基于第一性原理的WC-Co(0001)/cBN(111)界面结合性能研究

基于第一性原理方法,建立WC-Co/cBN4B、WC-Co/cBN4N、WC-Co/cBN1B-near OA、WC-Co/cBN1N-near OA、WC-Co/cBN1N-near OB和WC-Co/cBN1B-near OB六种界面模型,计算其界面粘附功、断裂韧性.结果 表明:WC-Co/cBN4B界面具有最大粘附功值9.705 J·m-2,界面最稳定,粘附功大于WC(0001)w界面的断裂韧性7.824 J·m-2,裂纹倾向于出现在基体中;WC-Co/cBN4N界面有最小粘附功4.470 J·m-2,界面最不稳定,粘附功小于WC(000l)w界面的断裂韧性,裂纹倾向于出现在界面处.在此基础上,为从电荷转移、成键方式和价电子分布的深层次角度解释界面稳定性,进行了差分电荷密度、态密度和Mulliken布居分析,结果表明:WC-Co/cBN4B模型中,界面处Co、B原子之间存在电荷转移,由Co-d、B-p轨道杂化成强Co-B共价键;WC-Co/cBN4N模型中,界面处Co、N原子之间亦存在电荷转移,由Co-d、N-p轨道杂化成弱Co-N共价键.两种模型的界面处,Co-B共价键的布居数更大且键长更小、键能更大,Co-B共价键的作用强于Co-N共价键作用,因此,WC-Co/cBN4B界面结合性能更好,界面更稳定.     

Ag-Cu-Ti连接SiC/SiC接头界面反应和界面结构

三元Ag-Cu-Ti活性钎料连接常压烧结SiC陶瓷。通过XRD(X-ray diffraction)、EPMA(electron probe microanalysis)和TEM(transmission electron microscopy)研究了SiC/Ag-Cu-Ti界面反应和界面结构。结果表明:焊料中的活性元素Ti与SiC发生化学反应在界面处形成连续致密的反应层,界面反应产物为TiC和Ti5Si3,整个界面形成SiC/TiC/Ti5Si3/Ag-Cu-Ti焊料的结构,其中TiC层晶粒大小约为10 nm左右并且连续分布,而Ti5Si3层晶粒大小差异大(100~500 nm)且不连续,这种差异是由于TiC的高成核率和Ti5Si3的低成核率而产生的。     

单粒子在金刚石(001)表面吸附与迁移的第一性原理计算

为了探究纳米金刚石复合薄膜中界面相粒子的微观行为,采用第一性原理方法计算了碳、硅单粒子在清洁金刚石(001)表面的吸附作用与迁移行为.包括C、Si粒子在金刚石(001)面四个高对称位置的构型总能和吸附能以及其在金刚石(001)表面的迁移激活能.结果表明:最稳定的构型是沿(001)生长方向沉积粒子与表面层两粒子相接,且C、Si粒子迁移激活能分别为2.824 eV、0.475 eV.两激活能的差异表明:添加Si能显著促进碳粒子的扩散并形成更加致密的纳米金刚石复合薄膜.     

金刚石膜/硅基体热残余应力场有限元分析

运用ANSYS软件建立了有限元模型,对化学气相沉积在硅基体上的金刚石膜内部和膜/基交界面处的各热残余应力分量的分布作了计算与分析.所建模型与已有的一维解析模型都能得出厚度截面上的法向应力分量的分布,且吻合较好,而前者的优点在于它还能模拟切向应力和剪应力等其它应力分量,这对分析膜/基界面的粘附与失效是至关重要的.     

Ti、V、Ni、Mo对CVD金刚石涂层形核影响

基于密度泛函理论,计算分析了CH₃基团在含有过渡金属元素Ti、V、Ni、Mo的孕镶金刚石颗粒硬质合金基底表面的吸附能、Mulliken电荷分布、电荷密度差和态密度(density of states, DOS)等一系列性质,研究Ti、V、Ni、Mo对孕镶金刚石颗粒硬质合金基底化学气相沉积(chemical vapor deposition, CVD)金刚石涂层形核阶段的影响及其作用机理。计算结果表明:与CH₃基团在WC表面及金刚石表面的吸附相比,Ti、V、Ni、Mo与C原子间有较强的弱相互作用,这使得其对CH₃基团有更强的吸附能力(其中Ti>V>Mo>Ni);吸附能力大小与各原子的价电子结构相关,含有Ti元素的表面对CH₃的吸附最稳定;CH₃基团与Ni原子间更易发生电荷的转移形成共价键,Mo有利于促进CH₃基团的脱氢反应;形核阶段适当添加Ti、V、Ni、Mo这几种过渡金属元素将有利于增加形核密度,改善CVD金刚石膜基界面结合强度。     

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.     

SiC晶片不同晶面的CMP抛光效果对比研究

化学机械抛光(CMP)已被认为是目前实现SiC晶片全局平坦化和超光滑无损伤纳米级表面的最有效加工方法之一,然而SiC晶片的化学氧化反应受其表面极性的强烈影响,从而导致其不同晶面表面原子在CMP过程中的可氧化性以及氧化产物去除的难易程度存在差异.采用K2 S2 O8作为氧化剂、Al2 O3纳米颗粒作为磨粒,对比研究了6H-SiC晶片Si面和C面的CMP抛光效果,并分析不同晶面对其CMP抛光效果的影响机理.结果表明,6H-SiC晶片Si面和C面的CMP抛光效果存在显著差异.6H-SiC晶片Si面的材料去除率在pH=6时达到最大值349 nm/h;相比之下,C面的材料去除率在pH=2时达到最大值1184 nm/h,抛光后的Si面和C面均比较光滑.氧化剂进攻C面上C原子的位阻明显小于其进攻Si面上的C原子的位阻,从而导致C面比Si面具有更高的反应活性和氧化速度.此外,C面上的氧化物比Si面上的氧化物更容易被去除,因此C面比Si面易于获得更高的材料去除率.     

SiC单晶生长热力学和动力学的研究

升华法生长大直径碳化硅(SiC)单晶一直是近年来国内外研究的重点,本文对Si-C系中的Si,Si2,Si3,C,C2,C3,C4,C5,SiC,Si2C,SiC2等气相物种的热力学平衡过程进行了研究,发现SiC生长体系中的主要物种为Si,Si2C,SiC2.生长初期Si的分压较高,从而SiC生长为富硅生长模式.对外加气体进行研究发现,氩气为最好的外加气体,它既可以有效地抑制Si物质流传输,又可以减缓扩散系数随温度升高而递减的趋势.建立了简单一维传输模型,对三个主要物种的动力学输运过程进行了研究,计算得到了两个温度梯度下的主要物种的物质流密度.     

低压Ar气氛下用PS/OCS/Si (111)叠层热解制备单晶4H-SiC薄膜及层错缺陷抑制机理

在一定压力的Ar气氛中对Si (111) 衬底上的PS/OCS(硅的有机化合物)凝胶叠层进行热处理,制备出单晶4H-SiC薄膜.用XPS、XRD、TEM、TED和SEM研究了热处理温度和压力对薄膜结晶质量和晶型的影响.XPS分析显示薄膜中C/Si比为1.09.SEM分析表明薄膜的表面平整,SiC/Si(111)界面清晰、无层错缺陷形成.进一步讨论了层错缺陷形成及抑制的机理.     

金刚石/金属触媒界面表征及金刚石生长的热力学分析

利用场发射扫描电子显微镜(FESEM)和X射线能谱仪(EDS)研究了高温高压触媒法合成金刚石后金刚石/触媒界面的物相组成,发现铁镍元素与碳元素的原子比为3.1: 1,并分析得出高温高压下界面中存在Fe3C、Ni3C物相结构.据此,利用热力学中经典的ΔG<0判定法,计算Me3C(Me:Fe,Ni)物相分解出金刚石的自由能变化.结果表明:在触媒法合成金刚石条件下(1500～1700 K、5～6 GPa),Me3CC(金刚石)+3Me比石墨金刚石的ΔG更负.因此,从热力学角度看,Me3C的形成,尤其是铁基触媒中Fe3C、Ni3C的形成,说明触媒法合成金刚石单晶是来自于Me3C型碳化物的分解,而并非石墨结构的直接转变.     

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.     

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.     

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...     

Study of the possibility of interactive control of the surface profile of X-ray optical elements

We investigate the possibility of controlling the curvature parameters of parabolic mirrors that are modular elements of two types consisting of a base and thin inserts placed at the opposite side of the work surface. In the first type of modular elements, bending is controlled by the difference in the coefficients of the thermal expansion of the base and inserts. In the second type of elements, the profile is changed by the piezoelectric straining of the inserts under an electric field. A correlation is established between the parameters of modular elements and their surface curvature profile.     

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.     

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.