晶形控制剂对α半水石膏结晶形态的调控研究

实验以石灰中和后的磷石膏为原料,分别以顺丁烯二酸、氨三乙酸、丁二酸为晶形控制剂,采用“半液相法”制备α半水石膏.利用XRD、SEM、XRF及EDS分别对原料及α半水石膏的物相组成、结晶形貌、成分含量等特征进行表征.结果表明:晶形控制剂在改善α半水石膏晶体形貌的同时并没有改变晶体的物相组成,可以有效抑制晶体一维方向的生长,生成短柱状的α半水石膏晶体.其中顺丁烯二酸用量在0.1;,制备的α半水石膏结晶形态最好,长径比接近1∶1,转化率可达到98;.抗压强度可达45.3 MPa.     

硅酸钠和重烷基苯磺酸盐对碳酸钙物相和形貌的影响

研究了硅酸钠及重烷基苯磺酸盐(HABS)对碳酸钙晶型和形貌的影响,采用FESEM、XRD和FT-IR等手段,对获得的产物进行了表征.结果表明,硅酸钠可促进不同形貌和不规则聚集体状碳酸钙的形成;当硅酸钠浓度大于250 ppm时,可以抑制部分无定形碳酸钙向方解石的转化;当HABS与硅酸钠同时存在时,优先形成麦穗状方解石.     

有机非线性光学晶体DAST的生长、形貌及透过光谱

采用自发结晶法和籽晶法制备了4-(4-二甲基氨基苯乙烯基)甲基吡啶对甲基苯磺酸盐(DAST)晶体,所得晶体尺寸为10 mm×10mm 1～2 mm.研究了不同生长位置对生长习性和晶体形貌的影响,在溶液中部或顶部生长时DAST晶体倾向于沿a轴方向生长,晶体呈片状;在溶液底部时DAST晶体c轴方向生长加快,晶体呈块状.测试了DAST晶体(001)面X射线衍射摇摆曲线,对比分析了不同生长方法对晶体质量的影响.另外,对所制备的DAST晶体的透过光谱及吸收系数进行了研究.     

聚合物与表面活性剂混合模板调控碳酸钙结晶

以聚乙烯醇(PVA)和聚苯乙烯磺酸钠(PSSS)分别与十六烷基三甲基溴化铵(CTAB)组成混合模板,在CaCl2、Na2CO3体系中调控合成CaCO3晶体.考察了不同CTAB浓度及结晶温度对碳酸钙晶体的影响.通过扫描电子显微镜(SEM)、红外光谱(FT-IR)及X射线衍射(XRD)等技术对晶体的形貌和结构进行了表征,并对不同形貌碳酸钙的形成机理进行了探讨.结果表明:在PVA和CTAB模板中,5℃为方解石椭球状聚集体,25℃时为菊花状、立方状的方解石和球霰石的混晶,90℃时得到针状文石晶簇.以PSSS和CTAB模板调控下的碳酸钙,5℃时为球状的方解石和球霰石的混晶,25℃为颗粒均匀的球形球霰石,90℃时得到了花朵状文石.不同形貌及晶型碳酸钙的生成源自聚合物与CTAB组成复合物结构的差异.     

不同形貌钛酸钡纳米晶体的光催化性能研究

采用水热法,分别利用聚乙二醇200(PEG200)和乙醇的调控作用,合成了十二面体和立方块两种不同形貌的钛酸钡(BaTiO3,BTO)纳米晶体,两种晶体分别具有(110)和(100)不同的晶面.利用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)以及UV-Vis漫反射光谱对BTO纳米晶体进行表征分析,结果显示十二面体BTO纳米晶体具有较小的粒径,较大的表面活性;而立方块BTO纳米晶体具有较大的粒径,较小的表面活性.在相同条件下对甲基橙进行光催化降解实验,十二面体BTO纳米晶体显示出优于立方块BTO纳米晶体的催化性能.光催化动力学理论模拟结果进一步证实了上述实验结果.     

双模板剂体系下层状镁碱沸石的合成研究

通过直接水热合成法在吡咯烷和四甲基氢氧化铵双模板剂体系下制备出具有层状薄片组成的球形镁碱沸石,并且考察了四甲基氢氧化铵加入量对镁碱沸石的结晶度、晶化曲线、晶体形貌、比表面和孔结构的影响,采用X射线衍射(XRD)、扫描电镜(SEM)、氮气吸附脱附等手段对合成样品进行分析表征.结果表明:随着四甲基氢氧化铵加入量的增加,其晶化过程逐渐延长,但最终得到的镁碱沸石相对结晶度无明显变化;四甲基氢氧化铵的加入可以显著改变镁碱沸石的晶体形貌、比表面和孔结构.     

DAST晶体的表面形貌、缺陷及显微硬度研究

利用自行合成的4-(4-二甲基氨基苯乙烯基)甲基吡啶对甲基苯磺酸盐(DAST)原料,用斜板法生长出了一定尺寸的DAST晶体.用X射线衍射仪(XRD)对所得样品进行了表征,用光学显微镜观察了不同晶体(001)面的形貌特征并对其进行了分析,对不同腐蚀剂作用下的腐蚀坑的特点和成因进行了研究,测定了不同载荷下DAST晶体(001)面的显微硬度值.     

磷酸盐和不同价态的阳离子氯化物对石膏硬化体结构与性能的影响

以不同种类的磷酸盐(Na3PO4、Na5P3O10和(NaPO3)6)和不同价态的阳离子氯化物(NaCl、MgCl2、AlCl3)为添加剂,借助SEM等其他测试手段分析石膏硬化体的显微结构,研究半水石膏浆成型和石膏硬化体性能的变化.结果表明,氯化物无机盐中阳离子价态的升高对半水石膏浆的凝结时间无明显影响,但会引起石膏硬化体的吸水率显著提高,硬化体强度略有下降;加入磷酸盐后石膏浆的缓凝时间显著增长,石膏硬化体的吸水率下降,强度提高,其中以(NaPO3)6影响最为显著.当磷酸盐添加量达到0.12;时,硬化体性能趋于稳定,添加了(NaPO3)6和Na5P3O10的石膏硬化体结构中存在着较多柱状晶体.     

负离子配位多面体生长基元的理论模型与晶粒形貌

本文介绍了一种新的形貌判定准则--配位多面体生长习性法则.首先在负离子配位多面体生长基元模型的基础上建立了晶体的生长机理模型和界面模型,在此基础上提出了晶体形貌判定法则.即晶体的各晶面的生长速度与其结构中的配位多面体在界面上显露的元素种类有关.显露配位多面体顶点的晶面生长速度快,显露面的晶面生长速度慢,显露棱的晶面生长速度介于两者之间.此外,晶体的各晶面的生长速度还与配位多面体在界面上显露的元素数目有关.显露配位多面体元素数目多的晶面生长速度快.根据此法则成功地解释了γ-AlO(OH)晶体和极性晶体ZnO,SiO2的形貌特征.最后,本文还提出了两种晶体形貌的调制方法,即添加剂调制法和过饱和度调制法.成功地调制了ZnO晶体的形貌.     

不同形貌二水草酸钙晶体的合成、表征及其对肾上皮细胞的损伤作用

合成了4种不同形貌和尺寸的二水草酸钙(COD)晶体,分别为尺寸20μm的花状、10μm的十字形、2μm的四方双锥形和1μm的棒状COD晶体.采用X射线衍射、傅立叶变换红外光谱、扫描电子显微镜(SEM)和比表面测试仪对上述4个COD晶体的理化性质进行了表征.花状和十字形COD晶体都具有尖锐的棱角;棒状、四方双锥形COD都具有完整的(100)面.随着晶体尺寸的降低和晶体表面正电荷密度高的(100)面比例增大,其Zeta电位绝对值不断减小.不同形貌COD晶体均对非洲绿猴肾上皮细胞(Vero)具有毒性作用,其细胞毒性大小与多因素相关,包括晶体的尺寸、晶面、尖锐程度、比表面积以及Zeta电位等.本研究有助于进一步阐明尿微晶形貌差异影响肾结石形成的分子和细胞机制.     

Relationship of Morphological Types of Dynamic Forms of Crystals

Crystallography Reports - The relationship of morphological spectra (sets of data on the morphological types of real polyhedral crystals and their probabilities under current physicochemical...     

A review of measurement of thermophysical properties of silicon melt

Measurements of thermophysical properties of Si melt and supplementary study of X-ray scattering/diffraction by the authors' group were reviewed. The values obtained differed variously from those of literature. Density was 2–3% larger, surface tension 20–30% smaller, viscosity up to 40% larger, electrical conductivity 8% smaller, spectral emissivity more or less in good agreement with literature values, and thermal diffusivity a few percent larger. An anomalous density jump was found near the melting point. Surface tension and viscosity also showed anomaly. A strange time-dependent change of density was observed over 3 h after melting. X-ray analyses suggested a slight change in local atom ordering, but showed no sign of cluster formation. An addition of 0.1 at% gallium caused the density jump to disappear, while that of boron caused no change. An EXAFS study of the former melt indicated a strong interaction between Ga and Si atoms as if molecules of GaSi₃ existed. The implications of the measured properties are a possibility of soft-turbulence in an Si melt in a relatively large crucible, a more complicated manner of intake of oxygen depleted molten Si from the free surface region to underneath the growing crystal, and a relaxation of the melt after melting arising from trapped gas species.     

Generation of crystal structures of heteromolecular compounds by the method of discrete modeling of packings

Within the method of discrete modeling of packings, an algorithm of generation of possible crystal structures of heteromolecular compounds containing two or three molecules in the primitive unit cell, one of which has an arbitrary shape and the other (two others) has a shape close to spherical, is proposed. On the basis of this algorithm, a software package for personal computers is developed. This package has been approved for a number of compounds, investigated previously by X-ray diffraction analysis. The results of generation of structures of five compounds—four organic salts (with one or two spherical anions) and one solvate—are represented.     

Development of Pauling's concepts of geometric characteristics of atoms

The evolution of the geometric characteristics introduced by Pauling and their dependence on the specific features of the structure and chemical bonds have been considered. The values of the covalent and van der Waals radii are given as well as their relationships and mutual transitions.     

Velocities of Disappearance and Lifetime of Faces of Growing Crystals

The formulae for absolute R_disap and relative R velocities of disappearance and lifetime τ of faces of growing crystals have been derived for stationary growth. It was shown that the quantities are determined by the relative growth velocity R_A/R_critA of the vanishing face A with respect to the critical growth velocity R_critA and by the geometry of a crystal expressed by the trigonometric functions of interfacial angles β and γ formed between face A and the adjacent faces. R increases and τ decreases with the increase in R_A/R_critA to certain limiting values. The calculations have been verified and illustrated by the experimental results for triclinic potassium bichromate (KBC) crystals. Results enable ones to predict values of velocities of disappearance and lifetimes of undesirable, supplementary faces of any real crystal.     

Comparative analysis of two methods of calculation of the orientation of domain walls in ferroelastics

Two types of domain-wall equations are analyzed: the equations derived by the Sapriel method and the equations obtained by interface matching of the thermal-expansion tensor. It is shown that, for W-type domain walls, these methods yield the same equations. For W′-type domain walls, the equations obtained by different methods coincide for proper ferroelastics and differ for improper ferroelastics.     

Dependence of the parameters of equations of viscous flow on chemical composition of silicate melts

The temperature dependence of viscosity of silicate melts is discussed in the framework of the Avramov–Milchev (AM) equation. The composition is described by means of two parameters: the molar fraction, x, and the “lubricant fraction”, l. The molar fraction is the sum of the molar parts x_i of all oxides dissolved in SiO₂, the molar fraction of the latter being 1 ? x. It is shown that, with sufficient precision, two of the parameters of the AM equation can be presented as unique functions of the molar fraction. On the other hand, x is not sufficient to determine properly the reference temperature T_r , at which viscosity is η_r = 10¹³ [dPa.s]. Therefore, additional parameter, “lubricant fraction” l, is introduced. For each of the components, l_i is a product of molar part x_i and a specific dimensionless coefficient 0 ≤ k_i ≤ 1 accounting for the specific contribution of this component to the increased mobility of the system. It is demonstrated that, for l > 0, the reference temperature is related to the “lubricant fraction” l through the reference temperature T_r,SiO2 of pure SiO₂.     

Mechanism of thermal expansion of structural modifications of zinc pyrovanadate

Crystal chemical characteristics of the α and β modifications of Zn₂V₂O₇ are calculated based on in situ high-temperature X-ray measurements. The expansion of the structure is found to be strongly anisotropic up to the negative volumetric thermal expansion of the α-Zn₂V₂O₇ unit cell in the temperature range of 300–600°С, α _V =–17.94 × 10^–6 1/K. The transformations of the “hard” and “soft” sublattices with an increase temperature and at the phase transition are considered in detail. It is shown that the negative volumetric thermal expansion of α-Zn₂V₂O₇ is due to the degeneracy of the zigzag-like shape of zinc–oxygen columns at constant distances between their vertices.