and interpenetrated microstructure was found in most cases, and interphase spacing decreased with growth rate following the Hunt–Jackson law. Hardness increased slightly as the interphase spacing decreased while toughness was low and independent of the microstructure. The rods presented very high bending strength as a result of the homogeneous microstructure, and their strength increased rapidly as the interphase spacing decreased, reaching a maximum of 2.7 GPa for the rods grown at 750 mm/h. The bending strength remained constant up to 1300 K and decreased above this temperature. The relationship between the microstructure and the mechanical properties was established from the analysis of the microstructure and of the fracture mechanisms

Effects of boron-strontium interactions on eutectic modification in Al-10 mass%Si alloys

The effects of boron and strontium interactions on the eutectic silicon in hypoeutectic Al-Si alloys have been studied. Samples were prepared from an AI-I 0 mass%Si base alloy with different Al-B additions, alone and in combination with strontium. In alloys containing no strontium, boron additions do not cause modification of the eutectic silicon, while in strontium containing alloys, boron additions reduce the level of modification of the eutectic silicon. Thermal analysis parameters and eutectic silicon microstructures were investigated with respect to the Sr to B ratio. In order to modify the eutectic silicon, a Sr/B ratio exceeding 0.4 is required.

Effects of boron on eutectic modification of hypoeutectic Al-Si alloys

The effects of boron on the eutectic modification and solidification mode of hypoeutectic Al-Si alloys have been studied adding different boride phases. The results show that boron does not cause modification of the eutectic silicon. Boron-containing samples display eutectic nucleation and growth characteristics similar to that of unmodified alloys. (C) 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Damage by eutectic particle cracking in aluminum casting alloys A356/357

The strain dependence of particle cracking in aluminum alloys A356/357 in the T6 temper has been studied in a range of microstructures produced by varying solidification rate and Mg content, and by chemical (Sr) modification of the eutectic silicon. The damage accumulates linearly with the applied strain for all microstructures, but the rate depends on the secondary dendrite arm spacing and modification state. Large and elongated eutectic silicon particles in the unmodified alloys and large pi-phase (Al9FeMg3Si5) particles in alloy A357 show the greatest tendency to cracking. In alloy A356, cracking of eutectic silicon particles dominates the accumulation of damage while cracking of Fe-rich particles is relatively unimportant. However, in alloy A357, especially with Sr modification, cracking of the large pi-phase intermetallics accounts for the majority of damage at low and intermediate strains but becomes comparable with silicon particle cracking at large strains. Fracture occurs when the volume fraction of cracked particles (eutectic silicon and Fe-rich intermetallics combined) approximates 45 pct of the total particle volume fraction or when the number fraction of cracked particles is about 20 pct. The results are discussed in terms of Weibull statistics and existing models for dispersion hardening.

Eutectic grains in unmodified and strontium-modified hypoeutectic aluminum-silicon alloys

Additions of strontium to hypoeutectic aluminum-silicon alloys modify the morphology of the eutectic silicon phase from a coarse platelike structure to a fine fibrous structure. Thermal analysis, interrupted solidification, and microstructural examination of sand castings in this work revealed that, in addition to a change in silicon morphology, modification with strontium also causes an increase in the size of eutectic grains. The eutectic grain size increases because fewer grains nucleate, possibly due to poisoning of the phosphorus-based nucleants, that are active in the unmodified alloy. A simple growth model is developed to estimate the interface velocity during solidification of a eutectic grain. The model confirms, independent of microstructural observations, that the addition of 100 ppm strontium increases the eutectic grain size by at least an order of magnitude compared with the equivalent unmodified alloy. The model predicts that the growth velocity varies significantly during eutectic growth. At low strontium levels, these variations may be sufficient to cause transitions between flake and fibrous silicon morphologies depending on the casting conditions. The model can be used to rationally interpret the eutectic grain structure and silicon morphology of fully solidified aluminum-silicon castings and, when coupled with reliable thermal data, can be used to estimate the eutectic grain size.

Segregation of particles and its influence on the morphology of the eutectic silicon phase in Al-7 wt.% Si alloys

A new modification phenomenon is reported for Al-Si alloys, where the Al-Si eutectic is refined by segregated TiB2 particles. The TiB2 particles are pushed to the Al-Si phase boundary during solidification of the eutectic and it is believed that at high concentrations the TiB2 particles restrict solute redistribution causing refinement of the Si. (c) 2005 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Interactions between iron, manganese, and the Al-Si eutectic in hypoeutectic Al-Si alloys

Sand-cast plates were used to determine the effect of iron and manganese concentrations on porosity levels in Al-9 pet Si-0.5 pet Mg alloys. Iron increased porosity levels. Manganese additions increased porosity levels in alloys with 0.1 pet Fe, but reduced porosity in alloys with 0.6 and I pet Fe. Thermal analysis and quenching were undertaken to determine the effect of iron and manganese on the solidification of the Al-Si eutectic. At high iron levels, the presence of large beta-Al5FeSi was found to reduce the number of eutectic nucleation events and increase the eutectic grain size. The preferential formation of alpha-Al15Mn3Si2 upon addition of manganese reversed these effects. It is proposed that this interaction is due to beta-Al5FeSi and the Al-Si eutectic having common nuclei. Porosity levels are proposed to be controlled by the eutectic grain size and the size of the iron-bearing intermetallic particles rather than the specific intermetallic phase that forms.

Melting and solidification of Zinc-Aluminium alloys

Following a scene-setting introduction are detailed reviews of the relevant scientific principles, thermal analysis as a research tool and the development of the zinc-aluminium family of alloys. A recently introduced simultaneous thermal analyser, the STA 1500, its use for differential thermal analysis (DTA) being central to the investigation, is described, together with the sources of support information, chemical analysis, scanning electron microscopy, ingot cooling curves and fluidity spiral castings. The compositions of alloys tested were from the binary zinc-aluminium system, the ternary zinc-aluminium-silicon system at 30%, 50% and 70% aluminium levels, binary and ternary alloys with additions of copper and magnesium to simulate commercial alloys and five widely used commercial alloys. Each alloy was shotted to provide the smaller, 100mg, representative sample required for DTA. The STA 1500 was characterised and calibrated with commercially pure zinc, and an experimental procedure established for the determination of DTA heating curves at 10°C per minute and cooling curves at 2°C per minute. Phase change temperatures were taken from DTA traces, most importantly, liquidus from a cooling curve and solidus from both heating and cooling curves. The accepted zinc-aluminium binary phase diagram was endorsed with the added detail that the eutectic is at 5.2% aluminium rather than 5.0%. The ternary eutectic trough was found to run through the points, 70% Al, 7.1% Si, 545°C; 50% Al, 3.9% Si, 520°C; 30% Al, 1.4% Si, 482°C. The dendrite arm spacing in samples after DTA increased with increasing aluminium content from 130m at 30% to 220m at 70%. The smallest dendrite arm spacing of 60m was in the 30% aluminium 2% silicon alloy. A 1kg ingot of the 10% aluminium binary alloy, insulated with Kaowool, solidified at the same 2°C per minute rate as the DTA samples. A similar sized sand casting was solidified at 3°C per minute and a chill casting at 27°C per minute. During metallographic examination the following features were observed: heavily cored phase which decomposed into ' and '' on cooling; needles of the intermetallic phase FeAl4; copper containing ternary eutectic and copper rich T phase.