一水甲酸锂晶体生长界面过饱和度的测量

本文采用激光全息相衬干涉显微术研究了有机非线性光学晶体一水甲酸锂晶体的生长,计算了晶体生长的界面过饱和度.我们的研究结果表明,晶体生长的界面过饱和度随体过饱和度的增加而非线性增加;不同晶面的界面过饱和度不同;当体过饱和度增加到一定程度时,不同晶面的界面过饱和度趋于相同.     

有机非线性光学晶体一水甲酸锂的研究综述

甲酸盐晶体是一族引人瞩目的非线性光学材料,一水甲酸锂(LFM)是甲酸盐系列中综合性能优良的晶体之一.本文较全面地介绍了一水甲酸锂晶体的发展、生长技术、生长机理及其非线性光学性能.指出一水甲酸锂是很有发展潜力的紫外非线性光学有机晶体,并提出了进一步开发其应用需要解决的问题.     

KDP晶体生长的溶液流动和物质输运计算

本文采用有限容积法,对KDP晶体生长过程中溶液的流动和物质输运进行了数值模拟.结果表明:随着入口溶液流动速度的增大,籽晶的上表面因自然对流而引起的抽吸作用减小,表面过饱和度的最小值沿x正向发生右移,其上表面的剪切力先减小后增大.随着入口溶液过饱和度的增大,籽晶上表面剪切力增大.不同尺寸的籽晶表面过饱和度的分布差异较大.籽晶的生长边界层厚度与溶液流动密切相关,入口溶液流动速度越大,厚度越小,但其受入口溶液过饱和度的影响较小.     

一水甲酸锂晶体生长动力学和生长机理的研究

本文实时测定了312.16K时一水甲酸锂晶体(LFM)(010)和(021)面的生长速率。根据Bennema修正的用于水溶液晶体生长的BCF表面扩散模型,计算了晶体生长过程的激活能以及动力学系数。结果表明LFM晶体生长主要是表面扩散控制的螺位错生长机制。     

溶液、熔体中负离子配位多面体生长基元的分布与缔合

根据对晶体生长溶液、熔体拉曼光谱的测试结果,剖析了溶液和熔体中负离子配位多面体的分布及其缔合过程,总结出了不同过饱和溶液和不同过冷度熔体中负离子配位多面体生长基元的缔合形式和维度的规律.在靠近晶体的边界层处已出现与晶体结构相同或相似的大维度生长基元.实验表明,生长基元的分布和缔合与溶液过饱和度和熔体过冷度密切相关,从而提出用拉曼光谱进行实时监控,寻找最佳生长物化条件,优化晶体生长边界层的厚度和大维度生长基元的数量,为选择最佳工艺条件提出理论依据.     

转晶法KDP单晶生长晶面溶质浓度场模拟

针对转晶法生长KDP单晶过程,进行了流动与物质输运数值模拟,以获得生长过程中晶面溶质浓度(过饱和度)的变化规律。文中展示了晶体表面浓度分布随时间的变化过程;分析了不同转速和晶体尺寸,对晶面时均浓度场的影响。结果表明,转速越快,晶体表面过饱和度越高;晶体尺寸对其表面过饱和度的大小和分布也有较大影响。此外,由于空间上不对称,Z向和Y向晶面过饱和度分布有较大差异。在晶体处于静止或低转速,自然对流可能会对晶体表面的过饱和度分布产生影响。     

脉冲激光烧蚀制备纳米硅晶粒成核生长的热力学条件研究

文中利用蒙特卡洛方法,引入成核生长模型,研究了纳米硅晶粒成核生长过程.结合宏观阻力模型,计算了纳米硅成核和生长所对应的过饱和度范围.结果显示,衬底的二次溅射,造成成核次数增多,生成小尺寸纳米晶粒的数量增加;晶粒成核过程和生长过程所需要的过饱和度范围不同,过饱和度较大(>2600)时成核次数多生长次数少;而过饱和度在250～2600时生长次数多成核次数少.     

人工可控氢氧化镁晶须生长

从负离子配位多面体生长基元模型出发,根据大维度生长基元的结构特性,讨论了人工可控氢氧化镁晶须生长,主要介绍了多元醇法及镁盐过饱和度法.多元醇法的实质是醇中的羟基在一定条件下与大维度生长基元中的羟基发生假联结(即吸附),使得与多元醇发生了假联结的晶面生长速率大大减小或甚至停止生长,而其他晶面仍然保持原有的速率生长以致形成晶须.镁盐过饱和度法就是使得生长基元[Mg-Ax](x-2)-(A≠OH-)的浓度很大,且要远比[Mg-(OH)x](x-2)-组分浓度大4倍以上,以先形成碱式镁盐晶须,碱式镁盐晶须再与适当的碱液反应,即可制备得氢氧化镁晶须.     

甲酸钠单晶及其复盐的研究综述

综述了甲酸钠单晶(SFA)及其复盐一水甲酸锂钠(LSFM),甲酸钠镉(SCF)等晶体的主要研究成果,指出它们的非线性光学性能具有很大的应用价值,并对其今后的研究工作提出建议.     

高掺镁铌酸锂晶体OH-吸收光谱的低温研究

本文测量了纯铌酸锂和高掺镁铌酸锂晶体的低温红外光谱,观察了OH-吸收峰的温度依赖特性.研究发现纯铌酸锂的OH-振动吸收峰基本不随温度而变化,而高掺镁铌酸锂晶体的OH-振动吸收峰的主峰峰位随温度的降低向高波数方向移动.通过分析两种晶体中不同的缺陷模型以及H+在晶格中的占位,我们提出高掺镁铌酸锂晶体中的H+紧邻高电性杂质缺陷(MgNb)3-分布,直接参与缺陷集团,完全不同于纯铌酸锂晶体中H+的分布情形,这造成了高掺镁铌酸锂晶体中OH-振动吸收峰随温度的变化.而集团内部缺陷之间相互作用随温度降低而增强的趋势是OH-振动吸收峰右移的主要原因.     

Study of potassium titanyl phosphate (KTP) flux growth by holographic phase-contrast interferometric microphotography

This paper describes a special set of equipment we designed, which is suitable to be used to study the high temperature solution growth process by optical method. The variation regularities of the solid-liquid interface boundary layer in the potassium titanyl phosphate (KTP) crystal growth and dissolution process have been investigated by holographic phase-contrast interferometric microphotography. It has been found that under the condition of free convection, the relation between the thickness of the boundary layer and supersaturation is linear. Moreover, the variation of refractive index caused by the change of solute concentration in the boundary layer will form an exponential function of the distance from the crystal face.     

不同pH值下磷酸二氢铵(ADP)溶液成核过程研究

利用全程摄像的方法测定了不同情况下ADP过饱和溶液的诱导期,研究了不同pH值、不同温度的ADP过饱和溶液的成核过程,讨论了pH值、温度和过饱和度S等因素对诱导期的影响.结果表明:改变pH值后,在同一过饱和度下,溶液的稳定性在不同温度间差异较小,更利于晶体在较高的温度下稳定快速的生长;改变pH值后,溶液在整个过饱和度范围内更趋向于均匀成核.根据经典均匀成核理论,针对ADP溶液均匀成核的状况计算出了不同pH值和温度下的固-液界面张力、临界成核功等成核参数,并从上述参数的相互比较中得到了改变pH值后溶液稳定性变强的微观原因.最后通过对表面熵因子的计算,确定了ADP晶体的微观生长机制为连续生长模式.     

EDTA和KCl双掺杂下KDP溶液的稳定性研究

研究了EDTA与KCl不同掺杂浓度和不同过饱和比下KDP溶液的成核过程,测定了不同条件下KDP过饱和溶液的诱导期;根据经典成核理论计算了成核热、动力学参数,并分析了溶液稳定性随掺杂浓度的变化情况。利用化学腐蚀法对KDP晶体(100)面进行了腐蚀,得到了清晰的位错蚀坑,并使用光学显微镜观察了(100)面位错蚀坑的分布特点。结果表明,当过饱和度为4%、掺杂浓度为0.01 mol%EDTA和1 mol%KCl时,不仅KDP过饱和溶液的稳定性比较高,而且位错蚀坑的分布比较均匀、密度小,适合高质量的KDP晶体生长。     

Metastability and crystal growth kinetics on L‐arginine phosphate

Stability of saturated L‐Arginine Phosphate (LAP) solution studied as a function of supercooling rate and crystal growth kinetics investigated as a function of supersaturation are reported in this communication. Solution stability was studied by observing the metastable zone width at different cooling rates employing a polythermal method. Analysis of the experimental data yielded the kinetic constant of nucleation and the order of nucleation. Crystal growth rates studied on small seed crystals with regular morphology, under normal growth conditions and at different supersaturation levels were found to satisfy BCF surface diffusion model. Crystal growth rates were investigated normal to the (100), (010) and (00 ) faces. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Mass transport effect within the boundary layers in solution crystal growth: Holographic study of KTP and KDP crystal growth

Using holographic phase-contrast interferometric microphotography, we have carried out real-time investigations of the mass transport processes taking place during the high temperature solution growth of KTiOPO₄ (KTP) crystal and low-temperature solution growth of KH₂PO₄ (KDP) crystal. Our experiments demonstrate that a mere diffusion boundary layer is not existing. The mass transport process within the boundary layers is a result of the coupled effect of diffusion and convection actions, no matter whether it is high-temperature or low-temperature solution growth. Under free convection state, the influence of bulk supersaturation on the thickness of solute boundary layer exists in the two different regions. The solute concentration distribution within the layer is an exponential function of the position.     

Influence of a polyacrylate antiscalant on gypsum nucleation and growth

Calcium sulphate dihydrate (gypsum) crystallization was studied under conditions, of supersaturation and temperature, simulating a brackish water desalination unit using solar energy. The effect of an commercial sodium salt of poly(acrylic acid), based compound known as RPI, on homogeneous nucleation and growth of gypsum was also examined. Gypsum was precipitated by mixing aqueous CaCl₂ and Na₂SO₄ solutions. It was found that, with increasing temperature or supersaturation, the induction time decreases and the growth rate increases. By using classical nucleation theory, the interfacial tension and the nucleation rate values were estimated. It was shown that the interfacial tension is temperature dependent. The addition of increasing quantities of RPI, in the same conditions of temperature and supersaturation, prolongs the induction time, decreases the nucleation rate and increases the interfacial tension. The addition mode of RPI (in calcium or in sulphate solution) was found as an important parameter in controlling the inhibition process of gypsum crystallization. XRD and SEM analysis showed that RPI antiscalant strongly affected the texture and the morphology of the deposit gypsum. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Evaluation of nucleation rate by in‐situ focused beam reflectance measurement in an unseeded batch cooling crystallization

Nucleation kinetics in the cooling crystallization of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX) from γ‐butyrolactone was studied by converting total counts/s measured by in situ focused beam reflectance measurement (FBRM) into number of crystals. The classical nucleation rate model, which is derived exclusively from the thermodynamic state for the nucleation and molecular collision frequency, was found to be inadequate to describe the experimentally measured nucleation rates. However, the nucleation rates predicted by the modified classical nucleation rate model, inclusive of an additional temperature term, were found to be in good agreement with those measured in the present work. Furthermore, the metastable zone widths are also found to be more accurately predicted by the modified classical nucleation rate model than the classical approach, which assumes that the mass‐based nucleation rate is an exponential function of supersaturation and is equal to the supersaturation rate.     

Oscillating crystal growth rates

A number of papers in the literature have reported that under certain conditions the growth rate of a crystal may not assume a unique value at a given supersaturation. These papers implied either that identical crystals growing in a supersaturated solution under identical conditions did not all grow at the same growth rate or that a given growing crystal was alternating between two values of growth rate. In this work the existence of such a phenomenon was clearly demonstrated by experiments with sodium chloride crystal whiskers in which the growth was monitored semi-continuously. It was observed that instead of being a continuous process, crystal growth was intermittent in nature. Growth was characterized by two alternating periods, a growth period during which rapid growth occurred and a period of small or non-existent growth. This work also showed that this type of intermittent growth could account for another phenomenon previously reported in an investigation with potassium alum crystals; that in certain supersaturation regions the growth rates appeared to be insensitive to changes in supersaturation. It is also pointed out that the existence of periodic rates will complicate the expressions for the kinetics of growth used in the analysis of crystallizers and that the insensitivity of growth rates to supersaturation may affect the stability of continuous crystallizers.