磺基水杨酸锶分光晶体生长的研究

本文采用液相法合成了高纯度磺基水杨酸锶(简称SSS)多晶粉末原料,并采用热分析、红外光谱和XRD分析对多晶粉末原料进行表征。以水为溶剂分别在不同pH值下(pH=2.50、1.50和0.60)进行了SSS结晶习性实验。结果表明,在水溶液中当pH=0.60时SSS结晶性最好,实验还测定了SSS晶体在不同pH值溶液中的溶解度曲线,并进行了过饱和溶液成核机理的研究。研究结果表明,当生长溶液pH为0.60时,控制单晶生长温度在40～50℃区间,采用水溶液降温法可生长出63 mm×25 mm×3 mm的透明单晶。     

pH值对KDP晶体溶解度和溶液稳定性的影响

测定了不同pH值(2.0～5.5)生长溶液中KDP晶体(KH2PO4)的溶解度曲线,实验结果表明:随着生长溶液pH值的改变,KDP溶解度明显增大.讨论了KDP晶体溶液pH值、溶液组成和溶液饱和点温度三者之间的关系.进行了高pH值(3.8～5.6)KDP生长溶液的稳定性实验,发现高pH值生长溶液中的临界成核半径rC增大,溶液的稳定性提高.在不同pH值溶液中进行了晶体生长实验,探讨了不同pH值生长溶液中配合物对KDP晶体生长习性的影响.     

K2SO4/KCl添加剂对脱硫石膏晶须结晶的影响

以提纯后的脱硫石膏为原料,分别以K2 SO4和KCl为添加剂,采用水热法制备了脱硫石膏晶须,研究了添加剂用量对晶须显微结构、长径比和溶液组成的影响,并探讨了其作用机理.研究结果表明:添加剂用量对晶须形貌影响较大,但并不影响其物相组成;当K2SO4、KCl用量分别为3;和5;时,制备的晶须结晶良好,长径比分别达80和50.加入K2SO4后,脱硫石膏在反应溶液中的溶解度减小,而加入KCl,其溶解度增大.强电解质离子K+的加入,促使晶须延c轴生长,从而使其长径比增大.     

点状籽晶法生长KDP晶体中散射颗粒分布

在不同的溶液pH值条件下进行了点状籽晶法慢速和快速生长KDP晶体实验,发展了观察晶体中散射颗粒分布的激光层析技术,通过图像处理得到了KDP晶体内部(100)面完整的散射颗粒分部图,对不同生长速度、不同pH值条件下点状籽晶法生长的KDP晶体的散射颗粒分部做了对比.利用表面光学投影技术观察了晶体表面宏观形貌,并由此分析了不同生长条件下生长机制对散射颗粒分布的影响.测定了散射颗粒密度不同部位的晶体透过率.     

不同pH值下ZTS晶体(100)面台阶生长动力学规律和位错缺陷的研究

通过利用光学显微镜,对不同pH值下ZTS晶体(100)面的台阶推移过程进行了实时观察,发现在同一过饱和度下,调高生长溶液的pH值会导致台阶推移速率降低;而调低pH值时,台阶的平均推移速率增大,当pH =4.2时,(100)面生长速度最快.计算出不同pH值下的台阶动力学系数βl和台阶活化能E的数值.对不同pH值下生长出的ZTS晶体的(100)面进行了位错缺陷观察,发现pH =4.2时,位错密度较低,有利于晶体生长质量的提高.     

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.     

ZnWO4纳米晶光催化剂的制备及表征

以Na2WO4·2H2O和Zn(NO3)2·6H2O为原料,采用水热法制备出ZnWO4纳米晶催化剂.以曙红B为目标降解物,研究了ZnWO4催化剂的光催化性能,探讨了水热温度、水热时间和水热溶液pH值对ZnWO4催化剂的结晶形态及光催化活性的影响规律,结果表明:在酸性条件下制备的ZnWO4为片状结构,链状分布,而在碱性条件下为棒状结构.在180 ℃,24 h的制备条件下,ZnWO4催化剂显示出最高的光催化活性.水热溶液pH=5和pH=8时制得的催化剂在2 h内对5 mg/L的曙红B溶液的脱色率分别达到86;和95;.制备过程中溶液的pH值,催化剂的晶态和比表面积是影响催化剂活性的重要因素.     

CdHg(SCN)4晶体的结构和光学性质的理论研究

采用密度泛函理论(DFT)和赝势方法,研究CdHg(SCN)4(CMTC)的晶体结构、电子结构和光学性质.计算结果表明:优化后的晶体晶格常数与实验值基本一致,CMTC晶体以-Cd-N=C=S-Hg-为链形成的无限三维网络结构具有较强的稳定性;能带结构具有明显的直接带隙结构,用LDA+U方法计算CMTC晶体带隙为3.223 eV,与实验值3.265 eV相接近;键合性质的计算显示S-C和C-N键具有明显的共价性,而Cd-N和Hg-S键具有明显的离子性.依据阴离子基团理论,计算了CMTC晶体的倍频系数,CMTC晶体倍频系数的计算值(d14=1.58～ 1.74 pm/V,d15=5.77～7.69 pm/V)与实验值(d14=1.4 ±0.6 pm/V,d15 =6.0 ±0.9 pm/V)基本一致,研究发现CMTC晶体的非线性光学效应主要来自于多面体Cd (NCS)4和Hg (SCN)4基团.     

前驱液pH值对2ZnO·2.2B2O3·3H2O∶Eu3+荧光粉发光性能的影响

采用水热法,通过氨水调节前驱液的pH值,制备了一系列2ZnO.2.2B2O3.3H2O∶Eu3+样品。对所制备的样品进行X射线衍射和荧光光谱分析。研究结果表明:前驱液的pH值影响2ZnO.2.2B2O3.3H2O的结晶程度,在中性条件下制备的样品结晶度最好。当前驱液的pH=5.7时,激发光谱中的Eu-O电荷迁移带的峰位波长最大(262 nm),这可能是由于在此条件下合成的样品中Eu-O键长最长。发射光谱表明:当前驱液的pH>5.7时,Eu3+的发射光谱中的红橙比(I614/I589)随pH值的增大而增大,且当前驱液的pH值在5.7～6.9区间,红橙比(I614/I589)随pH值的增大的速率要比pH值在6.9～9.3之间增加的速率要快。另外,随着pH值的增大,样品的发光强度呈先增大后减小的变化趋势。当前驱溶液pH=8.1时,样品的发光强度最大。     

KDP晶体的点状籽晶法生长及其缺陷研究

研究了溶液Ph值对KDP晶体生长形态的影响,进行了晶体生长实验和参数对比.以提高溶液Ph值为主要手段在低过饱和度下进行KDP晶体点状生长.对点状法生长的晶体进行了缺陷分析,测定了晶体不同区域的金属离子含量并进行了对比分析.实验表明溶液Ph值对晶体各向的相对生长速度有显著的影响.在Ph=5.0、低过饱和度(σ＜0.02)条件下生长出50×50×50mm3的晶体.     

Investigation on the Aqueous Solution for Growth of Bimetallic Thiocyanate Complex Crystal Materials

The stability of cadmium mercury thiocyanate (CMTC) crystal growth solution was mainly discussed. The effects of temperature, pH value, time and KCl concentration on CMTC crystal growth were investigated. The effects of pH value and KCl concentration on crystallization habit of CMTC were also studied. The results show that when pH value ranges from 2.5 to 3.8, the solution is relatively stable, under the condition of pH ≤ 2.0 or pH ≥ 4.0, the solution has poor stability and some powder appears. The solution becomes unstable at high temperatures. When the concentration of KCl is more than 27% there has not generated CMTC crystal in the solution, a new kind of material produced from solution. The pH value and KCl concentration affect crystalline morphology of CMTC crystal.     

Growth of cadmium mercury thiocyanate dimethylsulphoxide single crystal for laser frequency doubling

This paper reports the growth of an organometallic nonlinear optical (NLO) complex crystal, Cadmium mercury thiocyanate dimethyl-sulphoxide (CdHg(SCN)₄(H₆CP₂OS)₂, CMTD), which was grown from aqueous solution by a temperature lowering method. Its powder SHG intensity is higher than that of CMTC. The crystal size of CMTD can reach 25×23×15mm³. The solubility curve, and solubility variation with pH value are also reported. The growth habits of crystals of CMTD grown under different conditions are discussed and the optimized condition for the growth CMTD using a temperature-lowering method from aqueous solution are also discussed.     

Growth of cadmium mercury thiocyanate single crystals using acetone–water mixed solvent and their characterization studies

Cadmium mercury tetrathiocyanate single crystals were grown from acetone–water (4:1) mixed solvent by slow evaporation solution technique. The structure of the grown crystal was confirmed by single-crystal X-ray diffraction analysis. The crystalline perfection of cadmium mercury thiocyanate (CMTC) was ascertained by high-resolution X-ray diffraction (HRXRD) analysis. The presence of functional groups and the coordination of thiocyanate ion in the CMTC compound were confirmed by laser Raman spectroscopy. The optical transparency of CMTC single crystal was studied by UV–vis spectroscopy. Single-shot surface laser damage threshold of CMTC estimated using an Nd-YAG laser of wavelength 1064 nm was found to be 4.59 GW/cm² and second harmonic generation (SHG) output power was estimated through the Kurtz powder method. Dielectric constant and dielectric loss for various frequencies and temperatures were performed on CMTC single crystal.     

Atomic force microscopy studies on liquid inclusions and induced defects of cadmium mercury thiocyanate crystal

Liquid inclusions and various defects accordingly induced on a nonlinear optical material of CMTC crystal were investigated by atomic force microscopy. Liquid inclusions are chiefly caused by formation of macrosteps, which result from impurity‐induced inhibiting of step growth and meeting of step trains advancing along different directions. Liquid inclusions induce generation of dislocations and even cracks within the crystal by three‐dimensional nucleation growth. Liquid inclusions also provide screw dislocation growth sources, leading to formation of spiral hillock trains with ridged tails. Etching experiments reveal circular hollow cores, indicative of screw dislocation growth, and negative crystals resulting from further crystallization in the liquid inclusions. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

提拉法生长镓酸锂晶体及缺陷研究

研究了提拉法生长的镓酸锂单晶的生长习性和结晶质量.晶体表面呈乳白色且表面粗糙.通过光学显微镜、四晶X射线衍射、透射光谱和电感耦合等离子体发射光谱对样品进行了表征,结果表明,在(001)面的抛光样品上存在三种缺陷: [110]和[-110]方向的十字线、[010]方向排列的气泡包裹物以及平行于(010)面的界面,界面的产生起因于(010)晶面的滑移;晶体的结晶质量从顶部到底部逐渐下降,这是由于在生长过程中氧化锂的挥发导致熔体成分偏离化学计量比造成的.     

Effects of pH and temperature on CaCO3 crystallization in aqueous solution with water soluble matrix of pearls

Water soluble matrix (WSM) was extracted from pearls originated from Hyriopsis cumingii in Zhuji, Zhejiang province, China. WSM was regarded as an additive in mineralization experiments in order to study the effect of WSM on CaCO₃ crystallization. The experiments were carried out at different pH and temperatures by gas diffusion method and solution titration method, respectively. Scanning electron microscopy (SEM) and Raman spectroscopy (Raman) were used as powerful techniques to analyze the co-effect of pH value, temperature and WSM on crystal growth of CaCO₃. The results showed that WSM could induce aragonite at different pH values of mineralization solution, and the pH value had remarkable influence on morphology of calcite rather than aragonite due to distinct supersaturation and ionic strength related to various pH values. At different solution temperatures, WSM had little effect on crystal growth of calcium carbonate while the solution temperature had notable effect on polymorph and morphology of CaCO₃ crystals. This work can provide some basic information for the polymorph and morphology control of calcium carbonate.     

Growth morphology of {100} faces of L‐Arginine phosphate monohydrate single crystals investigated by atomic force microscopy

Morphology of the {100} faces of L‐arginine phosphate monohydrate (LAP) single crystal grown at 25 °C at a supersaturation of 0.32 has been discussed. The rectangular dislocation growth hillocks elongate along the b direction, which manifests the fast growth due to the strong Period Bond Chain (PBC) bonds along this direction. Apart from that, the growth hillocks are consistent with the macro‐morphology of the crystal grown at the pH value of about 4.2. The lopsided shapes of the hillocks result from step bunching. Triangular pits are assumed to form during the process of the steps getting across the impurities. The hollow cavities existing on the growth hillocks also elongate along the b direction and they can lead to the formation of other defects such as dislocations. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth of equiaxed dendritic crystals settling in an undercooled melt,Part 1: Tip kinetics

Experiments are conducted to measure the dendrite tip growth velocities of equiaxed crystals of the transparent model alloy succinonitrile–acetone that are settling in an undercooled melt. The tip velocities are measured as a function of the crystal settling speed and the Eulerian angle between the dendrite arms and the flow direction relative to the crystal. The ratio of the settling speed (or flow velocity) to the tip growth velocity ranges from 62 to 572. The ratio of the measured tip velocity to that predicted from a standard diffusion theory for free dendritic growth ranges from almost zero for dendrite tips growing in the wake of the crystal, about unity for dendrite tips with an orientation close to normal to the flow direction, and up to two for dendrite tips growing into the flow. Despite the relatively strong flow relative to the crystal, the average tip growth velocity of the six primary dendrite arms of an equiaxed crystal is found to be in excellent agreement with the standard diffusion theory result. The individual tip velocities are correlated using a boundary layer model of free dendritic growth in the presence of melt flow that is modified to account for the flow angle dependence. Using the same dendrite tip selection parameter, σ^*, as established previously under purely diffusive conditions (0.02), good agreement is achieved between the measured and predicted tip velocities. The model is also found to predict well the variations in the tip velocity that occur during settling due to crystal rotation and settling speed changes.     

Solubility and crystallization of BaHPO4 crystals

A study of growth of barium hydrogen phosphate (BaHPO₄) crystal from solution is reported. The raw materials of barium hydrogen phosphate were successfully synthesized through chemical reaction in water. The solubility in HCl and H₃PO₄ solution were studied. It increased when acid concentration and temperature become higher, and the fitted curve of solubility is nearly a line. The acid concentration affects crystalline morphology of BaHPO₄ crystal. The crystallization is well when the acid solution ranges from 0.5 to 0.8M. © 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

Growth rate of single acetaminophen crystals in supersaturated aqueous solution under different operating conditions

Single crystal growth experiments were conducted to investigate the growth rate of acetaminophen (paracetamol) crystals under carefully controlled conditions of temperature, supersaturation and pH value. The relative growth rate of the different faces was studied. Growth Rate Dispersion (GRD) was observed by studying the effect of supersaturation and temperature on the growth rate. The growth rate in all directions was found to be temperature dependant. Elongation of the crystals was measured due to the faster growth in the Y‐ direction and Xa direction compared to in the Xb direction. Dissolution of the crystals was observed at pH values greater than 8.5, and a growth rate retardation was observed when increasing the pH from 5.6, which is the normal value without additions, to higher values in both acidic and basic mediums up to 8.5. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)