乙烯基三氯硅烷合成陶瓷前驱体聚硼硅氮烷的研究与表征

聚硼硅氮烷高温裂解可制备性能优异的SiBCN陶瓷.随着SiBCN陶瓷的广泛研究和使用,越来越多的学者研究聚硼硅氮烷的合成和性能.本文以乙烯基三氯硅烷为原料合成出聚硼硅氮烷,并对其结构进行了表征.研究结果表明通过FT-IR分析确定了N-H、C-H、Si-C、C-B-C键的存在,但Si-N键的FT-IR谱蜂由于与Si-C键重叠,在FT-IR谱图中难以体现,但在29Si-NMR谱中得到证实.对聚硼硅氮烷的NMR分析发现CHCBSi基团的对称性较差,发生横向弛豫,使对应的13C-NMR谱的谱峰变宽.     

前驱体转化法制备TiSi2/YSZ陶瓷涂层

采用聚硅氮烷前驱体作为基体,添加惰性填料(YSZ)和活性填料(TiSi2)制备涂层浆料,在310s不锈钢表面利用前驱体转化法制备TiSi2/YSZ陶瓷涂层.通过TGA、XRD和SEM对涂层的物相组成和微观形貌进行了表征,并研究了TiSi2含量对涂层的隔热性能以及耐高温性能的影响.结果表明,所制备的涂层厚度在15～35μm之间,由于前驱体树脂裂解过程中的体积收缩,未添加TiSi2的涂层表面分布有大量裂纹且涂层部分脱落.裂解过程中,TiSi2氧化生成TiO2与SiO2后可使TiSi2体积膨胀,弥补了前驱体树脂的体积收缩.因此随着TiSi2含量的增加,涂层脱落面积减少,表面裂纹密度降低,当TiSi2的体积分数达41;时,涂层内部无裂纹产生,该涂层样品在1200℃氧化25 h后金属基底氧化增重降低88.8;,并表现出良好的隔热性能和抗热震性能.     

陶瓷先驱体聚硅氮烷(PSZ)加入Si、MoSi2填料制备石墨抗氧化复合涂层的研究

采用陶瓷先驱体聚硅氮烷(PSZ)为主要原料,并加入Si、MoSi2填料,于石墨表面制备高温抗氧化涂层.借助扫描电镜和X射线衍射仪等分析手段对复合涂层的微观结构和相组成进行表征,并对涂层的抗氧化性能进行了初步研究.结果表明,涂层厚度约为30μm,内层为化学结合的SiC-Si过渡层,外层为MoSi2-SiC-SiCN氧阻挡层,涂层表面较为平整、致密,与过渡层结合紧密.涂层试样抗氧化效果与氧化温度有关,当氧化温度为1200℃时,抗氧化能力较差,氧化失重率约为10.98;,当氧化温度高于1300℃时,高温封填剂的作用发挥充分,抗氧化性能显著提高,氧化失重率仅为1.15;.     

不同形态的铝对激光裂解聚硅氧烷制备SiAlCO陶瓷涂层的影响

采用激光裂解含Al聚硅氧烷法制备陶瓷涂层,通过扫描电子显微镜(SEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)等手段,分析了激光裂解含Al聚硅氧烷生成物的组成与结构.结果表明,Al元素的化学价态对激光裂解聚硅氧烷制备的涂层形貌有非常大的影响.在激光裂解含Al聚硅氧烷过程中,Al与聚硅氧烷中的C、O、Si发生反应产生新生陶瓷相,但加入Al粒子时生成晶态Al0.2Si0.8O2.2和非晶态Al2O3陶瓷相,加入异丙醇铝时生成非晶态的Al2O3和AlOx陶瓷相.新生陶瓷相对所制备的陶瓷涂层表面孔隙具有填补作用,使陶瓷涂层表面平整致密,孔隙、缝隙基本消失.     

低温合成PSN微球及其裂解制备Si-C-N空心陶瓷微球

以含乙烯基聚硅氮烷(PSN)为先驱体聚合物,二乙烯基苯(DVB)为交联剂,采用乳液工艺,在低温条件下交联固化合成聚硅氮烷(PSN)微球,并在高温下裂解制得Si-C-N空心陶瓷微球.研究了原料比例、固化时间和裂解条件对PSN微球及Si-C-N空心陶瓷微球形貌、尺寸和形成过程的影响.结果表明,当PSN与DVB的比例为2∶1、固化时间为6h时,可在80℃下得到表面光滑、尺寸较均匀、直径为600～ 800 nm的PSN微球;Si-C-N陶瓷微球随着PSN与DVB比例的增加,逐渐显现出空心结构;1000～ 1200℃裂解后,空心球形成,XRD表明此时产物呈非晶态;裂解温度1400℃时,空心微球表面变得粗糙,生成Si3N4和SiC晶粒.     

新型SiC/SiBCN复合陶瓷的析晶性能

通过热解聚碳硅烷(PCS)和聚硼硅氮烷(PBS)两种有机先驱体混合物,制得非晶态SiC/SiBCN复合陶瓷,然后对复合陶瓷进行高温热处理,研究其析晶规律及影响因素.利用热分析(TG-DTA)、X射线衍射(XRD)及透射电子显微镜(TEM)分别研究先驱体的热解机理,先驱体的组成、热解温度和时间对SiC/SiBCN复合陶瓷结晶性的影响,以及复合陶瓷的微观结构.结果表明,先驱体的组成和热处理温度对复合陶瓷的析晶行为有重要影响.当PBS/PCS=1(w/w),1100 ℃/2 h制得非晶态SiC/SiBCN复合陶瓷;1400 ℃/4 h PCS热解转变的非晶SiC开始结晶,晶粒尺寸～3 nm;1500 ℃/4 h 得到产物的相结构为～10 nm 的SiC纳米晶均匀弥散在PBS热解得到的非晶态SiBCN中;1700 ℃/2 h SiC的晶粒尺寸～16 nm;1800 ℃/2 h非晶态SiBCN开始析晶,SiC晶粒尺寸～35 nm.     

先驱体浸渍裂解结合反应熔渗法制备Cf/ZrC-SiC复合材料

以先驱体浸渍裂解结合反应熔渗工艺将Cf/C-SiC材料内部富余的自由碳相转变为ZrC超高温陶瓷,制备了Cf/ZrC-SiC复合材料.对Cf/C-SiC基材的孔隙进行了设计,利用XRD和SEM分析了Cf/ZrC-SiC复合材料的微观结构和物相组成.结果表明:采用PIP法可制备具有理想孔隙率的Cf/C-SiC基材;1800℃熔渗Zr-Si合金反应制得的Cf/ZrC-SiC材料主要由SiC和ZrC相组成;高温条件下熔融金属与基体反应的同时,还会侵蚀碳纤维.热解碳涂层能保护纤维.     

SiCf/SiC复合材料表面梯度抗氧化SiC涂层研究

SiC纤维增强SiC陶瓷基复合材料(简称SiCf/SiC复合材料)具有低密度、高温稳定性、抗氧化性、高耐腐蚀性等特点,在航天及航空发动机热结构部件及核聚变反应堆炉第一壁结构等方面有巨大的潜在用途.目前受工艺条件制约,SiCf/SiC复合材料中用来增强的SiC纤维纯度不高,C/Si原子比大于1.3,而采用传统先驱体浸渍裂解工艺(简称PIP)制备的基体材料除了纯度不高外,还含有孔隙和缺陷,不能满足高温氧化环境中服役要求.本文通过化学气相沉积工艺(CVD)在SiCf/SiC复合材料表面制备出一种高纯、低缺陷、耐高温、低氧扩散系数且与基体材料具有良好匹配性的SiC抗氧化梯度涂层,通过SEM分析基体与膜层的结合情况及涂层的微观形貌,通过XRD考察涂层的梯度组份及氧化前后涂层成份变化,进而探讨梯度涂层抗氧化机理.     

水基流延成型和热压烧结制备碳化硼陶瓷及性能研究

以工业碳化硼粉末为原料、采用Si3N4磨球磨损法引入Si3N4烧结助剂,采用水基流延成型和热压烧结方法制备了碳化硼陶瓷.研究了氧含量、分散剂、pH值等因素对B4C陶瓷浆料分散性能的影响,采用XRD、SEM等对碳化硼陶瓷的物相、显微结构和第二相分布进行了表征,并测试了样品的维氏硬度、断裂韧性、抗弯强度和弹性模量.结果表明:经醇洗后的碳化硼粉末中氧化硼含量降低,有利于B4C陶瓷浆料的分散稳定.采用球磨磨损引入了Si3N4粉,在B4C基体中通过原位反应形成第二相SiC和BN,SiC和BN第二相颗粒在B4C基体中弥散分布均匀.在2100 ℃热压烧结样品的维氏硬度、抗弯强度、断裂韧性和弹性模量分别达到30.2 GPa、596.5 MPa、3.36 MPa·m1/2和362.3 GPa.     

SiC/SiC复合材料高温力学性能研究

以聚碳硅烷为连续SiC陶瓷基体相的先驱体,三维四向SiC纤维预制体为增强相,采用聚合物先驱体浸渍裂解工艺制备了SiC纤维增强SiC陶瓷基(SiC/SiC)复合材料,分析表征了复合材料的组成、结构和力学性能.结果表明,SiC/SiC复合材料室温弯曲强度和断裂韧性分别为400 MPa和16.5 MPa·m1/2,优异的室温力学性能可以保持到1350℃.随着温度增加,弯曲强度基本不变,1350℃时因界面层受到破坏而断裂韧性稍有下降.     

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.     

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.     

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.     

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.