β-SiAlON晶须的诱导合成和生长机制研究

以β-SiAION粉料为晶种,SiC为基体,加入Si粉、AI粉和Al2O3粉在1900 K氮气气氛下合成β-SiAlON晶须,研究了晶须的显微结构、相组成和晶须增韧SiC复合材料的力学性能,并结合热力学研究了晶须的生长机制.结果表明:(1)以β-SiAlON粉料为诱导晶种时可以合成β-SiMON晶须材料,其生长机制为VLS机制和VS机制;(2)当以VLS机制生长时,晶须合成z值为1.56,直径约为200 -300nm,呈柱状和纤维状,当以VS机制生长时,晶须合成z值为1.76,直径为0.5～1.5 μm,呈柱状和竹节状,发育较为规则;(3)晶须相可有效提高复合材料的力学性能,相同组成的复合材料中,当β-SiAlON晶须相的含量较高时,材料可以在气孔率较高(32.1;)条件下获得了较好的抗折强度(55.2 MPa).     

磷酸盐低温烧结高强度SiC泡沫陶瓷及性能研究

通过有机模板复制法,以磷酸二氢铝为粘结剂,950 ℃烧成制备了高强度SiC泡沫陶瓷.研究了浆料中SiC含量和磷酸二氢铝含量对SiC泡沫陶瓷微观结构与性能的影响.结果表明:SiC微粉由A型Al(PO3)3粘结起来,烧成泡沫陶瓷通孔结构良好,开气孔率介于75;~91;之间.随着磷酸二氢铝含量的增加,烧成泡沫陶瓷的线收缩率、体积密度和抗折强度均逐渐增加,而开气孔率则逐渐减小;随着SiC含量的增加,烧成泡沫陶瓷的线收缩率和开气孔率均逐渐减小,而体积密度和抗折强度则逐渐增加.磷酸二氢铝含量为40;、SiC含量为60;时,泡沫陶瓷的抗折强度达(2.22±0.26) MPa.     

不同铝硅比对莫来石材料显微结构及性能的影响

选用铝矾土作为铝源,煤矸石为硅源,氟化铝和五氧化二钒为添加剂,通过固相反应原位制备了主晶相为莫来石相的晶体.利用X射线衍射仪和扫描电子显微镜以及相应的EDS等手段对莫来石进行了表征分析,并考察了在不同铝硅比的条件下对所制试样的显气孔率、吸水率、体积密度、抗折强度以及显微结构的变化特征.结果表明:当铝矾土与煤矸石的铝硅摩尔比为3.05:2时,显气孔率为23.6;、吸水率为10.55;、体积密度为2.3 g/cm3、抗折强度为114 MPa,试样的综合性能最优.     

碳酸钙晶须的制备及含硫化合物对碳酸钙晶须影响的研究

在碱性环境下(pH＞ 12)采用衬底溶液双滴加法制备了形貌均匀且长径比大于10的文石型碳酸钙晶须.探讨了衬底液浓度、温度等因素对碳酸钙晶须生长的影响;研究了硫化钠、硫酸钠、硫代硫酸钠对碳酸钙晶须生长过程的影响;通过扫描电子显微镜和X射线衍射对样品的形貌和物相进行了表征.结果表明:衬底液Ca2+浓度为0.4 mol/L、温度为80 ℃时最有利于文石型碳酸钙晶须的生长;随着含硫化合物的增加,文石型碳酸钙晶须的长径比与质量分数均逐渐减小,且方解石型碳酸钙含量逐渐增加.     

Al粉粒度及其添加量对SiC陶瓷材料结构和性能的影响

以Al粉为烧结助剂,采用无压烧结工艺于1600℃下保温3 h烧制SiC陶瓷材料,研究了不同Al粉粒度及其添加量对SiC陶瓷材料结构和性能的影响.结果表明:Al粉可促进SiC陶瓷材料的烧结和力学性能的提高,同时起抗氧化的作用,且粒度较小的Al粉对其性能提升的幅度较大.当添加4wt;粒度为48μm的Al粉时,SiC陶瓷材料的性能较佳,体积密度和显气孔率分别为2.69 g/cm3和5.8;,显微硬度和抗折强度分别为2790 HV和189 MPa.SiC陶瓷材料烧结性能和力学性能的提高可归因于Al粉的促烧结作用,及其氧化产物Al2 O3和原位生成的少量莫来石分布在SiC颗粒间所起的强化作用.     

合成温度对碳热还原法合成碳化硅晶须形貌的影响

以SiO2微粉为硅源,炭黑为碳源,氧化硼为催化剂,采用碳热还原法分别在1500 ℃、1550 ℃、1600 ℃制备了SiC晶须.通过扫描电镜,电子探针和透射电镜等分析手段,研究了合成温度对SiC晶须形貌的影响,探讨了晶须的生长机理.结果表明:当合成温度为1500 ℃时,所合成的SiC晶须形貌呈竹节状,选区电子衍射分析发现孪晶等面缺陷在晶须的生长方向上周期性出现;当合成温度在1550 ℃以上时,哑铃状晶须的数量会急剧增多,分析表明晶须表面包裹的串珠小球为β-SiC.在晶须的顶端发现催化剂熔球,由此推测生长机理为VLS机理,但当合成温度超过1550 ℃时,SiC会以VS生长机理沿径向沉积生成哑铃状晶须.     

无水硫酸钙晶须对不同种类石膏基复合材料性能的影响

将无水硫酸钙晶须掺入天然石膏,脱硫石膏和磷石膏三种石膏基体中,研究无水硫酸钙晶须对不同种类石膏基体性能的影响.并利用XRD和SEM分别分析三种石膏基体原材料的物相组成和掺有无水硫酸钙晶须石膏基复合材料的微观性能.结果表明,随着无水硫酸钙晶须掺量的增加,三种石膏基复合材料的凝结时间均缩短,气孔率都先降低后上升.天然石膏基复合材料在无水硫酸钙晶须掺量为15;时力学性能最优,抗折强度和抗压强度较空白样分别增长31.6;和10.7;.脱硫石膏基复合材料在无水硫酸钙晶须掺量为10;时力学性能最优,抗压强度较空白样提高18.5;.磷石膏基复合材料在无水硫酸钙晶须掺量为15;时力学性能最优,抗折强度较空白样提高98.3;.     

烧结法制备高炉渣CMAS系统微晶玻璃的研究

利用高炉渣及其它辅助原料制备基础玻璃,采用一步烧结法制备主晶相为辉石的CaO-MgO-Al2O3-SiO2(CMAS)微晶玻璃.综合运用DSC,XRD以及场发射扫描电子显微镜等测试手段,分析热处理制度对高炉渣CMAS微晶玻璃的析晶行为及性能的影响.结果表明:随着热处理温度上升,微晶玻璃的主晶相均为辉石,次晶相均为长石,晶相析出量增加,微晶玻璃的体积密度及抗折强度均呈现先增后减趋势.随着热处理时间增加,微晶玻璃的体积密度及抗折强度均呈现下降趋势.当热处理温度为1020 ℃,晶化时间30 min时,样品的机械性能最好,体积密度为2.690 g·cm-3,抗折强度为67.00 MPa.     

透辉石微晶玻璃的低温烧结制备及性能表征

以废弃建筑玻璃为主体原料,将废玻璃粉、高岭土和氧化镁进行球磨混和,压制成型后直接烧结,在低温下成功制备出具有单一透辉石晶相结构的微晶玻璃.采用X射线衍射、场发射扫描电子显微镜等测试手段,研究了MgO加入量和烧结温度对微晶玻璃样品的晶相组成、显微结构及性能等的影响.结果表明:随着MgO加入量的增多以及烧结温度的升高,微晶玻璃的体积密度和抗弯强度均呈现先增大后减小的趋势.MgO加入量和烧结温度的提高可以有效促进透辉石晶相的析出.当MgO加入量为4;、975℃烧结2 h时所制备得到的透辉石微晶玻璃性能最好,其体积密度为2.395 g·cm-3,抗折强度102.1 MPa.     

不同硅源原位合成莫来石及其性能

分别选用煤矸石、粉煤灰、黄沙、苏州土为硅源,工业氢氧化铝为铝源,氟化铝和五氧化二钒为添加剂,通过固相反应法原位合成了具有莫来石晶相的样品.采用X射线衍射仪和扫描电子显微镜对试样的物相结构和微观形貌进行了分析,研究了在不同的硅源下制备的试样性能及其结构的特征变化.结果表明:利用苏州土作为硅源能够合成具有针状形貌的莫来石晶相,分别以煤矸石和黄沙作为硅源合成了具有柱状形貌的莫来石和片状形貌的氧化铝晶相,而以粉煤灰作为硅源合成的主晶相为柱状的莫来石;并分别对不同硅源制备的试样的体积密度、显气孔率以及抗折强度进行了分析,探讨了莫来石的形成机理.     

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...     

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.     

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.     

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...     

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.     

A SAXS study of kinetics of aggregation of silica sols

SAXS in situ experiments on the evolution of TMOS solutions during hydrolysis and polycondensation lead to power laws with scaling exponents ≈ 2. It is suggested that this could be the result of the polydispersity of the samples and that only an apparent fractal dimension can be obtained in this way. Kinetic studies tend to indicate that agglomeration in the sol is the result of a diffusion-controlled process.