EVALUATION OF MORPHOLOGY-STABLE CRITICAL SIZE OF KNbO3 CRYSTALS

Skeletal form of KNbO3 crystals growing in Li2B4O7 solvent was in-situ observed at 900°C and it was found that shallow depression started to develop on the surface of KNbO3 crystals when the crystal size exceeded several micron, typically 7 micron.Based on the quantitative criterion derived by Chernov, the estimated critical size of KNbO3 crystals was 1 micron, which was consistent with the experimental measure ment. The kinetic coefficients, kcorner and kcr, in the criterion were experimentally obtained in the diffusive-convective and diffusive-advective flow states respectively.     

INTERFACIAL MASS TRANSPORT IN OXIDE CRYSTAL GROWTH

A space high temperature in situobservation instrument (SHITISOI) is dedicated to visualize and record the whole growth process of oxide crystal in high temperature melts and solutions. Model experiments using transparent liquids such as KNbO3,Li2B4O7+KNbO3 were chosen to investigate effects of interracial mass transport in oxide crystal growth. For the scaling of the coupled velocity, heat and concentration fields in KNbO3 crystal growth, a rotating crystal growth process was performed and the widths of interfacial concentration, heat and momentum transition zones (The "boundary layers") are obtained, which are 7.5×10-a, 8.6×10-2 and 4.4×10-1 cm,respectively. Hence one can expect that interfacial concentration gradient will be confined to a narrow layer and in region of major concentration change at the in terface. In order to study a mechanism based on the interfacial mass transport resulting from hydrodynamics, the growth of KNbO3 grain in high temperature Li2B4O7 and KNbO3 solutin was studied. The result shows that the pivotal feature in the KNbO3 crystal growth is the initiated by KNbO3 solute surface tension gra dient which is caused by the slow diffusion of KNbO3 solutes. Direct comparison of the model predictions and experimental observed phenomena demonstrate the predictive capability of this model.     

THE CONVECTIVE EFFECT ON THE MORPHOLOGICAL INSTABILITY OF KNbO3 CRYSTALS

Experimentally, it was observed that there were various morphologies of KNbO3 crystals in different regions of the melt of Li2B4O7 and KNbO3 mixture in Pt loop heater. Dendrites grew in the central area of the melt, the diffusive-advective region,in which the temperature gradient is negligible; whereas crystals with smooth sur face were observed in the marginal area, the diffusive-convective region, with large temperature gradient. Based on the solute concentration over the KNbO3 crystal surface examined by electronic probe analysis, it was proved that the combinative effect of buoyancy and surface tension convection induced by temperature gradient enhanced the homogeneity of the solute concentration around KNbO3 crystals and thus their morphological stability.     

VELOCITY FIELD OF THERMOCAPILLARY CONVECTION IN HIGH-TEMPERATURE OXIDE SOLUTION

We have investigated experimentally and theoretically the thermocapillary convec tive flow phenomena in a loop-shaped Pt wire heater of KNbO3 (20wt.%) and Li2B4O7 solutions. Optical evaluations in connection with thermocouple measure ments made it possible to get a new type of thermocapillary convective flow in the considered system. To study the kinematical behaviour of thermocapillary convec tion, we have measured the stream flow velocities. In a theoretical analysis, the flow velocity due to the thermocapillary effect alone was estimated by balancing the sur face tension forces by viscous forces. The velocity distribution in the solution near the margin of the heater was obtained, which is in agreement with the experimental result.     

EXPERIMENTAL AND THEORETICAL STUDIES ON VELOCITY FIELD OF BUOYANCY CONVECTION IN KNbO3 MELT

The Schlieren technique coupling with a differential interference microscope was applied to visualize the KNbO3 melt motion in a loop-shaped Pt wire heater. The natural convection in KNbO3 melt was traced by observing the movement of the tiny KNbO3 crystals (～10μm) and the stream velocities of these tracer crystals were measured. In theoretical analysis, the Navier-Stokes equation was solved as a stable field. The general solution for this system of the differential equation was expressed by an approximate power series of azimuth and radius vector. The expression was substituted in the differential equation; a non-trivial solution was obtained exactly.The velocity distribution in the vertical section was obtained which is in qualitative agreement with the experimental result.     

NUMERICAL MODELLING OF VELOCITY AND TEMPERATURE DISTRIBUTIONS OF THE BUOYANCY CONVECTION EFFECT IN KNbO3 MELT

Numerical modelling of velocity and temperature fields in high-temperature KNbO3 melt of a loop-shaped Pt wire heater is carried out by using the commercial com putational code ANSYS for the mathematical solution of the governing equations.Based on the experimental boundary conditions and the Boussinesq approximation,the numerical modelling of a steady and two-dimensional model is applied to study the process under consideration of the buoyancy-driven convection condition. The result is compared with the previous experimental and theoretical data obtained in our laboratory, and the former is in agreement with the latter. Thus a theoretical guide for reasonable growth conditions is provided by studying in depth the real fluid flow effects in the crystal growth from the melt.     

Strong magnetic field effect on the dissolution process of tetragonal lysozyme crystals.

Either a homogeneous or inhomogeneous magnetic field has been known to dampen the protein crystal growth. To date the mechanism is not clear. However, it was generally proposed that the magnetic field may dampen the convection in the solution, resulting in a reduced crystal growth rate and possibly a good crystal quality, similar to the case of protein crystal growth in space. To understand the mechanism of the magnetic field effect on protein crystal growth, further explorations on the magnetic field effect on protein solution, on the processes of crystal growth and dissolution, and on different crystallization (solution) systems, should be valuable. In this paper we present our recent efforts to study magnetic field effects on the dissolution processes of tetragonal lysozyme crystals under a strong magnetic field. A layer of oriented tetragonal lysozyme crystals was prepared under a temperature gradient and magnetic field, after that the crystals were dissolved by increasing the temperature of the solution. The lysozyme molecules will diffuse upwards due to the steep concentration gradient at the lower side of the cell caused by the dissolution. The evolution of the concentration in the solution was measured in-situ using a Mach-Zehnder interferometer. The results confirmed that the dissolution process of the crystals was slowed by the magnetic field. Judging from the concentration evolution versus time at different positions in the solution, we concluded that the apparent diffusion coefficient of lysozyme molecules was decreased by the magnetic field. The results were discussed using a suspended crystal model in the initial dissolution stage.     

Marangoni and buoyant convection in an open cavity under reduced and under normal gravity

We give the first full analysis of the microgravity experiment MKB ( arangoni onvektion im offenen oot) conducted on board of the space shuttle during the D1-mission in 1985, together with that of some ground based experiments on thermocapillary flow in a rectangular liquid volume with free upper surface. Streamlines and velocity profiles under μ-g and l-g are presented and discussed. Strong thermocapillary flow was observed under μ-g after the rupture of a dirt-film suppressing surface tension forces. The Nusselt-number under microgravity due to thermocapillary flow for Ma = 4.6 · 10⁵ is at least Nu = 6 ± 1. Under l-g a separation of the surface tension driven convection roll of hot fluid circulating on top of colder fluid was found for large Ma. The coupling and decoupling of buoyant and thermocapillary forces has been further studied in an experiment varying the temperature gradient along the free surface independently from that in the bulk fluid.     

微重力环境下蒸发液层热毛细对流的数值模拟

提出了一种新模型来研究由单一物质构成的液层在其纯蒸气中的蒸发.液层置于微重力环境中并且受到水平方向温度梯度的作用,液层的热毛细对流和蒸发耦合在一起,使得气液界面的传热传质规律更加复杂.用理论分析的方法求解了不考虑热毛细效应的纯蒸发模型,得出温度场分布和界面质量流量的解析表达式.对于热毛细对流和蒸发耦合情况,采用有限差分的投影算法同时求解Navier-Stokes方程和能量方程,得到了不同蒸发Biot数和Marangoni数下流场和温度场的稳态数值解.论述了蒸发Biot数和Marangoni数对界面传热传质的影响,提出并解释了蒸发和热毛细对流耦合的三种模式.      

Crystallization of calcium phosphate in microgravity.

Dilute solutions of CaCl2 and KH2PO4 + K2HPO4 were diffusing from either side into a mixing chamber with KCl solution. The microgravity experiment yielded aggregates of large crystals of OCP (Ca8H2(PO4)3,5H2O) and spherolites of smaller, but still visible crystals of HAP (Ca5OH(PO4)3), the stable final phase. Ground-based experiments yielded submicroscopic HAP crystals. Results of calculations of diffusion and crystal growth on the basis of previous knowledge agree well with observations.     

环形浅液池内低Prandtl数流体超临界热毛细对流演化

为研究低Prandtl数（Pr）流体热毛细对流演化过程，对环形浅液池内Pr=0.011的流体热毛细对流进行三维数值模拟.研究发现:当Marangoni数较小时，流动为轴对称稳态流动；当Marangoni数超过某一临界值后，流动失稳并转变为热流体波，其波数随Marangoni数增加而减小，而波动主频增大；随着Marangoni数增加，流动加强，沿周向运动的热流体波演变为沿径向运动的径向波，其波数大大减小；当Marangoni数继续增加时，波动频谱曲线噪声增加，呈广谱特性.因此，在计算范围内热毛细对流的演化过程为:轴对称稳态流动-热流体波-单周期径向波-多周期三维振荡流动.      

Travelling heater growth of GaSb under reduced gravity during the first spacelab-mission

Single crystals of binary III-V-semiconductors, e.g. GaAs or InP, are important basic materials for optoelectronic devices, e.g. LED's and lasers. Device production needs highly perfect substrate crystals with low defect densities and homogeneous dopant distributions. In our experiment we applied the Travelling-Heater-Method to grow the III-V compound GaSb. The aim of this research project was to improve the crystal quality by investigating convective transport phenomena and the origins of dopant inhomogeneities under earth and space conditions. Earth grown crystals show strong dopant variations mainly due to convective flow phenomena. The preliminary result of our SPACELAB 1 experiment reveals an increase of dopant homogeneity in the space grown crystal because of the absence of natural convection under reduced gravity.     

用国产装置进行的空间蛋白质结晶实验

使用国内研制的管式汽相扩散结晶装置,在我国返回式卫星上,成功地完成了两次空间蛋白质晶体生长实验,10种不同种类的蛋白质配制的48个样品在空间的出晶率分别达52%和80%,其中少数蛋白质生长出了较高质量的蛋白质晶体。结果表明,空间的微重力环境利于改善蛋白质晶体的生长,而且在结晶条件优化足够好的条件下,在空间里能生长出比地面晶体尺寸较大、形态较好和内部有序性较高的蛋白质晶体。本文还就微重力对蛋白质晶体生长的具体作用及其开发利用做了讨论。      

Hydrothermal instability of thermocapillary convection in large-Prandtl-number liquid bridges under microgravity

Linear stability analysis was performed to study the mechanism of transition of thermocapillary convection in liquid bridges with liquid volume ratios ranging from 0.4 to 1.2, aspect ratio of 0.75 and Prandtl number of 100. 2-D governing equations were solved to obtain the steady axi-symmetric basic flow and temperature distributions. 3-D perturbation equations were discretized at the collocation grid points using the Chebyshev-collocation method. Eigenvalues and eigenfunctions were obtained by using the Q–R method.The predicted critical Marangoni numbers and critical frequencies were compared with data from space experiments. The disturbance of the temperature distribution on the free surface causes the onset of oscillatory convection. It is shown that the origin of instability is related to the hydrothermal origin for convections in large-Prandtl-number liquid bridges.     

空间低温溶液晶体生长的地基实验

首次使用疏水型聚四氟乙烯微孔滤膜,利用其透气不透水的特性,密封晶体生长容器,采用恒温蒸发法进行晶体生长.溶剂通过蒸发离开生长容器后,被生长容器外的吸附剂吸附,使得溶液维持一定过饱和度,以实现单晶的连续生长.在此基础上研制出一套空间低温溶液晶体生长地基模拟装置.利用此装置进行了一系列地基模拟实验,获得一批高质量α-LiIO₃单晶,证实了该生长装置的溶剂蒸发量和容器密封性能够满足空间低温溶液晶体生长需要,为未来空间低温溶液晶体生长实验奠定了基础.      

Manipulation of Colloidal Droplets in Space and the Instability of Thermocapillary Convection in Large Prandtl Number Liquid Bridge in Microgravity

In 2016 and 2017, SJ-10 and TG-2 satellites were launched. In this short paper, we report recent progress on the studies of manipulation of colloidal droplets and instability of thermocapillary convection in large Prandtl number liquid bridge that based on the space experiments boarding SJ-10 and TG-2 satellites, separately. It was shown that the colloidal droplets can be successfully formed and manipulated in microgravity through the patterned substrates. In another aspect, the coffee-ring effect was observed at the first time in space. For the studies of the instability of thermocapillary convection in large Prandtl number liquid bridge in microgravity, our experiments in TG-2 broadened the way of such kind of study and abundant experimental results are emerging.      

Convection in melts and crystal growth

Convection plays a significant role in determining the electronic properties of semiconductor crystals grown from the melt. Inhomogeneities (doping striations) in these crystals can be caused by unsteady natural convection. Therefore, the origins of unsteady natural convection, which means fluctuating temperatures in a fluid, are investigated in this paper. Several effects have been found at increasing Rayleigh numbers Ra which cause fluctuating temperatures. But it was also observed, that unsteady convection became again steady if Ra was increased to higher values. This effect, which is called relaminarization, is very interesting for crystal growth and is discussed in this paper.     

THE SPACE EXPERIMENT OF PROTEIN CRYSTALLIZATION ABOARD THE CHINESE SPACECRAFT SZ-3

Using a new flight hardware, a Chinese mission of space protein crystallization has been performed on the Chinese spacecraft SZ-3 for seven days from March 25 to Apr. 1, 2002. The rate of yielding crystals in the 60 samples is 75%, a little higher than the ground control experiment. Preliminary analysis of the experimental results have shown that among the 16 proteins involved in the mission, about 4 kinds of better diffraction-quality protein crystals were produced in space. At least one kind of protein crystals, i.e. crystals of cytochrome b5 mutant could diffract X ray beyond the highest resolution reported so far. In addition, some rules derived from our numerical studies of the liquid/liquid diffusion protein crystallization were proved by the crystallization of lysozyme as model protein in this space experiment,which also clearly showed the advantages and disadvantages of the gelled protein solution used in microgravity growth of protein crystals. In order to exploit this mission, more diffraction work with the grown crystals and detailed analysis of data to be obtained will be done in the next few months.     

池沸腾现象中热毛细对流的成因

针对微重力条件下单组份液体池沸腾现象,探讨了有关热毛细效应作用及其成因的不同观点,指出正确描述气液相变界面两侧的温度关系是解决争议的关键.详细评述了现有的气液相变界面温度模型,发现气液相变的非平衡特征会导致气液界面上产生温度梯度,引起表面张力的显著差异,从而驱动热毛细对流的形成.但现有气液相变界面温度模型机理差异迥然,预测结果也差别很大,因此,需要更深入研究.      

Crystallization of germanium-silicon solid solution from the vapour phase in microgravity conditions

Mass transport has been investigated in the closed system Ge-Si-Br used for preparing germanium-silicon solid solution crystals by chemical transport reaction method in space. It has been shown that the experimental rate of mass transport may be analytically described in proposing a pure diffusion mechanism. In space, growth of needles and whiskers occured without practically formation of a polycrystalline layer characteristic of on-earth experiments.