Diffusionless crystal growth in rapidly solidifying eutectic systems

Using a local nonequilibrium model of solidification, experiments on rapid eutectic growth are analyzed. An analytical solution of a problem of rapid lamellar eutectic growth under local nonequilibrium conditions in the solute diffusion field is found. It is shown that solute diffusion-limited growth of a eutectic pattern is completely finished, and diffusionless growth of the chemically homogeneous crystalline phase begins to proceed at a critical point V = V(D), where V is the solid-liquid interface velocity and V(D) is the solute diffusion speed in bulk liquid. A suppression of eutectic decomposition occurs in the range V > or = V(D) that results in a growth of homogeneous crystal phase with the initial (nominal) chemical composition of the binary system.     

Influence of local nonequilibrium on the rapid solidification of binary alloys

A local-nonequilibrium model of the diffusion of a solute during the rapid solidification of a binary alloy is considered. The model has two characteristic parameters: the diffusion velocity through the interface V _Di and the diffusion velocity in the bulk of the liquid phase V _D. The influence of local nonequilibrium on the separation of an impurity, the stability of the interface, and the dependence of the temperature of the interface on the velocity of the solidification front is investigated. A comparison with experiment is made. Zh. Tekh. Fiz. 68, 45–52 (March 1998)     

Comparative study of solute trapping and Gibbs free energy changes at the phase interface during alloy solidification under local nonequilibrium conditions

An analytical model has been developed to describe the influence of solute trapping during rapid alloy solidification on the components of the Gibbs free energy change at the phase interface with emphasis on the solute drag energy. For relatively low interface velocity V < V _D , where V _D is the characteristic diffusion velocity, all the components, namely mixing part, local nonequilibrium part, and solute drag, significantly depend on solute diffusion and partitioning. When V ≥ V _D , the local nonequilibrium effects lead to a sharp transition to diffusionless solidification. The transition is accompanied by complete solute trapping and vanishing solute drag energy, i.e. partitionless and “dragless” solidification.     

Ternary eutectic growth of Ag-Cu-Sb alloy within ultrasonic field

The liquid to solid transformation of ternary Ag42.4Cu21.6Sb36 eutectic alloy was accomplished in an ultrasonic field with a frequency of 35 kHz, and the growth mechanism of this ternary eutectic was examined. Theoretical calculations predict that the sound intensity in the liquid phase at the solidification interface increases gradually as the interface moves up from the sample bottom to its top. The growth mode of (ε θ Sb) ternary eutectic exhibits a transition of "divorced eutectic- mixture of anomalous and regular structures-regular eutectic" along the sample axis due to the inhomogeneity of sound field distribution. In the top zone with the highest sound intensity, the cavitation effect promotes the three eutectic phases to nucleate independently, while the acoustic streaming efficiently suppresses the coupled growth of eutectic phases. In the meantime, the ultrasonic field accelerates the solute transportation at the solid-liquid interface, which reduces the solute solubility of eutectic phases.     

二元合金微观偏析的相场法数值模拟

使用耦合溶质场的相场模拟研究了Ni-Cu二元合金枝晶生长过程中固相溶质扩散系数D_s 对枝晶形貌和微观偏析等的影响.计算结果表明，随着D_s的减少，固液界 面前沿溶质扩散层越薄，枝晶生长越有利，枝晶尖端生长的速度越大，侧向分支越发达；D< sub>s越小，固相中溶质成分的波动越强烈，随着D_s的增大，固相中溶质 成分的波动相应减小；溶质微观偏析程度随D_s的增大而减小. 关键词： 相场方法 微观偏析 固相扩散系数 数值模拟     

Determination of the colloidal crystal nucleation rate density

Colloidal suspensions of charged latex microspheres in water exhibit liquid-like or crystalline ordering depending on particle interaction and concentration. By virtue of large particle spacing and slow dynamics, colloidal systems offer a unique opportunity to study interfacial structure and dynamics. This paper presents the first reported experimental study of the nucleation rate density, c, of an nonequilibrium (supercooled) colloidal liquid to colloidal crystal first order phase transition. Local and global observations of colloidal crystals growing from a metastable colloidal liquid were used to determine c. Microscopic local observations revealed homogeneous nucleation and constant interface velocity growth of quasispherical crystallites in the bulk and heterogeneous nucleation of a crystalline sheet with lower growth velocity at the cell wall. Complementary global observations of the recrystallization transition made by measuring the time dependence of the suspension transparency (the fraction of transmitted laser light) determined c by fitting this curve to a model based on an extension of Avrami's theory of crystallization.     

Asymmetrical contribution of eutectic growth kinetics on the coupled growth behaviour in rapid eutectic solidification

The interface undercooling in classical eutectic growth theories consists of solute and curvature undercooling with different expression formats. However, a significant difference in interface kinetic coefficients arises for a disordered non-facetted solid solution and an ordered facetted intermetallic compound in that different growth kinetics govern the attachment kinetics at the solid–liquid interface, which correspond to a typical eutectic reaction with a solid solution and an intermetallic compound as its terminal eutectic phases. Following the pioneering work of Jackson and Hunt (Trans. Metall. Soc. AIME 236 1129 (1966) ), the kinetic undercooling is supplemented to interface undercooling and two eutectic phases are considered separately so as to diagnose the effect of the asymmetrical contribution of kinetic undercooling on the coupled eutectic growth behaviour. Further analysis indicates that it is the asymmetrical contribution of kinetic undercoolings of the facetted and non-facetted phases that enables the coupled eutectic composition shift to the facetted phase side so as to weaken the solute undercooling of the facetted phase and balance the kinetic contribution in the rapid solidification of coupled eutectics.     

Crystal growth of high magnetostrictive polycrystalline Fe81Ga19 alloys

High magnetostrictive Fe₈₁Ga₁₉ alloy was prepared by induction heating zone melting method. The microstructure, solute partition behaviour, orientation evolution and magnetostriction are investigated. During the crystal growth process, the initial small grains gradually grow into large columnar crystals, and the solid-liquid interface shows slightly concave morphology. The equilibrium solute partition coefficient (k₀), effective solute partition coefficient (k_e) and solution diffusion coefficient (D) are calculated to be 0.74, 0.76 and 1.04×10⁻⁹ m²/s, respectively. In the steady growth stage, the composition distribution of the FeGa rod is uniform with average level about 18.50 at% Ga, which is close to the nominal composition. The deviation of the 〈001〉 orientation from the axial direction evolves from about 8° to 3° along the growth direction, and the corresponding magnetostriction increases from the initial 180 ppm to the final 305 ppm.     

层状共晶定向凝固

本文从理论和实验两方面研究层状共晶定向凝固。理论上将层状共晶定向凝固与胞晶列定向凝固及Hele-Shaw胞中粘性指发展进行类比,给出层状共晶稳态凝固条件下溶质扩散、热传输与界面张力效应之间的耦合系,导出λ²ν=consi标度关系。实验上考察了规则Al-Al₂Cu共晶和非规则Al-Si共晶定向凝固,证实耦合关系存在。还讨论了两种共晶凝固界面特征和热传输的影响。 关键词：     

Effective diffusivity of solute in multiphase materials with segregation

The effective diffusion coefficient D_eff for solute in a multiphase microstructure in which solute segregation can occur is related to D_eff for an isomorphic microstructure in which no segregation occurs. This permits analytical expressions (approximations, bounds, etc.) and methods of numerical calculation for D_eff that neglect solute segregation to be applied to systems that exhibit segregation. As an example, exact results are obtained for solute diffusion and segregation to grain boundaries in an idealized polycrystalline microstructure.     

Diffusion-stress coupling in liquid phase during rapid solidification of binary mixtures

An analytical model has been developed to describe the diffusion-viscous stress coupling in the liquid phase during rapid solidification of binary mixtures. The model starts with a set of evolution equations for diffusion flux and viscous pressure tensor, based on extended irreversible thermodynamics. It has been demonstrated that the diffusion-stress coupling leads to non-Fickian diffusion effects in the liquid phase. With only diffusive dynamics, the model results in the nonlocal diffusion equations of parabolic type, which imply the transition to complete solute trapping only asymptotically at an infinite interface velocity. With the wavelike dynamics, the model leads to the nonlocal diffusion equations of hyperbolic type and describes the transition to complete solute trapping and diffusionless solidification at a finite interface velocity in accordance with experimental data and molecular dynamic simulation.     

Determination of the nonequilibrium concentration of vacancies in silicon crystals by measuring the concentration of nickel atoms at lattice sites

A method is proposed for determining the nonequilibrium concentration of vacancies and vacancy complexes in silicon crystals by measuring the concentration of electrically active nickel atoms at the sites of the silicon lattice, [Ni _s ], after the diffusion of nickel at temperatures from 550 to 650°C. It is shown experimentally that, after the diffusion of nickel from the surface into silicon samples with different initial nonequilibrium concentrations of vacancy complexes, [V]_init, formed during crystal growth, the concentration [Ni _s ] in the bulk of a sample to a good degree of accuracy corresponds to the vacancy concentration [V]_init determined by a standard method based on the analysis of the concentration profiles of [Au _s ] after the diffusion of gold from the surface. This method for determining the concentration of vacancies is much simpler than the standard method and allows one to use lower temperatures and a lower thermal budget.     

Small-signal ac response of Ba1−xLaxF2+x crystals

The small-signal ac response of single crystalline Ba_1?xLa_xF_2+x solid solutions has been studied in the temperature region 300–820 K, and in the frequency range 4×10^?2–5×10⁴ Hz. At low temperatures the frequency dispersion is dominated by processes in the bulk. Apart from the bulk conductance these processes include a dielectric response determined by broad distributions of dipole-like relaxations. The increase of the static dielectric constant with increasing solute content is explained. At higher temperatures the frequency dispersion reflects interfacial phenomena. In addition to an almost ideal interface capacitance, phenomena are observed which indicate the growth of a surface layer due to a reaction between the electrolyte, and residual oxygen and/or water vapour from the ambient.     

二元合金等温凝固过程的相场模型

基于Ginzberg-Landau理论，发展了一个与WBM模型和KKS模型一致的新相场模型.并利用该相场模型与溶质场耦合计算，以Al-65%Cu合金为例模拟了不同过冷度条件下，二元合金凝固过程的等轴枝晶生长过程.研究过冷度对二元合金等温凝固过程的等轴枝晶生长以及溶质场分布的影响.结果表明：随着过冷度的增大，枝晶的二次枝晶更加发达，浓度Peclet数和枝晶尖端的生长速率增大，而枝晶尖端的曲率半径减小，枝晶前沿的溶质富集现象也更严重；另外，计算结果与Ivantsov理论符合较好. 关键词： 相场法 枝晶生长 溶质场 Ivantsov理论     

Photoemission and x-ray studies of metal hydrides and hydride formation at metal/hydride interfaces

Synchrotron radiation photoemission was used to investigate the concentration dependent intensity of hydrogen-induced states for a series of niobium hydrides. These intensities were found to be linearly related to the fraction of β phase hydride present in the sample, as deduced from the bulk phase diagram, and we conclude that fracturing did not produce a self-sustaining surface hydride layer. Photoemission studies of V overlayers on NbH_0.799 showed strong hydrogen outdiffusion and the formation of the interface hydride phase which is more stable than VH prepared in bulk form. X-ray diffraction studies of thick V-H overlayers subsequently showed the absence of long-range order. These results demonstrate that interfacial diffusion of hydrogen from NbH_0.799 into the V overlayer produced a stable hydride with electronic properties analogous to those of crystalline VH but with dominant local interactions.     

Mg-Al合金熔体中固液界面结构的分子动力学研究

本文采用分子动力学研究了Mg-3%Al合金熔体中固液界面结构及界面附近原子的扩散行为.计算结果表明,该二元合金的固液界面为粗糙界面.垂直于界面方向的数密度分布,表现出复杂波动的特征,这种波动一直延伸到液体中.在界面附近的区域,扩散系数的三个不同方向的分量表现出了明显的各向异性,并且这种各向异性一直持续到液相当中.对界面二维结构的分析表明,界面附近液相原子的二维排列呈现出从长程有序逐渐过渡到短程有序的变化.     

Thermal and chemical diffusion in the rapid solidification of binary alloys

Solidification of binary alloys is characterized by the necessity to reject away from the advancing front two conserved quantities: the latent heat released at the solid-liquid interface and the solute atoms that cannot be accommodated in the solid phase. As thermal diffusion is much faster than chemical diffusion, the latter is generally assumed to be the rate limiting mechanism for the process, and the problem is addressed through the isothermal approximation. In the present paper we use the phase-field model to study the planar growth of a solid germ, nucleated in its undercooled melt. We focus on the effects of a noninstantaneous thermal relaxation. The steady growth predicted at large supersaturation in the isothermal limit is prevented. Depending on the value of the Lewis number the growth rate is limited by either mass or heat diffusion; in the latter case we observe a sharp transition between two different regimes, in which originates a nonmonotonic time dependence of the interface temperature. The effects of this transition reflect in the composition of the solidified alloy.     

深过冷三元Ni-Cu-Co合金的快速枝晶生长

研究了深过冷条件下三元Ni₈₀Cu₁₀Co₁₀合金的快速枝晶生长, 采用电磁悬浮无容器处理方法获得了335 K(0.2T_L)的最大过冷度. X射线衍射分析与差示扫描量热分析均表明,凝固组织为α-Ni单相固溶体. 随过冷度增大, 凝固组织显著细化, 并且当过冷度达110 K时，凝固组织的形态由粗大形枝晶转变为等轴晶. 深过冷条件下溶质截留效应增强, 使得微观偏析程度减小. 对不同过冷度下合金枝晶的生长速度进 关键词： 深过冷 枝晶生长 快速凝固 溶质截留