添加聚碳硅烷(PCS)对ZrB2-SiC超高温陶瓷微结构和力学性能的影响

采用聚碳硅烷(PCS)和纳米ZrB2粉体为原料在不同温度下热压烧结制备了ZrB2-SiC超高温陶瓷,对比了PCS和颗粒状SiC的引入对ZrB2陶瓷微结构和力学性能的影响.结果表明:通过PCS替代颗粒状SiC制备ZrB2-SiC超高温陶瓷可以形成SiC均匀包覆基体ZrB2晶粒的微观结构,明显促进了材料的低温致密化并抑制了晶粒长大.但力学性能略有降低,其原因可能是PCS裂解产生的微量碳遗留在基体ZrB2的晶界处,弱化了晶界结合强度.本文验证了采用PCS和纳米ZrB2粉体进行热压烧结是实现ZrB2-SiC超高温陶瓷低温致密化的有效手段.     

ZrB2-SiC-Csf超高温陶瓷复合材料碳纤维损伤抑制研究

采用放电等离子烧结和热压烧结制备了短切碳纤维(Csf)增韧ZrB2-SiC超高温陶瓷复合材料(ZrB2-SiC-Csf),研究了制备工艺对ZrB2-SiC-Csf复合材料微结构演变、力学性能和抗热冲击性能的影响.结果表明:烧结温度是导致碳纤维结构损伤的主要因素,降低烧结温度能有效抑制碳纤维的结构损伤.采用纳米ZrB2粉体在1450 ℃低温热压烧结制备的ZrB2-SiC-Csf复合材料在断裂过程中表现出纤维拔出、纤维侨联和裂纹偏转增韧机制,其临界热冲击温差高达741 ℃,表现出良好的力学性能和优异的抗热冲击性能.从热力学的角度阐明了ZrB2-SiC-Csf复合材料中碳纤维结构损伤的机理,并揭示了该类材料的烧结温度应低于1500 ℃.     

ZrB_2-SiC-AlN超高温陶瓷材料力学性能及抗热震性能研究

采用热压烧结工艺制备了两种不同AlN含量(5 vol%,10 vol%)的ZrB2-SiC基超高温陶瓷材料,并对其微观组织与力学性能进行了考察。结果表明:当AlN含量为5 vol%时材料的致密度较高,弯曲强度和断裂韧性也较高,分别为815 MPa和6.16 MPa.m1/2,过量的AlN加入显著降低了材料的力学性能;材料的断裂方式以沿晶断裂为主,增韧机制主要是裂纹偏转。同时采用水淬法对ZrB2-15 vol%SiC-5 vol%AlN陶瓷材料的抗热震性能进行了考察,结果显示临界热震温差为300℃。     

反应热压烧结制备SiC/ZrB2复相陶瓷及其性能表征

以二硼化锆、硅和活性碳为原材料,在1850℃、20 MPa条件下,采用反应热压烧结工艺制备出了SiC/ZrB2陶瓷基复合材料.研究了添加剂(硅和活性碳)含量对ZrB2陶瓷烧结行为和力学性能的影响.借助X射线衍射和扫描电镜分析了复合材料的物相组成和微观结构.研究结果表明:添加剂可以显著提高复合材料的烧结致密度和力学性能.复合材料的XRD衍射图谱中只有ZrB2和SiC的衍射峰.当添加剂含量为12wt;时,复合材料的弯曲强度和断裂韧性分别达到584MPa和7.25MPa ·m1/2.显微结构分析表明,致密度的提高、晶粒粒径的减小以及断裂模式的转变是复合材料力学性能提高的主要原因.     

以MH2(M=Ti,Zr)为原料反应烧结制备MB2-SiC复相陶瓷

分别以TiH2,ZrH2为原料,结合原位反应与脉冲电流辅助烧结制备了TiB2-SiC及ZrB2-SiC复相陶瓷.研究发现,所制备的复相陶瓷表现出一定的织构化现象,TiB2及ZrB2晶粒在反应烧结过程中其(001)面沿垂直压力和电流方向生长.金属氢化物粉体的粒径大小对复相陶瓷的致密化及微结构有较大影响:粒径越小越有利于陶瓷的致密化和硼化物晶粒的定向生长.由于金属硼化物的定向,复相陶瓷的机械性能表现出各向异性.TiB2-SiC复相陶瓷具有较高的断裂韧性,最高可达7.3 MPa·m1/2,而ZrB2-SiC复相陶瓷具有更高的抗弯强度(937 MPa).     

粉体粒径及烧结工艺对ZrB2陶瓷致密化行为与晶粒长大的影响

利用热压烧结(HP)和放电等离子烧结(SPS)制备了ZrB2陶瓷,研究了粉体粒径和烧结工艺对ZrB2陶瓷致密化行为和晶粒长大的影响.结果表明,相同工艺下以平均粒径为200 nm的ZrB2粉体为原料替代平均粒径为2μm的ZrB2粉体可以明显促进粉体的致密化烧结,采用SPS替代HP工艺可以显著降低粉体的致密化温度,采用平均粒径为200 nm的ZrB2粉体在1900℃进行SPS工艺烧结即可实现ZrB2陶瓷的致密化烧结.     

ZrC薄膜对Nb与ZrB2-SiC相互作用的影响

以ZrB2、SiC粉体为原料,通过等离子活化烧结在1800℃,30 MPa,保温时间5 min条件下制得出组织结构均匀致密度的ZrB2-SiC陶瓷块体;采用磁控溅射在Nb箔表面镀微米级别的ZrC薄膜.然后将Nb箔与ZrB2-SiC叠层进行烧结.利用XRD检测了产物物相,采用SEM和能谱分析观测了断口显微结构和元素分布.结果表明,当Nb箔表面无ZrC薄膜或薄膜被破坏后,产物中基本不存在单质Nb.当Nb箔表面保持有完整ZrC薄膜时,Nb金属相可以大量保留下来.当烧结温度低于1500℃时,ZrC薄膜可以有效阻止铌箔的与ZrB2、SiC的反应.镀有ZrC薄膜的Nb箔做中间层与ZrB2/SiC叠层材料的断裂韧性有明显提高,断裂韧性达到了9.66 MPa·m1/2.     

ZrB2粒径对Si3N4-ZrB2陶瓷相组成、显微结构及电阻率的影响

以20vol; ZrB2粗粉和细粉为导电相,以3vol; MgO-2vol; YB2O3烧结助剂,通过热压烧结在1500℃制备了Si13N4-ZrB2复相陶瓷,研究了ZrB2粒径对致密度、相组成、显微结构以及电阻率的影响.结果表明,不依赖于Zrl2粒径,通过引入MgO-YB2O3烧结助剂,均可以获得高致密Si3N4-ZrB2陶瓷.以Zrl2粗粉为原料时,Si3N4-ZrB2陶瓷包含主要的αt-Si3N4 、β-Si3N4和ZrB2相以及微弱的Yb4 Si2N2O7相,由于ZrB2晶粒保持孤立状态,样品电阻率较高,为9.5×103 Ω·m;而以ZrB2细粉为原料时,其与Si3N4发生轻微的高温反应,除了包含主要的d-Si3N4、β-Si3N4和ZrB2相及微弱的Yb4Si2N2O7相之外,Si3 N4-ZrB2陶瓷还含有新生成的微弱ZrSi2和ZrN导电相,由于ZrB2晶粒保持连通状态,样品电阻率显著降低,仅有6.8 Ω·m.     

YF3/氧化物烧结助剂对碳化硅陶瓷热导率的影响

利用YF3/氧化物体系作为烧结助剂热压烧结碳化硅陶瓷,研究了此体系中氧化物的种类、含量对样品的致密度、导热性能、物相成分、微观形貌的影响.实验结果表明,在烧结温度1900 ℃、压力50 MPa条件下,YF3/氧化物体系烧结助剂对碳化硅陶瓷热导率有所提升,其中同时添加5wt;YF3+3wt;MgO双相烧结助剂的SiC陶瓷性能最优,其致密度为98.93;,热扩散系数为71.40 mm2/s,热导率为154.29 W/(m· K).     

凝胶注模成型Al2O3陶瓷的显微结构及力学性能研究

以Al2O3粉为原料,TiO2+MgO为烧结助剂,琼脂糖为单体,聚丙烯酸铵为分散剂,利用凝胶注模及无压烧结工艺制备了Al2O3陶瓷.研究了琼脂糖固化机制、烧结助剂作用机理以及琼脂糖含量对Al2O3陶瓷坯体及烧结体的显微结构及力学性能的影响规律.试验结果表明,琼脂糖利用内部氢键的结合,形成三维网络状结构,将Al2O3粉原位凝固成型.TiO2+MgO烧结助剂使材料实现了液相烧结机制,有利于降低材料的烧结温度及促进致密化进程.随着琼脂糖含量增加,坯体的致密度、坯体及烧结体的抗弯强度均呈先增大后减小趋势.当琼脂糖含量为0.5wt;时,Al2O3陶瓷的抗弯强度达到最大值.     

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...     

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.     

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.     

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.