水热条件对溶胶-水热法合成PZT陶瓷粉体的影响

采用溶胶-水热法,合成了具有单一钙钛矿结构的PbZr1-xTixO3反铁电陶瓷粉体,探讨了水热反应温度和反应时间对PZT粉体的结晶过程、晶体结构、微观形貌等的影响.实验发现,随着水热反应温度的升高或者水热反应时间的延长,溶胶-水热反应的产物由非晶态向晶态逐步过渡.当水热反应温度达到180 ℃,反应时间高于18 h时,合成了立方形貌、结晶良好且具有钙钛矿结构的PZT陶瓷粉体.继续升高水热反应温度或者延长水热反应时间,PZT陶瓷粉体XRD衍射峰的峰强增强,峰位不变.但进一步升高水热反应温度时,PZT粉体的粒径尺寸增加明显.而进一步延长水热反应时间,PZT陶瓷粉体的粒径尺寸略有增加.由此,实验确定,本研究中溶胶-水热法合成PZT反铁电陶瓷粉的最佳水热条件为:水热反应温度为180 ℃,反应时间为18 h.     

二乙醇胺辅助溶胶-水热法低温合成四方形貌Pb(Zr0.52Ti0.48)O3粉体

以醋酸铅、异丙醇钛、正丙醇锆为主要实验原料,采用改进的溶胶-水热复合法,在较低温度下制备出了四方形貌的Pb(Zr0.52Ti0.48) O3[简称PZT]纳米级粉体.探讨了二乙醇胺和水热反应温度对粉体结晶过程、粉体形貌、颗粒尺寸的影响.实验结果表明,二乙醇胺能够显著降低水热合成温度,有助于粉体在低温条件下合成.随着水热反应温度由150℃逐渐升高至200℃,PZT粉体由非晶态逐渐转变成含有少量杂质的四方相,最后形成了纯的四方相结构.粉体颗粒尺寸逐渐变小.当水热反应温度为180℃时,具有单一四方相结构的Pb(Zr0.52 Ti0.48)O3粉体呈现四方形貌,且团聚不明显.     

Pb过量对以Ti-Al为阻挡层的硅基铁电电容器极化翻转性能的影响

以射频磁控溅射法生长的La0.5Sr0.5CoO3( LSCO)为电极,采用溶胶-凝胶法在以Ti-Al为导电阻挡层的Si基片上生长了用不同Pb过量前驱体溶液(溶胶)制备的LSCO/Pb( Zro4Ti0.6)O3(PZT)/LSCO电容器,以此构造了Pt/LSCO/PZT/LSCO/Ti-Al/Si异质结.Pb过量对LSCO/PZT/LSCO电容器极化翻转性能的影响表明:不同Pb过量溶胶对电容器的极化翻转性能影响很大,其中Pb过量15;的溶胶制备的样品在550℃常规退火1h后相对具有较好的翻转性能.在5V的外加电场下,LSCO/PZT/LSCO电容器的矫顽电压和剩余极化强度分别为1.25V和24.6μC/cm2.疲劳和电阻率测试分析表明:在经过109翻转后,不同样品的抗疲劳性能均很好,而电阻率随前驱体溶液Pb过量的增加呈现下降的趋势.     

纳微米PZT/水泥基压电复合材料的研究

采用溶胶-凝胶法合成了锆钛酸铅(PZT)纳微米粉体.XRD与SEM分析结果表明,经700 ℃煅烧的PZT粉体的平均晶粒尺寸约为26.4 nm,粉体团聚体的平均尺寸约为200 nm.采用干压成型-水化法制备了纳微米PZT/水泥基压电复合材料,研究了复合材料的压电及介电性能.SEM结果表明,PZT陶瓷相在基体中呈网状分布.PZT颗粒之间的良好连通性使复合材料具有优良的压电性能.     

ZnNb2O6粉体的水热合成研究

以Zn(NO3)2溶液和氧化铌凝胶为原料,分别选取HCI、NaOH等为矿化剂调节pH值,采用水热法制备了ZnNb2O6微波介质陶瓷粉体,利用XRD、SEM等方法表征了所得粉体的相组成、颗粒尺寸大小等.实验结果表明:以Zn(NO3)2溶液和Nb2O5·nHt2O为前驱物按照2:1的化学计量比在碱性条件下200℃反应168 h后,可制得平均晶粒尺寸为29.6 nm的ZnNb2O6粉体.将合成的粉体在400℃热处理,制得颗粒尺寸均匀,分散性良好的ZnNb2O6粉体.将水热合成的ZnNb2O6粉体制成陶瓷,其室温介电常数达到27.9.     

纳米Al2O3/GdAlO3共晶陶瓷复合粉体的醇-水加热法制备与表征

为制备分散均匀的纳米尺度的共晶陶瓷复合粉体,采用Al(NO3)3·9H2O和Gd2O3作为原材料,通过醇-水加热法制备了纳米尺度的Al2O3/GdAlO3共晶成分陶瓷粉体.研究了溶液初始浓度配比和pH值等对复合粉体粒径的影响.通过SEM、TEM、FT-IR和BET N2吸附法等手段表征了前驱体颗粒大小和分散性3确定最佳的前驱体制备工艺,对前驱体进行煅烧制得Al2O3/GdAlO3复合陶瓷粉体.结果表明,前驱体粒径和分散性受制备工艺影响较大;特别是,最佳工艺制备的前驱体平均粒径20 nm,分散性良好,形貌多呈球形;1250℃煅烧后得到的Al2O3/GdAlO3共晶陶瓷粉体的晶化良好、成分均匀,粉体粒径100～200 nm.     

水热反应温度对CaTi2O4(OH)2粉体微观形貌与紫外光催化性能的影响

以钛酸正丁酯和无水氯化钙为原料,采用水热法制备了不同紫外光催化特性的CaTi2O4(OH)2粉体.利用X射线衍射仪(XRD)和扫描电子显微镜(SEM)对样品的相结构和微观形貌进行了分析,并结合粉体的紫外-可见吸收分光光谱表征了材料的吸收特性及带隙宽度.研究了不同水热反应温度对CaTi2O4(OH)2物相结构、微观形貌、晶体生长特性及紫外光催化性能的影响.结果表明:水热反应温度控制在160~200 ℃时,保温36 h都能得到纯的CaTi2O4(OH)2相,粉体的形貌随着水热反应温度的提高经历了由片状和颗粒垛堆到发育成完整的片状形貌过程,当水热反应温度在200 ℃时,片与片之间出现积聚现象;在水热反应温度为180 ℃时,制备的粉体具有最高的结晶度,在紫外光5 h下对罗丹明B的催化效率最佳.     

水热法制备铁酸铋及光催化性能研究

以金属硝酸盐、硝酸、氢氧化钠和去离子水为原料,采用水热合成法来制备铁酸铋.研究了水热温度、pH值、水热反应时间对合成反应的影响,并采用X射线衍射、扫描电镜、热重分析仪、振动样品磁强计等手段对制备的铁酸铋纳米粉体的相结构、微观形貌进行了表征.结果表明,水热产物和形貌依赖于水热反应条件,通过水热反应条件的调控,制备出平均粒径在300hm左右的BiFeO3纳米颗粒.最后,以甲基橙为目标降解物,研究了BiFeO3纳米颗粒在可见光下的光催化性能.光催化实验显示制备的铁酸铋纳米颗粒在可见光下具有良好的光催化活性.     

反应条件对水热合成铁酸钇(YFeO3)微晶的物相、粒径和磁性能的影响

以氧化钇、硝酸和硝酸铁为原料,氢氧化钾为矿化剂,采用水热合成法制备了钙钛矿结构铁酸钇正铁氧体(YFeO3)微晶.研究了水热反应时间、温度和溶液pH值对产物的物相组成、粒径大小和磁性能的影响,研究结果表明,在实验条件所在区间内,随着反应时间的增加和反应温度的升高,产物纯度逐渐变高.合成纯相YFeO3需要在一定的溶液pH值范围内.随溶液pH值的降低,产物颗粒的粒径变小,粒径分布变窄,并且晶粒的磁化强度增大.最佳的合成条件是pH值为9.5,温度为260℃,反应时间为60h.     

熔盐法制备高性能铌酸钾钠无铅压电陶瓷

用熔盐法合成铌酸钾钠(Na0.52K0.48NbO3,N52K48N)陶瓷粉体,用传统固相烧结工艺制备N52K48N陶瓷.研究了熔盐含量和烧结温度对N52K48N陶瓷粉体及其所制备陶瓷的相结构、微观形貌及电学性能的影响.结果发现,熔盐法在750℃就合成了单一钙钛矿结构的N52K48N陶瓷粉体;随熔盐含量增加,N52K48N陶瓷粉体粒径增大,粉体团聚现象明显减弱.当熔盐与反应物质量之比为1∶5,烧结温度T=1050℃时,所制备的N52K48N陶瓷具有优异的电学性能:压电常数d33=137 pC/N,机电耦合系数kp=32.6;,居里温度Tc=410℃,表明熔盐法是一种很有前途的铌酸钾钠陶瓷制备方法.     

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...     

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.     

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.     

Investigation of the Mechanism of Influence of Stress Corrosion on the Development of Macroplastic Instabilities of Aluminum–Magnesium Alloy

Crystallography Reports - Macroscopic jumps of plastic deformation (few percent in amplitude) on creep curves of aluminum–magnesium alloy, caused by a local effect of concentrated solution of...     

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.     

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.     

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.     

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.