KDP晶体的高温热行为及其热脱水反应动力学研究

采用热重(TG-DTA)、定压比热(Cp)和原位高温红外反射光谱等热分析手段研究了四方相KDP晶体室温至260℃之间的高温热行为.实验发现:KDP晶体在183℃附近并未发生四方相到单斜相的相变或发生脱水反应;且晶体于207 ～ 210℃左右开始分解,随温度上升,分解过程分为三个阶段.第一个分解阶段出现P2O72-基团的吸收峰,意味着第一阶段的分解朝着K4P2O7的方向进行;第二阶段是第一阶段产生的中间态产物继续分解的过程;第三个分解阶段为前两个过程的继续分解,最终KDP完全分解为KPO3.通过Kissinger法,根据热重数据计算了KDP在260℃前两个明显的分解过程的动力学参数,其热脱水活化能分别为101.7 J·mol-1和112.4 J·mol-1.     

掺铒硼酸钙镧晶体的合成、生长及光谱特性

本文合成并以CaO-L i2O-B2O3为助熔剂体系生长得到了掺铒硼酸钙镧(Er3 :La2CaB10O19,Er:LCB)的晶体。X射线粉末衍射分析表明,Er:LCB和LCB具有相同的晶体结构,均属于单斜晶系,C2空间群。Er:LCB晶体的熔点大约为1048℃。测试了Er:LCB晶体的吸收光谱和荧光光谱。Er:LCB晶体在790nm和970nm附近存在的吸收,对应于A lGaAs和InGaAs激光二极管输出波长,其吸收截面分别为1.94×10-20和2.39×10-20cm2。Er:LCB在1531nm附近有发射峰最强,峰宽为16nm。其荧光寿命为0.37m s。     

新型非线性光学晶体硼酸铯锂的研究

本文用顶部籽晶泡生法生长了新型非线性晶体--硼酸铯锂(CLBO).获得了40mm的透明晶体,用非定向的CLBO晶体,初步获得二倍频转换效率η＝37;,获得335nm的激光输出1.3mJ.     

硼酸钾锶晶体的高温溶液法生长研究

以摩尔比为3∶1的NaF和H3 BO3为复合助熔剂,采用高温溶液法生长出了尺寸达7×4 ×3 mm3的较透明的KSr4B3O9单晶,并探讨了生长KSr4B3O9晶体助熔剂体系的选择.该晶体属正交晶系,空间群为Ama2,晶胞参数为:a=109.87(2) nm,b =119.48(2) nm,c =68.865(2) nm.该晶体结构是由KO10基团,SrOx(x=8,9)基团和独立的BO3三角形相互连接构成的三维网络结构;UV-Vis-NIR漫反射光谱说明KSr4B3O9化合物在紫外区230 nm左右才表现为全吸收;粉末倍频测试结果表明该化合物总的倍频效应与KH2PO4 (KDP)相当.     

紫外非线性光学晶体三硼酸铯的生长和性能

采用泡生法和提拉法生长出三硼酸铯(化学式CsB3O5,简称CBO)晶体,研究了晶体生长工艺条件及晶体生长形态.泡生法生长的CBO晶体的尺寸为40mm×25mm×25mm;生长过程中晶体转速为10～20r/min,降温速率为0.1～0.2℃/d.用提拉法生长出20mm×30mm的CBO晶体;生长过程中液面温度梯度为60℃/cm,提拉速度为8mm/d.在生长过程中Cs2O的挥发速度大于B2O3的挥发速度.CBO单晶的晶面由[011]斜方柱和[010]斜方柱单形组成,属于[011]单形是4个较大的面,属于[101]单形是4个较小的三角形晶面.CBO在紫外波段具有较大的有效非线性光学系数.利用CBO进行Nd∶YAG激光和频获得了高转换率的波长355nm及266nm相干光输出.     

Halogen Form in Calcium Borate Glasses Containing Iron

Some halogen-doped calcium borate glasses containing iron have been prepared according to the precentage molar composition [(30-X)CaO · xCaX₂ · 10 Fe₂O₃ · 60 B₂O₃)] and annealed. Scanning electron micrographs of heat-treated glasses show that the microstructure consists essentially of two phases. By introducing the halogen ion one of the primary phases (Ca-rich borate) decreases in its volume and a new phase appears and exists as crystalline form. A secondary phase can also be produced which segregates in Ca-rich borate as droplets. Magnetic susceptibility, molar volume, and infrared measurements revealed that at concentrations of CaX₂ < 10 mol% the halide ions may be introduced as modifiers and as network formers at CaX₂ concentrations > 10 mol%.     

Effect of Halide Ions on the Electronic Conductivity in Calcium Borate Glasses

Some halogen-doped calcium borate glasses containing iron have been prepared according to the percentage molar composition [(30 – x) CaO · x CaX₂ · 10 Fe₂O₃ · 60 B₂O₃] and annealed. It is found that the conduction in the semiconducting glasses is mainly due to electronic conduction. The results show that the halide ions may be introduced as modifiers for CaX₂ concentration < 10 mol% (X >= F, Cl, and Br) but they are network formers at CaX₂ > 10 mol%. It is proposed that at 10 mol% the network structure for all glasses seems to be the same. The dependence of resistivity on the halide ions concentration as well as the slight variation of activation energies, could be explained on the basis of electron-lattice interaction. Mathematical expressions for fitting and describing the dependence of resistivity on CaX₂ concentration are deduced and formulated by the following equations: ϱ = ϱ₀ exp [± ac(1 – bc)] and ϱ ϱ= ±₁₀ exp [± a′c(1 – b′c)] for the two regions around the critical concentration.     

硼酸钙对电瓷结构和性能的影响

研究了硼酸钙掺量对电瓷的相结构、显微结构、电气性能和机械性能的影响.通过不同硼酸钙添加量的电瓷在不同烧结温度条件下的断裂强度、气孔率、电阻率,结合电瓷的晶相结构和显微结构的变化,探讨其构效关系.结果表明:硼酸钙含量的增加或烧结温度升高,电瓷的电阻率和气孔率降低.但当硼酸钙掺量超过10;,烧结温度超过1120℃之后,电阻率和气孔率的变化不明显.电瓷的断裂强度随着硼酸钙的添加而提高,当硼酸钙含量超过10;后开始降低,添加量为10;时电瓷的断裂强度随着烧结温度而提高,1120℃后无显著变化.硼酸钙促进莫来石相的析出,但硼酸钙含量过高时,会促进CaAl2Si2O8形成,降低莫来石相的析出量,并使其形貌从细针状向短柱状和粒状发生转变.硼酸钙掺量恒定时,提高烧结温度可促进细针状莫来石相的生成.     

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.     

几种形貌硼酸钙的微波水热合成与表征

以硼酸、无水氯化钙、氢氧化钠为原料,通过添加不同类型的修饰剂及采取前期预置的措施,在微波水热条件下可控制备了纳米片状和由纳米片自组装的球状花、灯笼状的CaO·3B2O3·4H2O型硼酸钙,以及由纳米颗粒自组装的棒状的CaO·3B2O3·5H2O型硼酸钙.通过组成分析、X射线粉末衍射(XRD)、热重分析(TG-DTA)、扫描电子显微镜(SEM)等手段对产物的结构、性质和形貌进行了表征.结果表明,在320℃时,添加10wt;不同形貌的硼酸钙CaO·3B2O3·4H2O可使木粉的残重率比未添加硼酸钙的提高28; ～ 32;,说明硼酸钙纳米结构具有良好的阻燃性.     

Dielectric Properties of Beta Barium Borate and Potassium Pentaborate Single Crystals

Single crystals of beta barium borate and potassium pentaborate (commonly known as β-BaB₂O₄ or BBO and KB₅O₈. 4 H₂O or KB5) were grown by high and low temperature solution growth methods, respectively. The dielectric constant and loss tangent were determined as a function of temperature. Frequency response of the dielectric constant and tan δ have been studied over a frequency range of 0.1 −100 kHz; it is found that both the dielectric constant and tan δ decrease with increase in frequency for both crystals. The dielectric constant and tan δ are found to increase with increase in temperature for both the crystals. Further, the dielectric constant and tan δ measured on different orientations of the grown crystals reveal the anisotropic nature of the crystals.     

A New Calcium Oxalate Monohydrate Produced by Thermal Dehydration of Weddellite

A high temperature-Guinier photograph of weddellite power showed at 118 °C a transition to a so far unknown phase which transformed to β-Ca(COO)₂ at 135 °C and during cooling down to whewellite at 103 °C. X-ray diffraction studies on single crystals revealed the new phase to have an orthorhombic symmetry with the lattice constant a = 12.088 Å, b = 10.112 Å, c = 14.634 Å, α = β = γ = 90°. There are very simple orientation relations to weddellite: a₁ (wed) ∥ a (new phase), a₂ (wed) ∥ b (new phase), c (wed) ∥ c (new phase). DTA/TG studies showed that the new phase is a calcium oxalate monohydrate.