KAl(SO4)2·12H2O晶体聚集体形貌及结晶学规律

采用双玻片凝胶法得到了等轴晶系水溶性晶体KAl(So4)2·12H2O(钾明矾)的晶体聚集体形貌.通过光学显微镜和扫描电镜下的形貌观察和分析,根据结晶学和晶体形貌学的基本原理,探讨了该晶体聚集体形貌中蕴含的结晶学规律.钾明矾晶体发育单形{111},以{100}贴在载玻片上生长,形成聚集体形貌时,晶粒{111}以平行连生的方式形成“十字形”枝晶或柱状枝晶,以(320)或(230)为共格晶界形成“Z”形枝状形貌.     

Di-Ab-An体系远离平衡枝状形貌的演化及枝体结晶学各向异性特征研究

对钠长石(Ab)-钙长石(An)-透辉石(Di)三元体系跨相界线的不同成分点在不同的降温速度条件下快速结晶形成的枝状形貌进行了研究.透辉石为枝晶,斜长石为球粒晶.当降温速度慢于1℃/min后,枝状形貌变为板-柱状形貌(即近平衡形貌).我们的实验结果中没有观察到如E.Brener 和H.Muller等人提出的形貌演化图一样的演化规律.当成分点靠近同结线后,出现两晶共结形成的"中空结构".通过光学显微镜下测试其光学性质发现,透辉石沿c轴方向延长,斜长石沿a轴延长,与晶体结构中的强键链方向一致,即快速结晶时晶体沿着结构中负离子配位多面体共角顶、共棱形成的强键链方向生长形成枝体.     

Di-Ab-An、Q-Lc体系非平衡结晶及枝晶结晶学方向测试研究

本文对两个典型的硅酸盐体系:Di(透辉石)-Ab(钠长石)-An(钙长石)体系和Q(石英)-Lc(白榴石)体中结晶物相系进行了枝状形貌、枝体结晶学方向测试及结晶能力方面的研究.通过偏光显微镜(PL)、扫描电镜(SEM)观察发现:透辉石、低鳞石英、α-方石英都发育为枝晶,而斜长石发育成放射状球粒晶和针状晶体.通过电子背散射衍射(EBSD)测试确定出透辉石是沿<001>方向发育成枝晶的主干、低鳞石英是沿<100>和<010>方向发育成枝晶主干、α-方石英是沿两个<100>方向发育成枝晶的主干.并发现两个体系在相同降温速度下的结晶能力不同.     

CuCl2·2H2O晶体聚集体形貌及晶体模型的建立

本文通过斜方晶系水溶性晶体CuCl2·2H2O的生长实验,得到了晶体聚集体,观察了结晶形貌,探讨了该晶体聚集体形貌中蕴含的结晶学规律,建立了该晶体在理想情况下的聚集体的结晶学模型.在该模型中,晶体生长方向为[001],发育晶面为(100)、(010)和(110),形成聚集体形貌时晶体结合的共格晶界分别为(012)与(0 10 1)、(103)与(120 1)和(112)与(991)或(113)与(1313 1).试验观察验证了模型的正确性.     

CuCl枝晶与单质Cu枝晶的生长与枝晶形貌结晶学分析

以锌粉和氯化亚铜为原料,采用水热法,制备了单质Cu枝晶与CuCl枝晶.利用X-射线衍射仪(XRD)、能谱仪(EDS)和扫描电子显微镜(SEM),对枝晶产物和生长机理进行了表征.结果表明:单质Cu枝晶多为黄色具有金属光泽的三维树枝状结构,也可见二维枝状结构;CuCl枝晶为白色二维叶片状结构.尽管CuCl叶片在整体的外形上略有不同,但结晶学特征是相同的,都可以观察到明显的主干,在主干的两侧均有侧枝,且侧枝与主干之间呈60°夹角关系,同侧的侧枝之间彼此平行排列.通过对叶片状枝晶的结晶学规律的分析发现:CuCl枝晶的主干是由四面体单体沿[121]方向以平行连生方式形成,侧枝是四面体单体分别沿[211]和[112]平行连生而成.     

Cu2+在晶体K2Cd(SO4)2·6H2O中的电子顺磁共振参量及局部结构的理论研究

在晶体场理论的基础上,由重叠模型建立了杂质中心结构参数与电子顺磁共振(EPR)参量之间的定量关系;利用3d9离子正交(D2h)伸长八面体对称EPR参量的高阶微扰公式计算了K2Cd(SO4)2·6H2O∶Cu2+的g因子gi(i=x,y,z)和超精细结构常数Ai.研究表明,K2Cd(SO4)2·6H2O晶体中络离子[Cu(H2O)6]2+的Cu2-H2O键长分别为Rx≈0.181 nm,Ry≈0.199 nm,Rz≈0.232 nm,局域结构为沿C4轴方向呈正交伸长八面体(D2h)结构.所得EPR参量理论计算与实验符合较好,并对上述结果进行了讨论.     

NaCl枝状形貌的制备及生长机理探讨

采用溶剂蒸发法,在不同的条件下分别获得了具有四次对称和二次对称的Na Cl枝晶、"Z"字形枝蔓晶以及主要由枝晶呈放射状分布的球粒晶。借助于X射线衍射仪、光学显微镜、扫描电镜以及电子背散射衍射仪(EBSD),对Na Cl枝状形貌进行了测试分析。结果表明,Na Cl球粒晶主要由主干沿着<111>方向生长的一系列枝晶组成。Na Cl晶体(111)面网由同号离子组成,且钠离子层与氯离子层相间分布,层与层之间的联结力强,且(111)的面网间距最小,是导致Na Cl枝晶优先沿<111>方向生长的主要原因。溶剂的蒸发速度等环境因素的变化对Na Cl枝状形貌的形成具有很大的影响。     

LiRb5(SO4)3·1.5H2SO4晶体铁弹相变的研究

本文利用慢度曲面法研究LRSHS晶体的铁弹相变.画出了LRSHS晶体在发生铁弹相变过程中一些温度下的慢度曲面图,得到了最大慢度.研究结果表明:晶体在三维空间的慢度最大值方向就是发生本征铁弹相变的方向,即声学软模软化的方向.确定出声学模的软化方向,即可确定出发生本征铁弹相变时软化显著的弹性劲度系数,再利用居里原理即可得到晶体铁弹相的对称性.     

Ca(H2PO4)2-H3PO4-K2SO4体系中石膏晶型及形貌调控

为将Ca(H₂PO₄)₂制备KH₂PO₄过程中的石膏资源化利用,以H₃PO₄与CaCO₃反应制备Ca(H₂PO₄)₂溶液,并与K₂SO₄溶液反应,进行Ca(H₂PO₄)₂-H₃PO₄-K₂SO₄体系中石膏晶型和形貌调控研究。结果表明:通过改变反应时间、反应温度、SO^2-₄过量系数和CaO含量等参数可对Ca(H₂PO₄)₂-H₃PO₄-K₂SO₄体系中石膏晶型和形貌进行调控,制得短柱状α-CaSO₄·0.5H₂O。体系在温度高于95 ℃和CaO含量为3.0%~5.0%(质量分数,下同)时形成α-CaSO₄·0.5H₂O,在CaO含量为5.5%主要形成CaSO₄·2H₂O;反应时间长于20 min和SO^2-₄过量系数大于1.4将形成K₂SO₄(CaSO₄)₅·H₂O,导致石膏晶体表面缺陷增加。本实验条件下,适宜反应条件为:反应时间10 min、反应温度95 ℃、SO^2-₄过量系数1.2和CaO含量5.0%,此条件下可制得长度42~70 μm、直径13~24 μm的短柱状α-CaSO₄·0.5H₂O,其抗折和抗压强度分别可达5.61 MPa和33.74 MPa,滤液中钾收率和脱钙率分别可达94.23%和83.80%。     

Ni(C6H12N4)2SO4·4H2O晶体的生长、热学和光谱性质

六次甲基四胺(C6H12N4,HMTA)部分取代六水合硫酸镍(NSH)晶体结构中的配位水,合成Ni(C6H12N4)2SO4·4H2O(NSH-HMTA)晶体材料.采用称量法测定了NSH-HMTA晶体的溶解度曲线,应用水溶液降温法在温度区间56 ～44℃之间生长出6 mm×6 mm×2 mm尺寸的晶体,生长速度约为0.5 mm/d.通过等离子发射光谱分析所生长晶体中镍离子含量,X射线单晶衍射用于验证晶体的结构.采用热重法(TGA)和差热分析法(DTA)测定晶体脱水温度和分解温度分别为93℃、1 14℃.测量晶体的紫外-可见光谱特性,其紫外波段透过峰位于波长为307 nm处,比NSH晶体(287 nm)红移了约20 nm,HMTA与Ni2+配位提高了Ni2+的3A2g光谱项的能级,3A2g→3T1g(P)所需能量更低,导致吸收谱红移.     

Piezo-optic properties of K2SO4 crystals

The effect of uniaxial stresses applied along the principal crystallographic directions on the dispersion and temperature dependences of birefringence of K₂SO₄ crystals is studied. The birefringence is found to be sensitive to uniaxial stresses. The spectral and temperature dependences of the combined and absolute piezo-optic coefficients of these crystals are investigated. Their significant anomalies are observed at the ferroelectric phase transition. They are caused by the change in the induced birefringence due to the occurrence of spontaneous deformation. The contributions of the electro-optic and elasto-optic effects to the spontaneous variations in the piezo-optic constants are separated.     

The Characteristics of the Mixed Crystals of the K2SO4-(NH4)2SO4-H2O System at 298 K

Equilibrium studies of the K₂SO₄-(NH₄)₂SO₄-H₂O system at 298 K have been conducted. The isotherm of solubility and the curve of distribution have been mathematically described. The parameters of the crystal lattice and the enthalpy of crystallization of the [K_x(NH₄)_1-x]₂SO₄ solid solutions as a function of their composition have been presented.     

硫酸钾枝状晶的生长与EBSD测定

采用单玻片溶液蒸发法、双玻片溶液蒸发法以及凝胶法,在不同条件下分别获得了硫酸钾枝晶和枝蔓晶,并利用EBSD技术对硫酸钾枝晶和枝蔓晶的结晶学取向进行了测试和分析.研究表明:硫酸钾(K2SO4)枝晶的主干主要沿着＜ 111＞方向生长;而硫酸钾(K2SO4)枝蔓晶中,组成枝蔓晶的相邻枝晶(晶粒)之间存在典型的双晶关系,其双晶轴为＜011＞,双晶面为(053).     

X-Ray Radiography Investigations of Solid Solutions with Limited Miscibility in K2SO4-(NH4)2SO4-H2O System

The measurements of crystal lattice parameters (a, b, c) were conducted and the volumes (v) and densities (∂) of solid solutions of (K, NH₄)₂SO₄ were calculated. It was established that in the system K₂SO₄-(NH₄)₂SO₄-H₂O at 25 °C mixed crystals with limited miscibility were formed. The gap in the continuity of solid solutions occurred in a very narrow range of concentrations of (NH₄)₂SO₄ in mixed crystals, namely from 69.5 to 72.5%. In order to get the confirmation of the above, the detailed equilibrium investigations nearby the peritonic point (the concentration of K₂SO₄ −3.32%, the concentration of (NH₄)₂SO₄ −38.66%) were carried out.     

Refractive and Photoelastic Properties of K2SO4 Crystals Doped with Copper

Crystallography Reports - The spectral dependences (in the range of 300–700 nm) of the refractive indices and birefringence of K2SO4 crystals doped with copper (1.7 and 3.0 wt %) have been...     

The growth of single crystals of langbeinites Rb2Cd2(SO4)3, Tl2Cd2(SO4)3, K2Co2(SO4)3, and their phase transitions

Single crystals of dicadmium dirubidium sulphate and dicadmium dithallium sulphate have been grown from non-stoichiometric aqueous solutions by various methods. Optical and thermal properties in the vicinity of their phase transitions have been studied. Polycrystalline samples of dicobalt dipotassium sulphate have been prepared using Bridgman method. Optical and specific heat measurements have shown a new phase transition at −148°C.     

Crystalloluminescence and Mechanoluminescence Spectra of Ba(ClO3)2 · H2O and 2 K2SO4 · Na2SO4 Crystals

Crystalloluminescence and mechanoluminescence of Ba(ClO₃)₂ · H₂O and 2 K₂SO₄ · Na₂SO₄ crystals are investigated. The crystalloluminescence spectra are almost similar to the photoluminescence spectra; however, they differ completely from the mechanoluminescence spectra. The crystalloluminescence excitations may take place due to the various processes: (i) the recombination of ions, (ii) from amorphous to crystalline transition, (iii) from the phase change during the crystallization, and (iv) from the dielectric breakdown by the electric field produced due to the creation of microfracture during the crystal growth. It is concluded that the crystalloluminescence excitation in Ba(ClO₃)₂ · H₂O and 2K₂SO₄ · Na₂SO₄ crystals may be chemical in origin.