温度对草酸钴腐蚀人造金刚石单晶的影响

在氢、氮混合气氛条件下,采用草酸钴对人造金刚石单晶进行表面腐蚀,利用扫描电镜和显微拉曼光谱对腐蚀后的金刚石进行了表面形貌、腐蚀深度和腐蚀前后结构成分的研究,分析了温度对草酸钴腐蚀金刚石的影响及腐蚀图案的各向异性,并对腐蚀机理做出推理.结果表明:温度的升高会促进金刚石{111}面和{100}面的腐蚀;相比较而言,{100}面比{111}面更易腐蚀;{111}面的腐蚀坑形状多呈六边形和三角形,{100}面倾向于形成四边形.腐蚀有三种可能的机制:(1)金刚石在草酸钴分解出的钴作用下发生石墨化并在钴中扩散;(2)金刚石碳原子在氢气气氛中氢化并扩散;(3)金刚石碳原子和草酸钴分解出的水和二氧化碳发生氧化还原.     

人工合成金刚石表面三角锥缺陷的存在机理研究

天然金刚石主要生长面为{111},在其表面经常会存在大量凹陷的金字塔状或者底面平整的三角锥蚀坑缺陷,这种缺陷很少出现在人工合成金刚石单晶的表面.本研究在高温高压5.4 GPa、1550 K的条件下,以FeNi合金作为触媒,FeS为添加剂,利用温度梯度法(TGM)直接合成金刚石单晶的{111}表面同样发现有大量凹陷的金字塔状或者底面平整的三角锥蚀坑缺陷.而在体系中加入微量单质B时,高温高压直接合成金刚石单晶的{111}表面不仅存在大量金字塔状的三角锥蚀坑,还出现了天然金刚石表面不曾发现的大量规则的三角凸起平台和凸起的金字塔状或者顶面平整的三角锥缺陷.由此推断,尽管天然金刚石{111}表面经常出现的三角锥缺陷可能是在自然环境中后期腐蚀出现的,而在FeNi-C-FeS体系高温高压直接合成的金刚石单晶{111}表面出现的三角锥缺陷却是在晶体生长过程中直接形成的,FeS在这种表面缺陷的形成过程中起着不可或缺的作用.     

高温高压生长宝石级金刚石单晶的表面特征研究

本文利用高温高压温度梯度法,NiMnCo合金作为触媒,分别采用籽晶{100}和{111}作为生长面,合成了Ib型宝石级金刚石单晶,对其表面特征进行了分析和讨论.结果发现,宝石级金刚石单晶的表面特征不具有唯一性,多数情况下,晶体{111}面明显较{100}面平整,而且{100}面生长台阶的棱角不清晰,经常会出现经触媒融融过的痕迹,并且这种现象的出现跟籽晶生长面不同和合成温度条件高低无关;{111}面有时也会出现明显的生长台阶,棱角清晰,并且形状较为规则.宝石级金刚石晶体表面特征的不唯一性说明晶体表面特征对生长条件稳定性有更高的要求.     

常压化学水解反应生长氧化锌晶体

采用ZnCl2·2H2O在常压下高温水解反应生长ZnO晶体,反应温度为500℃.当以SiC为衬底时,可以获得六棱柱形氧化锌晶体,直径约为10μm,长为30～100 μm.当衬底为蓝宝石时,氧化锌沿[0001]呈定向柱状生长,柱的直径为5～10 μm,柱之间具有较多的内部缺陷.当以ZnO为衬底时,在{0001}面,形成连续膜,表面扫描电镜分析表明,晶体具有明显的极性生长特征,[0001]方向呈螺旋柱状生长.在{0001}面,晶体的平整性较好,呈现台阶性生长.     

水热法BSO晶体腐蚀像及与晶体对称的关系

对水热法生长的两种不同结晶习性的 BSO晶体进行了腐蚀像的观察研究,得到了{100}、{110}、{211}、{111}晶面的腐蚀形貌特征,建立了BSO晶体腐蚀像在三维空间分布的立体模型。研究发现不同单形晶面的蚀坑形态不同,但都体现了晶体的对称性。不同晶面腐蚀难易程度与晶体结构有关。     

水热法BSO晶体微形貌及其成因研究

晶体宏观形态和表面微形貌特征是晶体生长机制的具体反映,通过对晶体形貌特征的研究,可以探寻晶体生长的规律,为进一步改善晶体的质量打下基础.本文利用双圈反射测角仪、微分干涉显微镜、倒置金相显微镜等测试手段,对两种不同结晶习性的水热法BSO晶体宏观形态和表面微形貌进行了观察和研究,并探讨了水热法生长的BSO晶体{100}、{110}、{211}、{111}等面族的生长形貌形成原因.     

硫镓银晶体(112)面蚀坑形貌研究

本文报道了一种能在室温下对硫镓银晶体(112)面进行择优腐蚀的新腐蚀液配方,采用新腐蚀液对改进的Bridgman法生长的AgGaS2晶体进行腐蚀,用扫描电镜对蚀坑进行了观察,得到了清晰的(112)面蚀坑形貌,形状为三角锥形.初步解释了蚀坑的形成原因.AgGaS2晶体低指数的{100}面的腐蚀速度较慢,在腐蚀过程中逐渐显露出来,最终使晶体(112)面呈现出三角锥形蚀坑形貌.     

氩气对直流弧光放电PCVD金刚石薄膜晶体特征的影响

本文采用自主研制的直流弧光放电等离子体CVD设备,在YG6硬质合金基体上进行了不同氩气流量下金刚石薄膜的制备研究.采用SEM对金刚石薄膜的晶体特征进行了观察.结果表明,氩气对直流弧光放电等离子体CVD金刚石薄膜的晶体特征有明显影响.在CH_4/H_2恒定时(0.8;),硬质合金基体上制备的金刚石薄膜表面形貌随Ar流量增加而变化的规律,即从以(111)八面体晶面为主→(111)和(100)立方八面体混杂晶面→以(100)立方体晶面为主→菜花状的顺序转变;当Ar流量为420～700 mL/min时,金刚石晶粒的平均尺寸由1.5 μm 逐步增大到7 μm;Ar流量为700～910 mL/min时,金刚石晶粒的平均尺寸由7 μm急剧减小到纳米尺度,约50 nm.     

NiMnCo-C-S系中掺硫金刚石单晶的研究

本文在5.5～5.7 GPa,1450～1550℃的条件下由镍锰钴-石墨-硫体系中合成金刚石单晶.合成的金刚石晶体具有完整的{111}和{100}面,内部有少量包裹体.晶体表面有凹坑,凹坑内有许多细小的孔洞,且有连晶出现.X射线荧光光谱检测结果表明,随着反应体系中硫含量的增加,晶体中硫和锰的含量明显增加,而镍和钴的含量却降低.这由于硫与触媒中的锰发生了反应,改变了合成触媒的成分配比,进而改变了触媒的性质.     

BGO熔体急冷自发结晶形貌

本文研究了BGO熔体在急冷的条件下自发结晶的显露形貌.在急冷的条件下,组成BGO的各个面族自由发育.{321}面族、{211}面族和{111}面族都是按[GeO4]4-四面体以顶角相连的化学键链生长发育的,生长速度快,优先显露,在熔体急冷时保留下来.表面形貌显露不完整的{100}面族是[GeO4]4-四面体以棱相连所对应的面族,生长速度较慢,尚未显露完全熔体就已冷却.从生长速度考虑,在实际生长晶体时以[321]、[211]、[111]方向生长可以获得较快的速度.     

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.     

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.     

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.     

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.