富勒烯结晶特性研究

用扫描电镜（ＳＥＭ）和Ｘ射线衍射（ＸＲＤ）方法研究了不同Ｃ６０／Ｃ７０含量比的甲苯溶液在单晶硅表面大气环境条件下等温蒸发Ｃ６０６ Ｃ６０／Ｃ７０的结晶特点。纯Ｃ６０的结晶表面为层状扩展的生长过程，生成的晶粒具有完整的晶面。而Ｃ７０的存在影响Ｃ６０的结晶过程，破坏晶面的完整性、晶粒成核速度加快、晶体生长表现为典型的非平衡态多核竞争生长过程从而使结晶产物的出现明显的分形结构。     

结晶生长的化学键合理论

针对一般晶体的生长过程,在测定相应溶液(熔体)组成结构的基础上,我们引入了晶体生长过渡相区的概念,并采用键价模型来衡量生长过程中发生变化的化学键的键强度。过饱和溶液(熔体)中的生长单元经过生长过渡相区时,依据彼此之间弱的化学键合作用来微调其内部强的化学键,并以单个生长单元或者生长单元的简单连接体的形式键合进入晶格。在整个结晶生长过程中,生长单元之间弱的键合作用对整个结晶过程(生长速度、晶相的形成)起着决定性作用;同时,中等强度的化学键在生长过渡相区中的变化情况对晶体的最终形貌具有重要影响。     

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.     

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.     

以晶体生长原理重塑蚕丝柔性材料世界的未来

本文通过先进的结构表征手段,证实了包括丝蛋白材料在内的多种柔性材料内存在典型的介观多级结构和晶体网络结构。由于柔性材料中介观结构特别是晶体网络结构对于其宏观性能的有决定性影响,全面深入了解内部晶体的生长动力学和晶体网络结构的介观重构尤为重要。根据丝蛋白分子折叠成丝蛋白材料的最新研究成果,将晶体研究的方法,包括结晶动力学,应用到柔性材料的研究之中后,确定丝蛋白材料的形成过程遵循典型的“成核-结晶”机理。不仅如此,通过定向设计和控制晶体网络的形成及关键结构参数,如晶体密度、取向度、掺杂分子成核引发剂等,还可以实现柔性材料的介观重构与介观功能化,为发展全新的柔性介观光、电子学提供了可能。     

胞外多糖调控碳酸钙结晶的研究

以黄原胶和韦兰胶为模板,在CaCl2-Na2CO3体系中调控合成CaCO3晶体.利用电导率法研究了黄原胶与韦兰胶模板与Ca2+之间的相互作用,同时研究了黄原胶和韦兰胶的浓度以及结晶时间对CaCO3晶体结构及形貌的影响.分别用X射线衍射(XRD)、扫描电镜(SEM)对CaCO3晶体的晶型和形貌进行了表征.结果表明,黄原胶和韦兰胶调控下得到的CaCO3晶体是方解石和球霰石的混合体.韦兰胶溶液中得到了球形产物,黄原胶溶液中得到球状和花状产物.随着结晶时间的延长,球霰石不断向方解石转变.     

Cd0.8 Mn0.2 Te晶体生长及结晶质量评价

采用垂直布里奇曼法生长了尺寸为φ30 mm×120 mm的Cd0.8Mn0.2Te晶锭.采用X射线粉末衍射及X射线双晶摇摆曲线分析了晶体的结构与结晶质量,结果显示所生长的晶体为单一立方闪锌矿结构,半峰宽为47.2aresec,结晶质量良好.采用化学腐蚀方法显示了晶体中的多种缺陷,包括位错,Te夹杂和孪晶.采用光学显微镜,扫描电镜和X射线能谱仪对缺陷形态和分布进行了研究.结果表明,晶体中位错密度在105～106cm-2之间.晶体局部存在Te夹杂相,尺寸为l～5μm.晶体中孪晶主要以共格孪晶存在.并提出了缺陷形成的原因和减少缺陷的方法.     

碳纳米管结构对聚乙烯/碳纳米管纳米杂化串晶的影响

通过溶液等温结晶技术制备了聚乙烯/碳纳米管纳米杂化串晶(Nanohybrid shish-kebab),利用透射电子显微镜观察了纳米杂化串晶的形貌,讨论了不同结晶条件,尤其是碳纳米管的直径对串晶形貌的影响.结果表明,聚乙烯片晶在多壁碳纳米管表面能够实现可控周期性修饰,较小直径的Ⅰ-MWNT的异相成核能力更强,在其表面所生长的kebab密度较大,但结构规整性较差,而在较大直径的Ⅱ-MWNT表面所生长的kebab结构更为规整.碳纳米管的直径对纳米杂化串晶的形成和形貌有重要影响.     

F-及SiF2-6对α型半水硫酸钙结晶成核及形貌的影响

本文模拟了半水法湿法磷酸生产过程中α型半水硫酸钙(α-HH)的结晶过程。在30%P₂O₅,反应温度95 ℃,过饱和度S=1.64~2.10条件下,通过浊度仪监测溶液中浊度变化,测定了不同F^-及SiF^2-₆浓度下α-HH结晶诱导时间,采用经典成核理论公式计算了α-HH的临界晶核半径及成核速率,并通过扫描电子显微镜(SEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)表征分析了F^-及SiF^2-₆对α-HH结晶过程的影响。结果表明:随着F^-、SiF^2-₆浓度的升高,α-HH晶体的结晶诱导时间延长,表面能和临界晶核半径都增大,然而成核速率减小。当过饱和度S=1.64时,加入0.06 mol·L^-1 F^-,α-HH结晶诱导时间延长了465 s,成核速率减小到0.403×10²⁹ 晶核数·cm^-3·s^-1,然而,加入0.06 mol·L^-1 SiF^2-₆,α-HH结晶诱导时间延长了710 s,成核速率减小到0.339×10²⁹晶核数·cm^-3·s^-1。SiF^2-₆对α-HH晶体抑制成核作用大于F^-。F^-、SiF^2-₆阻碍了α-HH晶体沿C轴方向生长,使得晶体长径比减小,晶体形貌向短柱状变化。F^-、SiF^2-₆影响了α-HH晶体(200)、(310)、(400)晶面衍射峰强度和结晶度。控制半水法湿法磷酸中F^-及SiF^2-₆浓度水平,可以得到短柱状的α-HH晶体,有利于过滤洗涤。     

Co2+掺杂Zn2SiO4结晶釉生长机理的研究

以高岭土、石英、钠长石、石灰石、氧化锌等矿物为原料,ZnO为晶核剂,并掺杂Co2+控温烧结Zn2 SiO4结晶釉.利用X射线衍射仪(XRD)分析样品物相,白度色差计测量釉料色度(L*、a*、b*),EDS能谱仪分析样品组成含量.采用Johnson-Mehl-Avrami (JMA)方程对釉的结晶动力学进行分析,探讨釉中晶体的生长机理.结果表明:高温时Co2+置换了Zn2SiO4结晶釉中的Zn2+.随着保温时间的延长,掺杂了Co2+的Zn2SiO4晶体颗粒不断长大,在1140℃下保温170 min晶花达到最大,其晶花面积均值为410.91 mm2.模拟动力学分析,釉中晶体的Avrami指数n1100℃ =0.82,n1140℃=1.23,n1180℃=1.12,表明晶体的形成由扩散机制向成核机制转变.拟合Arrhenius方程,晶体的活化能Ea=148.2 kJ/mol.     

Implementation of Temperature-Controlled Method of Protein Crystallization in Microgravity

An experimental scientific equipment for implementing temperature-controlled protein crystallization in capillaries under microgravity has been developed, fabricated, and tested. This crystallization method, providing on-line separate control of crystal growth both in the stage of nucleation of crystals and during their further growth, requires small amounts of protein solution. The equipment has been tested on board of Foton-M4 spacecraft (growth of lysozyme protein crystals of high structural quality in microgravity) using a cyclogram developed in ground-based experiments. The results obtained have demonstrated efficiency and importance of the developed equipment and method for growing biomacromolecular crystals of high-structural quality.

     

Study of lactose crystallization in water‐acetone solutions

This paper describes a study on the process of lactose crystallization using a water‐acetone solution. The selection of lactose was based on its significance for the pharmaceutical and food industries and on the fact that the crystallization of this organic compound has been little studied and is, unlike inorganic compounds, complex. The objective was to achieve lactose batch crystallization of solutions by analyzing the crystal growth under different operating conditions. To determine solubility curves, the experiments were carried out based on gravimetric methods. All the crystallization experiments were performed according to the methodology proposed by Nývlt in 1985, who uses the temperature at which the first crystals appear (nucleation) to establish the width of the metastable zone and the induction time. The results showed that crystals with different average diameters, shape factors, and recovered mass were obtained for different water‐acetone compositions. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystallization mechanisms of acicular crystals

In this contribution, we present an experimental investigation of the growth of four different organic molecules produced at industrial scale with a view to understand the crystallization mechanism of acicular or needle-like crystals. For all organic crystals studied in this article, layer-by-layer growth of the lateral faces is very slow and clear, as soon as the supersaturation is high enough, there is competition between growth and surface-activated secondary nucleation. This gives rise to pseudo-twinned crystals composed of several needle individuals aligned along a crystallographic axis; this is explained by regular over- and inter-growths as in the case of twinning. And when supersaturation is even higher, nucleation is fast and random.In an industrial continuous crystallization, the rapid growth of needle-like crystals is to be avoided as it leads to fragile crystals or needles, which can be partly broken or totally detached from the parent crystals especially along structural anisotropic axis corresponding to weaker chemical bonds, thus leading to slower growing faces. When an activated mechanism is involved such as a secondary surface nucleation, it is no longer possible to obtain a steady state. Therefore, the crystal number, size and habit vary significantly with time, leading to troubles in the downstream processing operations and to modifications of the final solid-specific properties.These results provide valuable information on the unique crystallization mechanisms of acicular crystals, and show that it is important to know these threshold and critical values when running a crystallizer in order to obtain easy-to-handle crystals.     

Crystallization of mefenamic acid and polymorphs

The crystallization of Mefenamic Acid, (MA), which has a prevalent usage in drug formulation, was investigated. MA is a high‐dose, anti‐inflammatory, analgesic agent used for pain in menstrual disorders. Some negative properties of MA are a high hydrophobicity and propensity to stick to surfaces, which cause great problems during granulation and tabletting. To facilitate tabletability, enhance dissolution rates, and develop a stable and reproducible dosage form, investigation of the physicochemical properties of mefenamic acid is necessary. Pharmaceutical drugs are commonly crystalline materials and are therefore subject to polymorphism. Polymorphism, the ability of a substance to exist in more than one crystalline form, is a significant phenomenon in the field of chemical engineering sciences, including pharmaceutical development. Establishing the polymorphic behaviour of a drug molecule early in development minimizes the number of unsuitable candidates developed and reduces the risk of encountering issues later which may have a major financial and time impact. Mefenamic acid crystals were recrystallized from five different solvents of N, N‐dimethylformamide (DMF), acetone, N, N‐dimethylacetamide (DMA), Dimethylsulfoxide (DMS) and Ethyl Acetate (EA). In order to characterize the Mefenamic Acid crystal structure and the polymorphic forms of the crystals obtained by recrystallization, the scanning electron microscopy (SEM), Raman diffractometry and X‐ray pattern were used. From the industrial crystallization point of view, the crystal size distribution (CSD), the crystal shape, the polymorphic form and the crystallization steps are important factors that affect the quality and bioavailability of a drug. For the determination of crystal size distribution of MA, The Focused Beam Reflectance Measurement (FBRM) technique was practiced and CSD profiles were obtained. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

复合晶核剂对黄磷炉渣微晶玻璃析晶的影响

以黄磷炉渣为主要原料,通过添加不同种类的复合晶核剂,采用熔融法制备了黄磷炉渣微晶玻璃.借助化学热力学软件FactSage 6.4模拟计算晶相类型,借助Kissinger方程分析析晶能力,利用X射线衍射仪(XRD)和扫描电子显微镜(SEM)进行验证.结果表明:相比添加单一晶核剂TiO2,复合晶核剂TiO2+CaF2或复合晶核剂TiO2+P2O5均能够降低黄磷炉渣基础玻璃的析晶活化能E,促进其析晶,复合晶核剂TiO2+Cr2O3能够提高黄磷炉渣基础玻璃的析晶活化能E,抑制其析晶;无论添加单一晶核剂TiO2,还是添加复合晶核剂TiO2+CaF2、复合晶核剂TiO2+P2O5或复合晶核剂TiO2+Cr2O3,黄磷炉渣微晶玻璃晶相类型相同,主晶相为硅灰石(CaSiO3),副晶相为铝透辉石(Ca(Mg,Al)(Si,Al)2O6)和氟磷灰石(Ca5(PO4)3F),这与化学热力学软件FactSage 6.4模拟计算结果基本一致.     

Study on crystallization kinetics and the crystal internal defects of HMX

In this paper, the solubility data of HMX (1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocane) in acetone from 323.15 K to 293.15 K were accurately measured by use of the laser‐monitoring observation technique. Intermittent dynamic method was utilized to study crystallization kinetics of HMX in acetone. The data of crystallization kinetics were obtained by moment analysis, and the parameters of the growth rate and nucleation rate equations were derived by using multiple linear least squares method. Subsequently, growth rate and nucleation rate at different conditions were calculated according to these equations. In addition, Optical Microscopy Images (qualitative) and Particle Apparent Density (quantitative) experiments were applied to study the crystal internal defects of HMX under different crystallization conditions. It can be found that the crystal apparent density of HMX is in the range of 1.8993 g·cm⁻³ to 1.9017 g·cm⁻³, very close to the theory density of HMX; the internal defects and the crystal size do not increase after 25 °C, from which we predict that the HMX crystal growth reaches the steady growth segment. These results suggest that the nucleation rate is a significant factor influencing the crystal internal defects, and larger nucleation kinetics can reduce crystal internal defects.     

Initial stages of SiC crystal growth by PVT method

Initial stages of SiC crystal growth by Physical Vapor Transport method were investigated. The following features were observed: (a) many nucleation crystallization centres appeared on the seed surface during the initial stage of the growth, (b) at the same places many separate flat faces generated on the crystallization front, (c) the number of facets was dependent on the shape of the crystallization front and decreased during growth, (d) appearance of many facets lead to decrease of structural quality of crystals due to degradation of regions where crystallization steps from independent centres met. The results revealed that the optimal crystallization front should be slightly convex, which permits the growth of crystals with single nucleation centre and evolution of single facet on the crystallization front. The subjects of study were the shape and the morphology of growth interface. Defects in the crystallization fronts and wafers cut from the crystals were studied by optical microscopy, atomic force microscopy (AFM) combined with KOH etching and X‐ray diffraction. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

流动电位法对降温结晶过程的研究

对过饱和溶液在施加一定的流体压力差使之循环流动,实验结果测算草酸、草酸钠、硼酸和磷酸氢二钠等在不同温度下饱和溶液降温结晶时流动电位随时间的变化规律.实验结果表明流动电位大小与结晶物质的种类、温度和浓度有关,同时易受外界因素的干扰,实验数据的严格重现较难.但多次实验结果都显示:过饱和溶液在某一温度下形成晶核过程中其流动电位均发生显著变化;当饱和溶液起始结晶温度较高时,其流动电位突变点温度也更高.