定向结晶条件下聚乙二醇6000的强动力学效应

在单向温度场条件下, 采用不同抽拉速度实现了聚乙二醇6000的定向生长、界面形貌的实时观测及界面温度的测量, 进而揭示了其生长机制. 实验结果表明, 随着抽拉速度的增大, 界面的温度逐渐减小, 过冷度逐渐增大. 运用高聚物结晶的次级形核理论模型, 对实验数据进行了计算, 得到在界面过冷度为13.5 K左右时, 生长机制发生了由区域Ⅱ向区域Ⅲ的转变. 实验数据与等温结晶数据的比较发现等温结晶方法中获得过冷度相对较大, 是因为其包含了热过冷. 聚乙二醇6000定向结晶过程中需要的最大动力学过冷度为20 K, 说明由于高聚物的二维形核, 其生长主要由界面动力学控制, 具有较强的动力学效应.     

简单金属固液界面固化过程生长机制的分子动力学研究

采用分子动力学方法,研究两种简单金属Ni、Al固液界面的动力学过程.结果表明：两种金属表现出相同的特征,即界面温度存在某个特征值（T^*）,生长速度在这个特征温度附近达到最大值.高于这个温度时,随着过冷温度（熔点温度与界面温度差）的增加生长速度单调增加,低于这个温度时,Ni的生长速度几乎不变,而Al的生长速度随过冷温度的增加而快速减小到零.在此基础上,基于高温BGJ碰撞约束模型和低温W-F扩散模型分析界面的生长机制,发现在小过冷温区和深过冷温区存在碰撞机制和扩散机制的渐变过程,不同温区二者所起的主导作用不同,生长机制的转变是T^*存在的原因.     

过冷沸腾气泡行为的实验研究

本文采用拍摄速度为10000帧/秒的高速摄影仪对不锈钢箔表面的过冷沸腾现象进行了可视化实验研究。实验结果与用微液层模型理论预测的结果一致。高过冷度区域的沸腾换热机理主要是由气泡生长、消失过程中温度边界层的强制排除(所谓强制对流)引起的。气泡周期主要由等待时间构成,这在过冷度高的情况下尤为显著。对等热流密度换热面,微液层模型预测的气泡周期与实验值比较吻合。     

Cu固液界面能的分子动力学计算

本文使用分子动力学方法对液相Cu中不同半径晶胚的生长和熔化行为进行了研究. 随着半径的增加, 晶胚生长的临界温度升高. 临界形核过冷度和晶胚半径倒数成正比关系, 这和经典形核理论一致. 由上述关系计算得到Cu的Gibbs-Thomson系数为1.12×10^-7 K·m, Cu的固液界面能为0.146 J/m², Cu的Turnbull系数为0.416, 这些计算值均与实验值一致. 关键词： 分子动力学 经典形核理论 固液界面能     

界面动力学对过冷熔体中球晶生长界面形态的影响

考虑了在非平衡凝固条件下球晶生长过程中界面动力学系数随界面温度的变化,利用渐近分析方法求出了在过冷熔体中球晶生长温度场和界面的近似解析解,研究了非线性界面动力学过冷对于过冷熔体中球晶界面形态和生长速度的影响.研究表明,界面动力学系数越大,球晶的生长速度越快; 反之,表明界面动力学系数越小,球晶的生长速度越慢.与忽略界面动力学的情形比较,在球晶生长过程中依赖于界面温度变化的界面动力学显著地减缓了晶体生长的速度. 关键词： 球晶 界面形态 渐近分析     

微重力条件下Ni-Cu合金的快速枝晶生长研究

采用落管方法实现了Ni-50%Cu过冷熔体在微重力和无容器条件下的快速枝晶生长.对微重力条件下的晶体形核和快速生长进行了研究，发现随着过冷度的增大，晶体生长形态由粗大枝晶向规划均匀的等轴晶转变.实验中最大冷却速率达到8×103K/s，获得了218K(014TL)的最大过冷度.理论分析表明，过冷熔体中优先发生异质形核，形核率可达1012m-3s-1以上；Ni-50%Cu过冷熔体中的枝晶生长随过冷度的增大发生由溶质扩散控制向热扩散控制的生长动力学机理转变.在68K过冷度条件下，生长界面前沿的偏析程序最大. 关键词： 落管 微重力 深过冷 枝晶 熔体     

纳米通道内界面温度阶跃与能量输运特性研究

纳米尺度固–液相传热过程中界面处存在温度阶跃现象。本文采用分子动力学方法分析宽度为3.44～14.69 nm通道内固–液界面温度阶跃变化规律与水能量输运特性。模拟结果表明,随纳米通道宽度的增加,固–液界面处的温度阶跃与界面热阻降低。此外,纳米通道内水液膜的能量输运具有尺度效应,随着纳米通道宽度增加,液相水分子间作用势能降低,水分子均方位移与扩散系数增加,水液膜的导热系数升高。     

生长温度、过冷度对InAsPSb外延层表面形貌影响的研究

本文采用恒温液相外延生长方法,研究了InAsPSb四元材料外延层表面形貌与生长温度、过冷度之间的关系.实验结果表明,生长温度、过冷度对外延晶体质量及表面形貌的影响较为明显,同时对其它因素的影响也做了分析.     

三维多相场数值模拟共晶CBr4-C2Cl6合金在不同抽拉速度下的形态选择

利用KKSO多相场模型对定向凝固共晶CBr4-C2Cl6合金的三维恒速及变速生长过程进行了研究,再现了不同抽拉速度下共晶形态演化及选择过程,建立了形态选择图,研究了变速过程的界面平均生长速度及界面平均过冷度的变化.结果表明,变速前后的形态选择与恒速下的形态选择一致;变速过程的形态演变、界面平均生长速度和界面平均过冷度的变化均产生滞后效应;界面平均生长速度和界面平均过冷度之间的关系与理论结果符合较好.     

纳米特性表面圆柱型高速喷流沸腾临界热流密度的实验研究

制备了分别具有亲水和疏水特性的2种纳米特性表面,对具有不同固液接触角的传热面上圆柱型高速水喷流沸腾的沸腾临界热流密度(CHF)进行了系统的稳态实验研究,重点考察了喷流速度,过冷度和传热面固液接触角对CHF的影响。通过研究整理了传热面固液接触角和CHF之间的实验关系。对作者过去提出的饱和液与过冷液圆柱喷流沸腾CHF的半理论关系式进行了扩展和改进,使公式扩展到高流速范围和广泛的固液接触角范围。改进的关系式与实验数据符合得很好.     

Determination of the supercooling dependence of the (211) facet of BGO crystal on growth rate from the temporal dependence of supercooling at a prescribed melt-cooling rate

The results of determination of the supercooling dependence at the interphase boundary on the rate of growth from melt of the monocrystal Bi₄Ge₃O₁₂ in the [211] direction are presented. Determination of supercooling was based on optical pyrometer measurements of the intensity of heat emission from the interphase boundary through the growing crystal. The crystal was grown by the AHF method (axial heat flux near the front of crystallization) by cooling the AHF heater at a specified rate. The growth rate corresponding to the measured supercooling value was determined by calculations. The study has shown that the supercooling is high and varies nonlinearly with the growth rate.     

Dislocation Generation in Dislocation-Free Germanium

A dislocation structure is studied in germanium single crystals grown in a regime of minimum temperature gradients at the crystallization front and low supercooling. The investigations show that the distortion of the flat crystallization front arising during crystal droplet detachment in the completion growth stage results in the dislocation generation in the lower parts of dislocation-free single crystals. The dislocations are generated at the phase boundary and propagate in the thermoplasticity zone. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 5, pp. 21–24, May, 2005.     

Investigation of the Melt‐Crystallization of Polypropylene by a Temperature Slope Method

Abstract

To investigate the in‐situ ordering process of isotactic polypropylene (iPP) from a melt state, a stationary growth front was prepared by the temperature slope crystallization (TSC) method. During the melt‐crystallization, iPP was crystallized into the α‐phase or β‐phase depending on the crystallizing conditions. The mechanism of the melt‐crystallization at the growth front was precisely observed by wide‐angle and small‐angle x‐ray scattering (WAXS and SAXS) using a strong synchrotron beam. In the TSC apparatus, the sample was crystallized in between a heater, controlled to 220°C, and a cooler, cooled by water to 25°C. We define the z‐axis parallel to the temperature gradient. A‐lamellae and B‐lamellae are also defined as those whose lamellar normal are perpendicular and parallel to the z‐axis, respectively. In a sample‐stop (SS) stage before the TSC, the original α‐phase lamellae became thicker, approaching to the melt‐solid boundary by annealing. The annealing process showed that the α‐phase B‐lamellae remained and the SAXS reflection was stronger on the meridian near the melt‐solid boundary in the SS stage. In the beginning of the TSC, the α‐phase B‐lamellae developed as a primary crystallization. During secondary crystallization under high supercooling, the SAXS cross pattern appeared showing that the α‐phase developed both A‐ and B‐lamellae. As the growth direction of A‐lamellae is parallel to the z‐axis, A‐lamellae grow faster than B‐lamellae. By the self‐epitaxial mechanism on the side surface of the A‐lamellae, the B‐lamellae grow on the base of the A‐lamellae. Following appearance of a spontaneous β‐nucleus, the β‐phase lamellae grew preferentially, excluding the α‐phase, and occupied the whole area of the sample. In this case also, A‐lamellae are advantageous to grow because of the growth direction parallel to the z‐axis. As a result, the SAXS β‐phase reflection appeared on the equator.     

The kinetics of solidification of Al-Si eutectic alloys under high pressure

Abstract

The kinetics of crystallization of eutectic alloys Al_100-xSi_x (χ=12, 18, 26 at.%) was investigated under pressures p=0.5, 2.5, 4.5 GPa. The values of supercooling and average grain size of silicon crystals were determined for alloys quenched from melt under different pressures with the cooling rate 10³ K/s. The data obtained were used to evaluate quantitatively the pressure dependences of surface tension (between melt and crystal) and activation energy of crystal growth which, in turn, have made it possible to determine the relative change of nucleation frequency and of the rate of crystal growth with pressure.

The possibility is shown, based on the investigation of mechanical properties of the samples obtained under high pressure, for improving the strength and the plasticity of A1-Si alloys by means of high pressure-high temperature treatment.     

Structure formation of supercooled polymers in confined geometries -- A molecular-dynamics simulation study

Molecular-dynamics simulations of thin polymer films are performed with a recently introduced coarse-grained model. This model reproduces many features of polymer crystallization from the melt. In this work, we show how confining walls influence the structure formation depending on the degree of supercooling. Already in the melt at high temperature a preorder is induced near the walls. On lowering the temperature, crystalline order nucleates at the walls, from which it propagates into the film. We show how this growth can be influenced by prestructuring the wall.Received: 1 January 2003, Published online: 21 October 2003PACS: 61.20.Ja Computer simulation of liquid structure - 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling - 68.55.-a Thin film structure and morphology     

Isothermal Crystallization and Miscibility of Isotactic Polypropylene/Poly(cis-butadiene) Rubber Blends

Isotactic polypropylene/poly(cis-butadiene) rubber (iPP/PcBR) blends were prepared by melt mixing. Isothermal crystallization and miscibility for neat iPP and blends of iPP/PcBR were investigated by differential scanning calorimetry. The presence of PcBR remarkably affected isothermal crystalline behaviors of iPP. An addition of PcBR caused shorter crystallization time and a faster overall crystallization rate, meaning a heterogeneous nucleation effect of PcBR upon crystallization of iPP. For the same sample, the crystallization peak was broader and the supercooling decreased as the crystallization temperature increased. The Avrami equation was suitable to describe the primary isothermal crystallization process of iPP and blends. The addition of PcBR led to an increase of values of the Avrami exponent n, which we suggest was because the blends had a stronger trend of instantaneous three-dimensional growth than neat iPP. The equilibrium melting point depression of the blends was observed, indicating that the blends were partly miscible in the melt.     

Growth kinetics of polymer crystals in bulk

Temperature-dependent measurements of spherulite growth rates carried out for i-polystyrene, poly(ε -caprolactone) and linear polyethylene show that the controlling activation barrier diverges at a temperature which is 14K, 22K and 12K, respectively, below the equilibrium melting points. We discuss the existence of such a “zero growth temperature” T _zg in the framework of a recently introduced thermodynamic multiphase scheme and identify T _zg with the temperature of a (hidden) transition between the melt and a mesomorphic phase which mediates the crystal growth. The rate-determining step in our model of crystal growth is the attachment of chain sequences from the melt onto the lateral face of a mesomorphic layer at the growth front. The necessary straightening of the sequence prior to an attachment is the cause of the activation barrier. A theory based on this view describes correctly the observations. With a knowledge of T _zg it is possible to fully establish the nanophase diagram describing the stability ranges of crystalline and mesomorphic layers in a melt. An evaluation of data from small-angle X-ray scattering, calorimetry and optical growth rate measurements yields heats of transition and surface free energies of crystals and mesophase layers, as well as the activation barrier per monomer associated with the chain stretching. According to the theory, the temperature dependence of the crystallization rate is determined by both the activation energy per monomer and the surface free energy of the preceding mesomorphic layer. Data indicate that the easiness of crystallization in polyethylene is first of all due to a particularly low surface free energy of the mesomorphic layer.     

AlN晶体物理气相传输法生长坩埚的热场分析

采用物理气相传输法在钨制坩埚上制备AlN单晶.通过采用COMSOL软件中的固体传热和磁场模块,对AlN晶体生长的坩埚的热场进行仿真,同时针对不同的线圈直径以及不同的线圈位置对坩埚热场的影响进行模拟,提出了相应的处理方式.结果表明:当线圈直径增大,坩埚结晶区和升华区的温度在相同的加热时间下会增加,并且增加的温度存在峰值.当线圈的垂直位置发生变化的时候,结晶区和升华区的温度场也会发生变化,从上向下移动的过程中仍然存在温度的峰值,并且结晶区和升华区的温度关系会发生翻转,导致温度梯度阻碍晶体生长.在晶体生长过程中升华区和结晶区的温度关系依旧会发生翻转.但是通过线圈跟随籽晶表面生长层的变厚而同步移动,可以保持相对稳定的温度关系,维持晶体正常持续生长.     

Linear stability analysis on a spherical particle growing from a binary melt under the far-field flow

The solutions of temperature and solute fields around a spherical crystal growing from a binary melt under the far-field flow are obtained.Based on the results,a linear stability analysis on the spherical interface growing from the binary melt under the far-field flow is performed.It is found that the constitutional supercooling effect ahead of the spherical crystal interface under the far-field flow is enhanced compared with that without the flow.The growth rate of the perturbation amplitude at the up-wind side of the spherical crystal interface is larger than that at the down-wind side.The critical stability radius of the crystal interface decreases with the increasing far-field flow velocity.Under the far-field flow,the whole spherical interface becomes more unstable compared with that without the flow.