Thermophysical properties and structure of stable and metastable liquid cobalt

The thermophysical properties and structure of liquid cobalt are investigated in the temperature range from 1000 to 2400 K. The properties include density, molar volume, enthalpy and specific heat at both normal and undercooled states. The density decreases linearly with the increase of temperature. At the melting point, the value of density is 7.71 g cm⁻³, and its temperature coefficient is . The molar volume increases with the increase of temperature in a nonlinear manner. The enthalpy increases linearly with the rise of temperature. This indicates that the specific heat changes little with temperature: 40.11 J mol⁻¹ K⁻¹. Furthermore, the liquid structure is studied by analyzing the pair correlation function. With the increase of undercooling, the degree of short range order of liquid cobalt becomes more and more remarkable, which is deduced by the appearance of a saddle at the second neighbor distance.     

Undercooling and metastable phase formation in a Bi95Sb5 melt

High undercoolings have been obtained in bulk Bi₉₅Sb₅ alloy melts by the cyclic superheating and cooling technology. The highest undercooling that was achieved in this paper is 121 K. The influence of various processing factors on the undercooling behavior is examined. Undercooling of 121 K leads to the formation of a metastable solid phase with the tetragonal crystal structure. The phase selection and the metastable phase formation have been discussed based on the classical nucleation theory. A criterion that contains the relative melting temperature, the relative molar volume of the solid, the relative structure-dependent factor, and the undercooling has been developed to interpret the formation of the metastable tetragonal phase. Received: 12 January 2000 / Accepted: 28 March 2000 / Published online: 13 July 2000     

Phase field theory of heterogeneous crystal nucleation

The phase field approach is used to model heterogeneous crystal nucleation in an undercooled pure liquid in contact with a foreign wall. We discuss various choices for the boundary condition at the wall and determine the properties of critical nuclei, including their free energy of formation and the contact angle as a function of undercooling. For particular choices of boundary conditions, we may realize either an analog of the classical spherical cap model or decidedly nonclassical behavior, where the contact angle decreases from its value taken at the melting point towards complete wetting at a critical undercooling, an analogue of the surface spinodal of liquid-wall interfaces.     

Thermophysical properties of stable and metastable liquid copper and nickel by molecular dynamics simulation

Molecular dynamics simulation combined with an embedded atom method (EAM) potential was applied to the calculation of the specific heat and the diffusion coefficient for superheated and undercooled liquid copper and nickel as functions of temperature. The system contains 108,000 atoms. The calculated results show that the enthalpy increases linearly with the rise of temperature. There are no breaks at their melting temperatures of 1356 and 1726 K. It is found that the calculated specific heats of Cu and Ni are 32.75 and 36.11 J/mol/K respectively. The calculated mean square displacements increase linearly with calculated time. The diffusion coefficients are exponentially dependent on temperature. Moreover, the calculated results are in good agreement with the reported experimental results for the specific heat and diffusion coefficient.     

Thermophysical properties of Ni-5%Sn alloy melt

The surface tension and specific heat of Ni-5%Sn alloy melt were measured by the oscillating drop method and the drop calorimetric method using electromagnetic levitation, respectively. The temperature coefficient of surface tension is 6.43×10⁻⁴ N·m⁻¹K⁻¹ within the temperature regime of 1464–1931 K. The enthalpy change was measured in the temperature range from 1461 to 1986 K, and the average specific heat was obtained as 43.03 J·mol⁻¹K⁻¹. Some other thermophysical properties, such as viscosity, solute diffusion coefficient, density, thermal diffusivity and thermal conductivity of this alloy melt, were derived based on the experimentally measured surface tension and specific heat. Using these thermophysical parameters, the relation between solute trapping and undercooling in rapidly solidified α-Ni was calculated, and the theoretical prediction shows a good agreement with experimental data.     

Ultrafast solid–liquid–vapor phase change of a gold film induced by pico- to femtosecond lasers

Melting, vaporization and resolidification processes of thin gold film irradiated by a femtosecond pulse laser are studied numerically. The nonequilibrium heat transfer in electrons and lattice is described using a two-temperature model. The solid–liquid interfacial velocity, as well as elevated melting temperature and depressed solidification temperature, is obtained by considering the interfacial energy balance and nucleation dynamics. An iterative procedure based on energy balance and gas kinetics law to track the location of liquid–vapor interface is utilized to obtain the material removal by vaporization. The effect of surface heat loss by thermal radiation was discussed. The influences of laser fluence and duration on the evaporation process are studied. Results show that higher laser fluence and shorter laser pulse width lead to higher interfacial temperature, deeper melting and ablation depths.     

Specific heat and related thermophysical properties of liquid Fe-Cu-Mo alloy

The specific heat and related thermophysical properties of liquid Fe77.5Cu13Mo9.5 monotectic alloy were investigated by an electromagnetic levitation drop calorimeter over a wide temperature range from 1482 to 1818 K. A maximum undercooling of 221 K (0.13 Tm) was achieved and the specific heat was determined as 44.71 J·mol-1·K-1. The excess specific heat, enthalpy change, entropy change and Gibbs free energy difference of this alloy were calculated on the basis of experimental results. It was found that the calculated results by traditional estimating methods can only describe the solidification process under low undercooling conditions. Only the experimental results can reflect the reality under high undercooling conditions. Meanwhile, the thermal diffusivity, thermal conductivity, and sound speed were derived from the present experimental results. Furthermore, the solidified microstructural morphology was examined, which consists of (Fe) and (Cu) phases. The calculated interface energy was applied to exploring the correlation between competitive nucleation and solidification microstructure within monotectic alloy.     

Phase transitions and kinetic properties of gold nanoparticles confined between two-layer graphene nanosheets

The thermodynamic and kinetic behaviors of gold nanoparticles confined between two-layer graphene nanosheets (two-layer-GNSs) are examined and investigated during heating and cooling processes via molecular dynamics (MD) simulation technique. An EAM potential is applied to represent the gold–gold interactions while a Lennard–Jones (L–J) potential is used to describe the gold–GNS interactions. The MD melting temperature of 1345 K for bulk gold is close to the experimental value (1337 K), confirming that the EAM potential used to describe gold–gold interactions is reliable. On the other hand, the melting temperatures of gold clusters supported on graphite bilayer are corrected to the corresponding experimental values by adjusting the ε_Au–C value. Therefore, the subsequent results from current work are reliable. The gold nanoparticles confined within two-layer GNSs exhibit face center cubic structures, which is similar to those of free gold clusters and bulk gold. The melting points, heats of fusion, and heat capacities of the confined gold nanoparticles are predicted based on the plots of total energies against temperature. The density distribution perpendicular to GNS suggests that the freezing of confined gold nanoparticles starts from outermost layers. The confined gold clusters exhibit layering phenomenon even in liquid state. The transition of order–disorder in each layer is an essential characteristic in structure for the freezing phase transition of the confined gold clusters. Additionally, some vital kinetic data are obtained in terms of classical nucleation theory.     

铝纳米颗粒的热物性及相变行为的分子动力学模拟

采用分子动力学方法模拟了纳米金属铝在粒径为0.8-3.2 nm 时的熔点、密度和声子热导率的变化, 研究了粒径为1.6 nm的铝纳米颗粒的密度、比热和声子热导率随温度的变化. 采用原子嵌入势较好地模拟了纳米金属铝的热物性及相变行为, 根据能量-温度曲线和比热容-温度曲线对铝纳米颗粒的相变温度进行了研究, 并利用表面能理论、尺寸效应理论对铝纳米颗粒熔点的变化进行了分析. 随着纳米粒径的不断增大, 铝纳米颗粒的熔点呈递增状态, 当粒径在2.2-3.2 nm时, 熔点的增幅减缓, 但仍处于递增趋势. 随着纳米粒径的增大, 铝纳米颗粒的密度呈单调递减, 热导率则呈线性单调递增, 且热导率的变化情况符合声子理论. 随着温度的升高, 粒径为1.6 nm的铝纳米颗粒的密度、热导率均减小. 该模拟从微观原子角度对纳米材料的热物性进行了研究, 对设计基于铝纳米颗粒的相变材料具有指导意义.     

Heat and mass transfer at the ignition of a liquid substance by a single “Hot” particle

The results of a numerical solution to the problem of heat and mass transfer at the ignition of a liquid flammable substance by a single particle heated to a high temperature located on its surface are presented. The problem is solved within the framework of a gas phase model of ignition. A mathematical model is formulated. It describes the following processes in a two-dimensional statement: the heat conduction and evaporation of a flammable liquid and the diffusion and convection of the combustible vapors in the oxidizer medium in the system “particle heated to a high temperature-liquid flammable substance-air.” The numerical investigations established the relation between the ignition delay time, the particle temperature and sizes, and the particle minimum temperature and sizes at which ignition of a combustible liquid is possible.     

Studies of pulsed laser melting and rapid solidification using amorphous silicon

Pulsed laser melting of ion implantation-amorphized silicon layers, and the subsequent solidification of undercooled liquid silicon, have been studied experimentally and theoretically. Measurements of the time of the onset of melting of amorphous silicon layers, during an incident laser pulse, have been combined with measurements of the duration of melting, and with modified melting model calculations to demonstrate that the thermal conductivity, K_a, of amorphous silicon is very low (K_a0.02 W/cm K). K_a is also found to be the dominant parameter determining the dynamical response of amorphous silicon to pulsed laser radiation; the latent heat of fusion and melting temperature of amorphous silicon are relatively unimportant. Transmission electron microscopy indicates that bulk (volume) nucleation occurs directly from the highly undercooled liquid silicon that can be prepared by pulsed laser melting of amorphous silicon layers at low laser energy densities. A modified thermal melting model has been constructed to simulate this effect and is presented. Nucleation of crystalline silicon apparently occurs at a nucleation temperature, T_n, that is higher than the temperature, T_a, of the liquid-to-amorphous phase transition. The model calculations demonstrate that the release of latent heat by bulk nucleation occurring during the melt-in process is essential to obtaining agreement with experimentally observed depths of melting. These calculations also show that this release of latent heat accompanying bulk nucleation can result in the existence of buried molten layers of silicon in the interior of the sample after the surface has solidified. It is pointed out that the occurrence of bulk nucleation implies that the liquid-to-amorphous phase transition (produced using picosecond or ultraviolet nanosecond laser pulses) cannot be explained by purely thermodynamic considerations.     

Hydrodynamic fluctuations in heavy fermion systems

A theory of hydrodynamic fluctuations in heavy fermion systems is presented. It is used to compute the attenuation and velocity of longitudinal ultrasound. The attenuation is dominated by the coupling of phonons to electronic density fluctuations. A discrepancy is resolved between theory and experiments on UPt₃, which has been existing with respect to the absolute magnitude of the temperature dependent attenuation. The latter provides direct proof for a large Fermi liquid parameterF ₀ ^s . The phonon Green's function is found to have a four-pole structure, resulting in two diffusive modes. One is the conventional one due to heat diffusion while the other is due to electron density diffusion and is a characteristic feature of heavy fermion systems. The two modes are coupled at finite temperatures. With the help of a model Hamiltonian (slave boson mean-field formulation of the Anderson lattice Hamiltonian) the ultrasound attenuation is calculated for low temperatures.     

液态Ti-Al合金的深过冷与快速枝晶生长

采用电磁悬浮和自由落体两种试验技术研究了液态Ti-25 wt.%Al合金的亚稳过冷能力、晶体形核机制和枝晶生长过程. 试验发现, 即使电磁悬浮无容器状态下仍难以消除润湿角θ ≥60°的异质晶核, 合金熔体过冷度可达210 K (0.11T_L). β-Ti相形核的热力学驱动力随过冷度近似以线性方式增大, 其枝晶生长速度高达11.2 m/s, 从而在慢速冷却条件下实现了快速凝固. 理论计算表明, 随着过冷度的逐步增大, β相枝晶生长从溶质扩散控制转变为热扩散控制. 当过冷度超过100 K时, 非平衡溶质截留效应可使合金熔体发生无偏析凝固. 然而, 单靠深过冷状态不足以抑制β相的后续固态相变. 对于落管中快速凝固的直径77-1048 μm合金液滴, 其冷却速率最高达1.05×10⁵ K/s, 深过冷与快速冷却的耦合作用能更有效地调控凝固组织形成过程.     

The effect of ultrasonic waves on the nucleation of pure water and degassed water

In order to clarify the mechanism of nucleation of ice induced by ultrasound, ultrasonic waves have been applied to supercooled pure water and degassed water, respectively. For each experiment, water sample is cooled at a constant cooling rate of 0.15 °C/min and the ultrasonic waves are applied from the water temperature of 0 °C until the water in a sample vessel nucleates. This nucleation temperature is measured. The use of ultrasound increased the nucleation temperature of both degassed water and pure water. However, the undercooling temperature for pure water to nucleate is less than that of degassed water. It is concluded that cavitation and fluctuations of density, energy and temperature induced by ultrasound are factors that affect the nucleation of water. Cavitation is a major factor for sonocrystallisation of ice.     

Effect of voids and pressure on melting of nano-particulate and bulk aluminum

Molecular dynamics simulations are performed using isobaric–isoenthalpic (NPH) ensembles to study the effect of internal defects in the form of voids on the melting of bulk and nano-particulate aluminum in the size range of 2–9 nm. The main objectives are to determine the critical interfacial area required to overcome the free energy barrier for the thermodynamic phase transition, and to explore the underlying mechanisms for defect-nucleated melting. The inter-atomic interactions are captured using the Glue potential, which has been validated against the melting temperature and elastic constants for bulk aluminum. A combination of structural and thermodynamic parameters, such as the potential energy, Lindemann index, translational-order parameter, and radial-distribution functions, are employed to characterize the melting process. The study considers a variety of void shapes and sizes, and results are compared with perfect crystals. For nano aluminum particles smaller than 9 nm, the melting temperature is size dependent. The presence of voids does not impact the melting properties due to the dominancy of nucleation at the surface, unless the void size exceeds a critical value beyond which lattice collapse occurs. The critical void size depends on the particle dimension. The effect of pressure on the particulate melting is found to be insignificant in the range of 1–300 atm. The melting behavior of bulk aluminum is also examined as a benchmark. The critical interfacial area required for the solid–liquid phase transition is obtained as a function of the number of atoms considered in the simulation. Imperfections such as voids reduce the melting point. The ratio between the structural and thermodynamic melting points is 1.32. This value is comparable to the ratio of 1.23 for metals like copper.     

Solidification mechanism transition of liquid Co–Cu–Ni ternary alloy

We report a solidification mechanism transition of liquid ternary Co₄₅Cu₄₅Ni₁₀ alloy when it solidifies at a critical undercooling of about 344 K. When undercooling at ΔT<344 K, the solidification process is characterized by primary S (Co) dendritic growth and a subsequent peritectic transition. The dendritic growth velocity of S (Co) dendrite increases with the rise of undercooling. However, once ΔT>344 K, the solidification velocity decreases with the increase of undercooling. In this case, liquid/liquid phase separation takes place prior to solidification. The minor L₂ (Cu) droplets hinder the motion of the solidification front, and a monotectic transition may occur in the major L₁ phase. These facts caused by metastable phase separation are responsible for the slow growth at high undercoolings.     

亚稳相的高压暴露

 很久以前,便有人指出,气态冷凝成固态时,要连续经历液相及各种高温相,才达到平衡结晶相。但是,液态及高温相往往需靠很大的冷却速度才能冻结下来,这在当时对绝大多数合金,是不可能的。近些年,随着超急冷等技术的进步,关于非晶等亚稳相得研究十分活跃。当超过一定临界冷却速度时,液态合金可固化为非晶态。虽然,亚稳结晶相较非晶应更容易冻结,但是,由于产生各种亚稳相所需的过冷条件各不相同,以及对冷却速度的选择不能是任意的,因此有时它们较非晶还难于形成。与液相凝固过程相似,非晶合金的晶化也服从构型最小重排原理,即在晶化完成之前,存在某些亚稳相变态阶段。但是,限于热力学上的不稳定性及动力学因素,在常压下这些亚稳相同样是难以发现的。作者根据对多种合金系的研究,提出高压暴露亚稳相的设想,并利用非晶等亚稳相的高压变态过程,将进行液态急冷时的速度控制方式,改为便于掌握的高压退火方式,来获得新亚稳相。本文对压力暴露亚稳相的原理和实践,加以论述。     

Melting, freezing and nucleation in nanoclusters of potassium chloride

Molecular dynamics simulations of the melting, freezing and nucleation are presented for unconstrained nanoclusters of KCl with a number of ions between 512 and 10648. The maximum extent of the probed liquid supercooling is analysed to the light of theoretical predictions and compared with experimental data. The fraction of the solid-like ions in the supercooled liquid is used as an indicator of heterogeneities within the liquid. Induced nucleation by seeding the supercooled liquid indicates that solid-liquid coexistence is stable, and sustained during the lifetime of the clusters, relatively to the supercooled liquid. A phenomenological analysis on the relaxation times of the crystal growth process is made. Critical nuclei sizes computed from the effectiveness of the seeds in the heterogeneous nucleation of the supercooled liquid, and from the residual crystallites in clusters not totally melted, are presented as a function of the temperature. The behavior of the systems is followed through various properties such as liquid and solid molar fractions, enthalpies of melting, heat capacities, self-diffusion coefficients and relaxation times related to the freezing process. The consistency of the simulation results for the heterogeneous nucleation is assessed by means of a classical nucleation model, from which an estimate of the interfacial surface tension is also worked out and compared with experimental data.     

脉冲激光烧蚀过程中靶材表面熔融前温度分布与激光功率密度分布的研究

用较为符合实际的高斯分布表示了脉冲激光输出功率密度分布，讨论了脉冲激光功率密度分布函数形状变化对烧蚀过程中靶材表面熔融前温度分布的影响。建立了考虑热源项的热传导方程，并给出了相应的边界条件。以Si为例，用有限差分方法模拟了温度随时间、位置的变化规律，模拟过程中强调了对边界条件的处理，使整体截断误差保持最小。通过改变脉冲激光功率密度分布函数的形状，分析了温度分布的变化。结果表明，相比恒定脉冲功率密度输出，功率密度高斯分布的激光束与靶材作用时高温阶段的温度变化率变大，靶材表面熔融时刻热扩散距离增加；当激光器上升沿变陡时，在有效作用时间内温度上升得更快，对加工区域周围热效应的影响明显减弱，而热扩散距离变小。     

Localization and dephasing driven by magnetic fluctuations in low carrier density colossal magnetoresistance materials

Localization and dephasing of conduction electrons in a low carrier density ferromagnet due to scattering on magnetic fluctuations is considered. We claim the existence of the “mobility edge”, which separates the states with fast diffusion and the states with slow diffusion; the latter is determined by the dephasing time. When the “mobility edge” crosses the Fermi energy a large and sharp change of conductivity is observed. The theory provides an explanation for the observed temperature dependence of conductivity in ferromagnetic semiconductors and manganite pyrochlores. Received 17 January 1999 and Received in final form 12 March 1999