The Influence of Impurities on Crystallization Kinetics of Sodium Chloride

The influence of impurities on the crystallization kinetics of NaCl was investigated in a fluidized bed crystallizer. The growth and dissolution rates were related to the supersaturation and impurity concentrations. The effect of different impurities on the growth rate of NaCl crystals can be divided into thermodynamic effects where the impurities influence the solubility and kinetic effects where the impurities will suppress the growth rate compared to the pure NaCl. A mathematical model describing crystal growth rates from aqueous solution as a function of impurity concentration is presented. The model explains impurity concentration effects on the crystal growth rate in terms of an impurity effectiveness factor and a Langmuir adsorption isotherm for the impurity.     

Crystallization Kinetics of NaCl in Multicomponent Solutions

Experimental results of solubility and growth kinetics measurements of sodium chloride crystals in multicomponent systems at 303 K are given. The effect of several solutes in elevated concentrations on the growth and dissolution kinetics is analysed on volume diffusion and surface integration steps: While the diffusion of ions within the solution decreases by the presence of foreign ions, the integration resistance can increase (mobile or immobile adsorption of foreign ions) or may even be reduced in some cases (due to a decreased surface energy).     

铝诱导非晶硅薄膜晶化动力学研究

为探讨其晶化过程及动力学机理,本文采用磁控溅射技术制备Al/Si薄膜,并利用快速光热退火制备微晶硅.通过采用不同的衬底温度及对铝膜进行退火处理,探究其晶化动力学过程.利用拉曼散射光谱(Raman)仪和X射线衍射(XRD)仪对薄膜进行性能表征.结果表明:退火及衬底加热均能在界面形成非共融的硅铝化合物;延长退火时间能使Al/Si界面充分扩散,达到成核条件.较大的铝晶粒及其择优取向,能有效改善铝诱导晶化效果.     

Onset Temperatures and Kinetics of Quartz Glass Crystallization

Crystallography Reports - A complex analysis of the crystallization of quartz glass from quartzites of the Bural-Sardyk deposit (the Eastern Sayan) has been performed. A mineralogical and...     

定位锌结晶釉的析晶动力学分析

本文以ZnO作为定位结晶剂在1100℃下制备了ZnSiO3结晶釉,测试了其在不同析晶保温时间下釉面晶花大小,并根据结晶动力学理论,对结晶釉中ZnSiO3晶花的生长规律和结晶机理进行了分析探讨.结果表明:当析晶保温时间超过30 min,晶花的形成速率随时间增加而显著提高,并在45 min到60 min范围内达到最大值;当析晶保温时间超过90 min,晶花形成速率随时间增加而快速下降,并在析晶保温时间超过150 min后,晶花基本上不再生长,形成速率达到稳定值.采用ZnO作定位晶种的釉面结晶稳定性好,釉面晶花大小与析晶保温时间符合S型生长曲线关系,可用Logistic函数拟合,本研究为实现锌结晶釉的可控生长提供了参考.     

Chiral Symmetry Breaking in Sodium Chlorate Crystallization from Unstirred Solution

Statistics of nucleation of chiral forms of sodium chlorate from unstirred, achiral solutions was studied. The trimodal distribution of enantiomers was obtained in which apart from the peak for the same probability of the creation of L and D crystals, two other maxima for the large enantiomeric excesses of L and D forms were present. The first nucleated crystals govern the handedness of the secondary crystals and the formation of pure enantiomers and high enantiomeric excesses in crystallization from unstirred, unseeded solutions are caused by the process of chiral symmetry breaking rather than statistical fluctuations.     

脱硫石膏制备硫酸钙晶须结晶动力学研究

结晶动力学能够揭示结晶过程本质,通过测定溶液中Ca2浓度来确定硫酸钙晶须的转化率,从而确定硫酸钙晶须结晶动力学参数,得到转化率与时间的关系式:X=1/｛1+e6^[-10.01977t(0.0956-c)+1.1188]｝,(0≤t≤6.0).研究了影响硫酸钙晶须结晶动力学的影响因素降温速率和陈化时间,利用SEM对制备的硫酸钙晶须进行表征.结果表明:自然冷却条件下,陈化时间6h,制备出的硫酸钙晶须结晶发育完整,晶须平均长径比达到150,平均直径为2.1 μm.     

定位硅酸锌结晶釉析晶动力学研究

本文利用定位结晶法研究了氧化锌和硅酸锌两种晶种对硅酸锌结晶釉釉面晶花的影响,根据结晶动力学理论,对结晶釉中硅酸锌晶体的生长规律和结晶机理进行了探讨,并比较了不同晶种对硅酸锌晶体生长规律的影响.实验结果表明:采用氧化锌和硅酸锌作定位晶种的釉面晶花外观效果基本相同;釉熔体中硅酸锌晶体生长半径与保温时间成线性关系;不同的定位晶种对硅酸锌晶体的生长基本没有影响;结晶常数随着析晶保温温度的提高而增加,当析晶保温温度分别为1150 ℃,1100 ℃和1050 ℃时,所对应的结晶常数依次为1.0911,0.9996和0.7177;即使在同一析晶保温温度下,不同的保温时间段其结晶常数也不同.     

纳米氧化镱对熔融石英析晶动力学机制的影响

本文研究引入纳米氧化镱对熔融石英析晶机制及动力学过程的影响.通过X射线衍射仪(XRD)测试结果分析了纳米氧化镱的引入对熔融石英陶瓷析晶率的影响,采用动力学方法分析了纳米氧化镱的引入对熔融石英陶瓷析晶机制的影响,同时探讨了其等温析晶动力学过程.研究表明,熔融石英陶瓷的晶粒向二维兼有一维及三维的方式生长,引入纳米氧化镱的熔...     

Crystallization Kinetics of Silicalite-1: Use of Tetrapropylammonium Bromide and Chloride as Templates

Silicalite-1, the aluminum-free end number of the ZSM-5 zeolites, was synthesized from a batch composition of 3.25 Na₂O · 40.0 SiO₂ · 552 H₂O · 2.00 TPA by using tetrapropylammonium bromide (TPA-Br) or chloride (TPA-Cl) as templates in the temperature range of 100 to 175 °C in a batch system. Conversion of silica in the starting batch composition into silicalite-1 in the product was followed quantitatively. The activation energies of nucleation and crystallization were determined as 37.2 and 66.5 kJ/mol, respectively. The use of TPA-Cl as the template instead of TPA-Br results in longer induction period for crystallization to start and a larger crystal size in product.     

A Study of the Nucleation Kinetics,Linear Growth and the Overall Crystallization Kinetics of Meltspun Pd80Si20 Amorphous alloy

Nucleation kinetics, linear growth rate and overall isothermal crystallization kinetics of Pd Si amorphous alloy are studied by means of DSC and optical microscopy. It is found that both the histograms of the crystallite sizes and the DSC isotherms (resp. the time dependences of the degree of transformation α(t)) are best described by the model comprosing the simultaneous occurrence of two reactions of crystallization: heterogeneous as well as homogeneous non-stationary nucleation with subsequent three-dimensional growth in both cases. From the fit of the experimentally measured and the calculated according the model thus proposed distribution curves N_i(Φ) the stationary rates of heterogeneous and homogeneous nucleation, the number of quenched-in nucleation sites and the transient time lags of heterogeneous and homogeneous nucleation have been estimated. Using the values of these parameters kintic curves degree of transformation vs. time have been generated, which are closed to the exerimental x(t) curves obtained by means of DSC at isothermal conditions.     

Influence of Magnetic Field in the Kinetics of Crystallization of Diamagnetic and Paramagnetic Inorganic Salts

The influence of the magnetic field on some kinetic crystallization parameters of the systems zinc sulfate - water and copper sulfate - water were investigated in a series of controlled batch cooling experiments. The solutions were exposed to magnetic fields with different intensities, up to a maximum of 0.7T. A clear influence of magnetic field on the zinc sulfate crystallization parameters was found: an increase in the saturation temperature, a decrease in the metastable zone width, and increased growth rate and average crystal size. These effects were observed for the diamagnetic zinc sulfate, but not in similar experiments with paramagnetic copper sulfate.     

不同冷却方式黄磷炉渣微晶玻璃析晶动力学研究

以水淬黄磷炉渣和自然冷却态黄磷炉渣为研究对象,采用熔融法制备CaO-Al2O3-SiO2系微晶玻璃.通过差热分析、X射线衍射和扫描电镜,并利用修正后的Johnson-Mehl-Avrami (JMA)方程和Augis-Bennett方程,分析了不同冷却方式下黄磷炉渣制备微晶玻璃的析晶规律.结果表明:不同冷却方式对微晶玻璃的析晶行为有所不同,水淬黄磷炉渣微晶玻璃的析晶活化能E为352.609 kJ/mol,自然冷却黄磷炉渣微晶玻璃的析晶活化能E为405.685kJ/mol;两种不同冷却方式的黄磷炉渣微晶玻璃的晶化机制均为三维体积晶化.水淬黄磷炉渣微晶玻璃中主晶相为硅灰石(CaSiO3)并含有少量的石英矿物;自然冷却黄磷炉渣微晶玻璃中主晶相为钙蔷薇辉石类(Ca(Mn2,Ca)Si2O6)和含铁硅灰石类固溶体((Ca,Fe) SiO3).以自然冷却渣制备的微晶玻璃性能优于水淬渣制备出的微晶玻璃.     

Study of Isothermal Crystallization Kinetics of 5CB with Differential Scanning Calorimetry and Broadband Dielectric Spectroscopy

The isothermal crystallization kinetics of 4-n-pentyl-4–cyanobiphenyl (5CB) has been studied with Differential Scanning Calorimetry (DSC) and Dielectric Relaxation Spectroscopy (DRS). 5CB is a well characterized material which makes it ideal for a dielectric and thermal comparative study. The effect that isothermal crystallization exerts on the behavior of relaxation processes α and δ by cooling the isotropic liquid below the nematic phase or through the process of cold crystallization by heating it from the supercooled state is explored by comparing the DRS and DSC. Furthermore, by employing the Avrami equation, we compare the ability to probe the crystallization with each technique.     

Differential Thermal Analysis Studies on the Crystallization of Strontium Tungstate from Sodium Tungstate Melts Thermodynamic and Kinetic Parameters

From the estimated diffusion rate-constants (k_D1) of strontium tungstate crystal growth from sodium tungstate melts in platinum crucibles, energy (E), enthalpy (ΔH_a), entropy (ΔS_a) and free-energy (ΔG_a) of activation and the pre-exponential factor (k₀) for the process were estimated using an ordinary Arrhenius equation k_Dl = k₀e^−E/RT. These thermodynamic parameters were virtually unaffected by the changes in crystallization temperatures (T₀) and cooling rates (R)_T. The distance (r₁₂), between a diffusing species and its host necesary for a successful diffusion, increased with T₀ and T_T but there was no direct correlation.     

Drawning-out Crystallization

Equations for the modelling of a continuous perfectly agitated crystallizer with drowning-out reaction are presented. Because the supersaturation of the solution is usually limited by the materials balance resulting from the technology used and the crystal growth rate is thus rather low, an agglomeration mechanism is considered in order to obtain larger particles. The results are demonstrated on an example of drawning-out of KCl by NaCl.     

药物结晶中的经典与非经典结晶路径

晶体的结晶路径分为经典结晶路径和非经典结晶路径。经典结晶路径往往涉及一些简单的化学结构,晶体的成核、生长是通过单体的依次添加实现的,经过长期研究,目前研究人员已对其有了较为深刻的理解并形成了一套相对完善的理论体系;但对于非经典的结晶路径,由于涉及复杂中间态粒子的形成和多步结晶过程,尚未获得全面、统一的理论支持。在药物结晶领域,有机分子构象自由度的引入增加了体系的复杂性,分子间弱的相互作用使得固态药物分子存在多晶型现象。由于药物的理化性质及生物利用度与其晶型息息相关,同时,药物结晶过程中出现的一些复杂中间态粒子往往会改变最终得到的药物晶型,因此迫切需要加强对药物晶体成核和生长路径的研究,以期发展能实现对药物晶体成核和生长过程主动控制的方法。本文简要综述了目前药物在溶液或熔体中结晶的经典与非经典结晶路径,包括奥斯特瓦尔德阶段定律、独立成核、交叉成核。从溶液化学的角度看,分子在浓溶液中会通过自组装形成结构合成子,成核与溶液中的生长单元、结构合成子密切相关。从分子水平上探索溶液中有关分子运动的信息、分析各体系下晶核与结构合成子之间的关系是区分两种结晶路径的关键所在,非经典结晶在药物结晶领域是机遇也是挑战。     

Crystallization of gel-derived glasses

The crystallization behaviors of gels, gel-derived glasses and melted glasses are reviewed, and comparisons are effected among the observed behaviors. These comparisons are related to the behavior expected on the basis of models for the nucleation frequency and crystal growth rate, as well as the anticipated differences in material characteristics among gels and the two types of glasses. Different temperature regimes are identified where different comparisons between melted and gel-derived materials are expected. It is concluded that a need exists for more definitive, detailed data on the crystallization behavior of gel-derived materials.