Selection of stable growth conditions for the parabolic dendrite tip in crystallization of multicomponent melts

Free growth of a dendrite crystal in a stationary multicomponent melt is investigated. A mathematical model of the process is developed and its analytic solution is constructed. A stability criterion is obtained for a 2D parabolic dendrite and the refined relation is derived for the growth rate of the dendrite tip taking into account the anisotropy of surface tension at the solid phase-melt interface. It is shown that the accumulation of impurity in the front of a dendrite makes it tip thinner and reduces its velocity. The theory contains limiting transitions to the familiar dendrite growth criteria for one-component and binary systems.     

On the Mechanisms of Recrystallization After Melting in Semicrystalline Polymers: The Effect of the Initial Melt State

The mechanisms of recrystallization after melting during a heating scan of syndiotactic polypropylene (sPP) and isotactic polystyrene (iPS) were studied. This was done by monitoring the structure evolution during the recrystallization process and its changes during a subsequent heating scan via time- and temperature-dependent SAXS measurements, respectively. The results of this study showed that the sPP samples exhibited a recrystallization mechanism similar to the multistage route found upon initial crystallization of semicrystalline polymers from an entangled melt. Meanwhile, a different recrystallization mechanism was shown by the iPS samples. In this case, the recrystallization process proceeded as a direct growth into the melt in a one-step process. This is the first time we observed such a mechanism that resembles the picture presented by the classical models for crystallization from an entangled polymer melt. The reason for such different mechanisms may be related to the initial melt state prior to crystallization. It seems as though when crystallization sets in in an entangled polymer melt, it follows the multistage route, whereas if the melt is locally disentangled, it proceeds by a direct growth mechanism.     

非晶一次晶化过程微观组织演化和生长动力学的相场法研究

在晶化物理模型中添加扩散系数对晶化过程的影响, 采用相场方法研究初始形核率和初始形核半径对一次晶化过程中微观组织和生长动力学的影响。结果表明: 随着初始形核率的增加, 相同时间内非晶一次晶化的晶粒数量逐渐增加, 晶粒尺寸逐渐减小。晶化分数随着演化时间和初始形核率的增加逐渐增大, 初始形核率越大, 相同演化时间内的晶化分数越高。不同初始形核半径情况下, 非晶一次晶化过程中的晶粒数量和尺寸随着演化时间的增加基本保持不变。晶化分数随着演化时间的增加而增大。不同初始形核率和初始形核半径情况下所对应的生长指数均小于1, 表明初始形核率和初始形核半径对晶化方式无影响, 均为一次晶化。改变初始形核率和初始形核半径可调控一次晶化微观组织结构, 而晶粒尺寸及晶化分数直接关系到合金性能。     

The mechanisms of recrystallization after melting in syndiotactic polypropylene and isotactic polystyrene

Several semicrystalline polymers show a recrystallization after melting during a heating scan. We have studied the mechanisms of such recrystallization processes for two different polymers, namely syndiotactic polypropylene (sPP) and isotactic polystyrene (iPS). This was done by monitoring the structure evolution during the recrystallization process and its changes during a subsequent heating scan via time- and temperature-dependent SAXS measurements, respectively. The results of this study showed that the sPP samples exhibited a recrystallization mechanism similar to the multi-stage route found upon initial crystallization of semicrystalline polymers from an entangled melt. Meanwhile, a different recrystallization mechanism was shown by the iPS samples. In this case, the recrystallization process proceeded as a direct growth into the melt in a one-step process. This is the first time we have observed such a mechanism which resembles the picture presented by the classical models for crystallization from an entangled polymer melt. The reason for such different mechanisms may be related to the initial melt state prior to crystallization. It seems as though, when crystallization sets in an entangled polymer melt, it follows the multi-stage route, whereas if the melt is locally disentangled, it proceeds by a direct growth mechanism. Received 23 July 2001 and Received in final form 4 October 2001     

Kinetics of nonconservative liquid phase epitaxy of semiconductors

An expression is obtained for the stationary growth rate for two- and three-component systems in the diffusion mode on the basis of a detailed analysis of the components in the liquid phase and on its boundaries. It is shown that the solution-melt experiences a hydrodynamic flow opposite to the crystallization boundary at a velocity close to the growth rate in value. Also revealed are the singularities of the kinetics of the process in three-component systems that are associated with unbalanced identically directed diffusion fluxes of components forming a stoichiometric semiconducting compound.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 15–19, August, 1988.     

Effect of high-frequency vibrations on oriented crystallization of binary alloys

The effect of high-frequency rotational vibrations with small amplitude on the oriented crystallization of binary alloys has been numerically studied. The calculations have been made in the framework of the quasi-static approach for succinonitrile-acetone and succinonitrile-salol binary systems. It has been shown that at a large solidification rate and/or high impurity concentration both for a lighter impurity (acetone) and for a heavier one (salol) a pit is formed on the axis of symmetry during growth which accelerates the development of morphological instability. Rotational vibrations make a strong stabilizing effect. The threshold for morphological instability increases with an increase in the vibration intensity, the radial segregation of an impurity decreases, and the pit is not formed.     

Crystallization of poly(ethylene-co-octene): II Melt memory effects on first order kinetics

Dilatometric and X-ray scattering experiments of the crystallization kinetics of a sample of poly(ethylene-co-octene) show pronounced melt memory effects, i.e., the shapes of isotherms and characteristic times vary systematically with the temperature of the melt prior to cooling to the crystallization temperature. The temperature range of the effect is limited; crystallization kinetics remains constant below a melt temperature Tm l and above a melt temperature Tmh and varies only in-between. Analysis shows that the melt memory effect is caused by a variation of the characteristic time of a first order crystallization process. The process can be assigned to the in-filling of crystallites into objects of a previously generated precursor structure.     

Nonisothermal Crystallization of the Polypropylene/Organosilica Nanocomposite

Abstract

Nonisothermal crystallization of the neat isotactic polypropylene homopolymer (PP‐0) and of the nanocomposite containing 4.68 wt.% of organosilica (PP‐4.68) was studied in the standard differential scanning calorimetry (DSC) mode during constant‐rate cooling from the melt state. Analysis of the nucleation parameters derived from cooling rate dependencies of the temperatures for the onset of crystallization exotherms suggested a slight increase of the nucleation barrier for lamellar crystallization of PP within a confined space between neighboring nanoparticles of an infinite cluster of the nanocomposite, concomitant to stronger restrictions to transport of PP segments across the melt/lamellar crystal interface. The overall crystallization rate data for PP‐4.68 were consistent with the assumption of two separate contributions from the initial (unconstrained) and the subsequent (constrained) nucleation mechanisms, respectively. The obtained results were considered as evidence for a coexistence in an undercooled PP melt of the nanocomposite of initial nucleation sites characteristic for the neat PP‐0, and the basically different nucleation sites (presumably, PP chains anchored by both ends to the surfaces of two adjacent nanoparticles).     

ON THE PHYSICAL PROCESS OF POLYMER CRYSTALLIZATION

Polymer crystallization is a process that connects the initial amorphous state and the final semicrystalline state. It is important to take due consideration of the initial state before crystallization, which determines the path of the crystallization process. New physical ideas are presented in regard to the processes of polymer crystallization from a dilute solution, from a melt or rubbery state, and from an oriented state, all based on experimental facts available with detailed discussions.     

Si中Pt的复合行为

本文在不同本底掺杂浓度的n-Si与p-Si的扩Pt深扩散结样品中,利用暗电容瞬态法观察到了零偏压偏置结的耗尽区内,在E_F以上kT范围的深能级处的电子发射与俘获瞬态过程。这类瞬态行为满足该处不同起始条件的深能级的电子变化率方程的解。本文并对发射瞬态的产生提出了一种机理,认为它的存在是与深扩散结的结构密切有关,至于俘获瞬态则与不同杂质的俘获特性密切有关。 关键词：     

Crystallization of a Mechanically Activated CuTi Alloy

The atomic structure and amorphous-crystalline transition dynamics in CuTi metallic glass synthesized by high-energy ball milling have been studied. Using high-resolution transmission electron microscopy (HRTEM), it has been shown that the initial amorphous phase contains crystalline inclusions, which are up to 8 nm in size and may serve as crystallization centers. In contrast to the earlier studied amorphous CuTi alloys synthesized by melt spinning, the process of crystallization in the mechanically generated amorphous alloy begins at a lower temperature (250°C) and lasts for 20–30 s. A conclusion about the diffusion mechanism of crystallization in this material has been made.     

基于图像扩散去噪的距离特征量提取研究

距离特征量反映了目标运动过程中的距离变化率,该观测量可由目标辐射噪声LOFAR谱图的干涉条纹中提取得到。低信噪比情况下,由于噪声的影响,干涉条纹特征会变模糊,提取的距离特征量值精度会降低。为提高提取精度,提出了一种边缘定向增强型扩散方程去噪方法,对LOFAR谱图进行处理,使条纹特征更加明显。迭代次数对扩散方程去噪效果影响很大,根据相关性原理,提出了一种迭代次数选择方法。为了使条纹特征更加易于区分,提出了一种基于区域分割的图像二值化方法。数值模拟实验和海试数据处理结果表明,LOFAR谱图经过处理后,提取出的距离特征量精度明显提高。     

On the theory of stoichiometric binary compound films by reactive magnetron sputtering

The theoretical model of reactive sputtering of binary compounds has been improved; the model makes it possible to calculate the stoichiometry condition for these compounds by taking into account the adhesion of molecules of the reacting gas at the regions of the surface occupied by a binary compound, followed by their diffusion to free titanium atoms. It is shown that surface diffusion of reacting gas molecules facilitates the formation of a stoichiometric binary compound, stabilizes the sputtering process, increases its rate, and makes the synthesis of the binary compound on a getter prevailing over cathode sputtering of this compound.     

Comment on “preparation of amorphous films of tin by quench condensation with impurities”

A recent paper by Buck [1] reported on a detailed investigation of quenchcondensed tin films with additions of various impurities. It was shown that the highest temperature to which an amorphous lattice order persisted scaled with the concentration of valence electrons, thus indicating that the amorphous state would be dependent on the electronic structure. Here, we show that the same crystallization temperatures also scale with the melting point of the impurity element in agreement with our previous observations [2], i.e. crystallization can be understood as due to the onset of impurity diffusion. It is also shown that the latter explanation, but not the former, can account as well for data on lead and thallium based compounds, indicating the more universal nature of the scaling of the crystallization temperature with the impurity element melting point.     

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.     

熔体初始温度对液态金属Ni凝固过程中微观结构演变影响的模拟研究

采用量子 Sutton-Chen多体势, 对熔体初始温度热历史条件对液态金属Ni快速凝固过程中微观结构演变的影响进行了分子动力学模拟研究. 采用双体分布函数g(r)曲线、键型指数法、原子团类型指数法和三维可视化等分析方法对凝固过程中微观结构的演变进行了分析. 结果表明: 熔体初始温度对凝固微结构有显著影响, 但在液态和过冷态时的影响并不明显, 只有在结晶转变温度T_c附近才开始充分显现出来. 体系在1×10¹² K/s的冷速下, 最终均形成以1421和1422键型或面心立方(12 0 0 0 12 0)与六角密集(12 0 0 0 6 6) 基本原子团为主的晶态结构. 末态时, 不同初始温度体系中的主要键型和团簇的数目有很大的变化范围, 且与熔体初始温度的高低呈非线性变化关系. 然而, 体系能量随初始温度呈线性变化关系, 初始温度越高, 末态能量越低, 其晶化程度越高. 通过三维可视化分析进一步发现, 在初始温度较高的体系中, 同类团簇结构的原子出现明显的分层聚集现象, 随着初始温度的下降, 这种分层现象将被弥散开去. 可视化分析将更有助于对凝固过程中微观结构演变进行更为深入的研究. 关键词： 液态金属Ni 熔体初始温度 微观结构 分子动力学模拟     

Study on the Non-isothermal Melt Crystallization Kinetics of PTT/PBT Blends

Macro-kinetic models, namely the modified Avrami, Ozawa, Mo, and Kissinger models, were applied to investigate the non-isothermal melt crystallization process of PTT/PBT blends by DSC measurements. It was found that the modified Avrami model can describe the non-isothermal melt crystallization processes of PTT/PBT blends fairly well. When the cooling rates range from 5 to 20°C/min, the Ozawa model could be used to satisfactorily describe the early stage of crystallization. However, the Ozawa model didn't fit the polymer blends in the late stage of crystallization, because it ignored the influence of secondary crystallization. Under the conditions of the non-isothermal melt crystallization, it was found that the cooling rates and the blend composition affect the crystallization for blends according to Kissinger crystallization kinetics parameters. The crystallization kinetics constant K_a increases with increasing cooling rate, indicating the crystallization rates of PTT, PBT, and PTT/PBT blends were improved. The crystallization kinetic activation energy parameters are good agreement with the results from isothermal crystallization processes of the polymer blends. The crystallization activation energy of PTT/PBT blends is higher than the activation energy of PTT and PBT.     

X-ray topography characterization of the structural response of Ge(Ga) crystals to variation in gravity force vector orientation during crystallization

The influence of crystallization process disturbances connected with the variation of the crystallization front orientation relative to the gravity force vector (characteristic for crystal growth under conditions of microgravity onboard space vehicles) on the real crystal structure has been investigated by plane-wave X-ray topography. It has been found that these disturbances can result in a local disorder in the impurity distribution in the form of microsegregation growth striations. Quantitative estimations of the amplitude for the composition variation based on the analysis of contrast in growth striation images obtained by the method of plane-wave X-ray topography have been carried out.     

Conduction and the impurity-center parameters in compensated CdTe single crystals

An investigation is made of the conduction and the optical and galvanomagnetic properties of CdTe single crystals grown from a homogeneous melt modified by the Bridgman method at a rate of directed crystallization of 0.2 mm/h. It is established that conduction of constant-type isothermal annealing of the initial crystals in large volumes of Cd + LiCl salt melts at 900°C for 9–17 h provides additional purification from uncontrollable impurities and considerably increases the degree of compensation. An account is given of the change in conduction and the mechanism of electron scattering with change in the parameters of the impurity-center energy spectrum in the extractive purification of CdTe single crystals.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 40–43, March, 1977.