A位阳离子平均半径对La0.3Nd0.37Sr0.33-xCaxMnO3多晶陶瓷电运输性能的影响

采用溶胶-凝胶法制备一系列La0.3Nd0.37Sr0.33-xCaxMnO3(x=0.00,0.05,0.10,0.125,0.15,0.20)多晶陶瓷,用XRD分析多晶陶瓷的晶体结构,用SEM对多晶陶瓷的晶粒尺寸和表面形貌进行分析,用标准四探针法测量电阻-温度关系.实验结果表明,随着Ca掺杂浓度的增加,晶体结构从菱方晶系向正交晶系转变,绝缘体-金属转变温度(7P)往低温方向移动,电阻率不断增加,电阻温度系数(TCR)也在不断增加.这主要是因为用离子半径较小的Ca2替换离子半径较大的Sr2,引起A位阳离子平均离子半径减小,导致容忍因子也随之减小.Mn-O-Mn键的弯曲程度增加,导致MnO6八面体畸变增大,eg电子局域性增强,Mn3+-O2--Mn4+之间的双交换作用减弱,电阻率增大,TP往低温方向移动,且转变温度宽度变窄,使得TCR增大.     

Bi1.7Pb0.3Sr2Ca2Cu3O10多晶制备工艺对其电学性能影响的研究

采用溶胶-凝胶法成功制备了Bi1.7Pb0.3Sr2Ca2Cu3O10(BPSCCO)粉末,通过优化制备工艺获得了电学性能优良,转变温度在114 K左右的Bi1.7Pb0.3Sr2Ca2Cu3O10多晶靶材.利用X射线衍射仪测试了样品的物相和结构,并利用四探针法测试了靶材的电阻-温度曲线.对比了不同螯合剂对溶胶-凝胶法制备BPSCCO多晶的影响,发现以葡萄糖酸为螯合剂克服了传统工艺周期长、pH难调控的缺点.在此基础上,探究了热处理工艺对Bi1.7Pb0.3Sr2Ca2Cu3O10多晶电学性能的影响,得到了其最适预烧温度(600 ～ 700℃)、烧结温度(820～830℃)及烧结时间(48 h).     

烧结工艺对La0.67Ca0.33MnO3多晶物理性质的影响

利用溶胶-凝胶法成功制备了La0.67Ca0.33MnO3粉末,并通过优化烧结工艺获得了物理性能优异的La0.67Ca0.33MnO3多晶靶材.利用X射线衍射仪和扫描电子显微镜分别测试了样品的物相、结构和微观形貌,并利用四探针法测试了靶材的电阻率-温度曲线.结果表明,影响TCR的主要因素有晶粒的化学均匀性、晶粒尺寸和晶界的数量,样品具有接近室温的金属-绝缘转变温度(TM1 =274 K)和高的电阻温度系数(TCR=13.5;).     

溶胶-凝胶法制备Na0.5Bi0.5TiO3-K0.5Bi0.5TiO3体系无铅压电陶瓷的研究

采用溶胶-凝胶法制备(1-x)Na0.5Bi0.5 TiO3-xK0.5Bi0.5TiO3体系无铅压电陶瓷.XRD分析表明,用溶胶-凝胶法可以在650℃下合成具有钙钛矿结构的(1-x)Na0.5Bi0.5TiO3-xK0.5Bi0.5TiO3粉体,且在x=0.18～0.30之间存在三方-四方准同型相界(MPB).陶瓷的压电性能参数表明,该体系在MPB组成范围内具有最佳的压电性能:x=0.30时,压电常数d33达到最大值(d33=150 Pc·N-1),平面机电耦合系数kp与介电常数εH33T/ε0均在x=0.26时达到最大值,分别为36.7;和1107.     

高电阻温度系数(La0.67Ca0.33MnO3)1-x∶Agx多晶陶瓷的研究

采用溶胶-凝胶法制备了(La0.67Ca0.33 MnO3)1-x∶Agx(x=0.00、0.10、0.15、0.20、0.3、0.4、0.5)系列多晶陶瓷样品,通过XRD、SEM和标准四探针法对材料晶体结构、表面形貌和电学性能的分析研究Ag的添加对材料性能的影响.结果表明:随着Ag添加量的增加,样品的晶格常数逐渐增大,这是由于Ag取代La3+、Ca2+进入晶格使其发生膨胀;并且样品的金属-绝缘体转变温度(Tp)随Ag添加量的增加而升高,从270 K(x=0)升高到281 K(x=0.5),这是由于Ag对La3+、Ca2+的替换导致Mn4+/Mn3+比例增大而提高了双交换作用.值得注意的是,当0.00≤x≤0.15时,TCR值随x的增大而增大,当x=0.15时达到最大值58.6;·K-1;0.15≤x≤0.5时,TCR反而随之降低,这可能是由于高添加量导致材料的烧结质量降低.     

退火升温速率对LaNiO3薄膜结构和电学性能的影响

采用溶胶-凝胶法在SiO2/Si(100)衬底上制备了镍酸镧(LaNiO3,LNO)薄膜,并利用XRD、SEM、AFM和半导体参数分析仪等研究了退火升温速率对LNO薄膜结构和电学性能的影响.结果表明,溶胶-凝胶法制备的LNO薄膜呈现赝立方钙钛矿型多晶结构,呈(110)择优取向生长;薄膜表面平整、均匀、无裂纹.随着退火升温速率的增加,LNO薄膜的晶粒尺寸先增大后减小;其电阻率先减小后增大.在退火升温速率为20℃/min时,LNO薄膜晶粒尺寸达到最大值94 nm,电阻率达到最小值9.5 x10-4 Ω·m.     

预烧温度对La0.67Ca0.33MnO3陶瓷结构及电学性能的影响

采用溶胶-凝胶法成功制备了La0.67Ca0.33MnO3粉末,并通过改变预烧温度获取电学性能优异的陶瓷.利用X射线衍射(XRD)、扫描电子显微镜(SEM)、四探针法对不同预烧温度处理后的La0.67Ca0.33MnO3陶瓷的物相、结构、微观形貌和电学性能进行测试,分析预烧温度对材料的晶粒尺寸和电学性能的影响,从而摸索出最佳预烧温度.实验结果表明:样品的结晶性能好物相纯,随着预烧温度的增加,晶粒尺寸、致密度、收缩率和电阻温度系数(TCR)在不断减小,电阻率先减小后增加.在300℃预烧,1450℃烧结得到的样品具有较高的TCR值达到了40.8;·K-1.     

La2Zr2O7陶瓷在高温及高温湿氧环境中的组成结构演化

采用溶胶-凝胶法制备了锫酸镧(LZO)陶瓷,对比研究了LZO陶瓷在1300～ 1500℃空气环境及水汽环境中的组成、结构演变.采用电感耦合等离子体原子发射光谱(ICP-AES)仪,X射线衍射(XRD)仪、场发射扫描电子显微镜(SEM)、透射电子显微镜(TEM)对LZO陶瓷及经不同环境处理后的组成、物相与形貌进行了研究.结果表明:溶胶-凝胶法制备所得LZO陶瓷为烧绿石结构,平均晶粒尺寸为44nm,陶瓷中的La和Zr摩尔比为0.94∶1;LZO陶瓷在高温空气环境中的组成与结构基本稳定,1500℃下出现了较为明显的高温烧结和晶粒生长;LZO陶瓷在高温水汽环境中失重明显,且发生了严重的分相和高温烧结,生成了m相ZrO2和c相La2O3,平均晶粒尺寸达到2μμm.     

室温铁磁Sr3YCo4O10.5+δ多晶的制备及其性能研究

采用传统简便的固相烧结法制备了四方相的室温铁磁Sr3YCo4O10.5+δ多晶.热分析、X射线衍射和扫描电镜结果表明Sr3 YCo4 O10.5+δ多晶最终烧结温度应在963℃以上,较佳的烧结温度为1180℃.Sr3YCo4O10.5+δ多晶在80～300K为半导体电输运行为,较佳烧结温度多晶的室温电阻率～78.8 mΩ·cm;多晶热电势在317～1018 K随温度增加而减小,317 K时为70.74 μV/K.磁化强度-温度曲线、磁滞回线结果表明,多晶在受外加磁场、温度及晶体场的影响下,内部Co3+自旋态及磁畴壁、磁矩方向发生改变,导致多晶磁化强度变化及多晶磁性的改变.外磁场(0.1 T)下的ZFC曲线在320 K出现磁化强度最大为0.46 emu/g的Hopkinson峰,居里温度(Tc) =323 K,而FC曲线在奈尔温度(TN)=264 K时磁化强度达到最大为1.1 emu/g,TC=320 K.ZFC、FC方式下多晶均表现为室温铁磁性.     

钇掺杂铌酸锶陶瓷的微观结构与电性能研究

采用固相法制备了Nb2Sr2-xYxO7陶瓷.研究了掺Y对陶瓷的晶体结构、表面形貌、铁电、介电和压电性能的影响.研究结果表明:钇掺杂Sr2 Nb2 O7陶瓷,Y3+取代了A位Sr2+,形成Nb2 Sr2-xYxO7固溶体,并提高了铌酸锶陶瓷铁电、介电和压电性能.在x=0.05时,Nb2 Sr2-xYxO7陶瓷的铁电性能达到最大(剩余极化强度Pr=0.254μC/cm2);在x=0.1时,Nb2Sr2-xYxO7陶瓷的介电性能达到最大(相对介电常数εr=90,介电损耗tarδ≤0.01).     

Modelling of mechanism of agglomeration of KCl crystallization

The article presents an analysis into agglomeration during KCl vacuum crystallization. The theoretical and experimental investigations into the mechanism of agglomeration during mass crystallization result in an extension of the growth phenomena within the known model equations. The basis for this is essentially constituted by the collision model concepts of the theory of floculation in disperse systems. The parameters derived from the microprocess analysis (energy dissipation, content of solids, growth rate of individual grains) lead to model equations which are confirmed by laboratory and test trials.     

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...     

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.     

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.     

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.     

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.