On phase diagrams and on cBN formation in the system BN-Ca3B2N4

Abstract

The phase diagrams of Ca₃B₂N₄ and of the system BN-Ca₃B₂N₄ has been studied by high pressure differential thermal analysis Ca₃B₂N₄ has 3 structural phases and melts at higher temperature. The system BN-Ca₃B₂N₄ formes an eutectic melt and cBN is synthesized by nucleation and crystal growth.     

High pressure produced textured wurtzitic BN with unusually low thermal stability

Abstract

An abnormally low wBN thermal stability, caused by the imperfection of the structure, has been observed for the material produced under high static pressures from pyrolytic rBN. Endothermic wBN→rBN transformation occurs in 490–710 K range by the inverse crystallographic mechanism.     

Thermal phase stability of rhombohedral boron nitride

Abstract

Thermal phase stability of rhombohedra] boron nitride has been studied between 0 and 8 GPa from 300 to 2700 K. Analysis of the data obtained points to the decisive role of kinetic factors in the rBN phase transformations, the structure and dispersity of the samples under study being of great importance. rBN phase transformations in the cBN thermodynamic stability region of the equilibrium p,T phase diagram for boron nitride occur according to Ostwald stepwise principle by the rBN→hBN→(wBN)→cBN scheme.     

A new boron nitride phase diagram and chemical interaction in the B-N system at high pressures

Abstract

The analysis of the experimental data on the interaction of boron and its compounds with ammonia, nitrogen and hydrazine at 0.5–8.0 GPa and 600 to 1600 K was carried out in the frame of the new conception of phase p, T-diagram for the boron nitride. The results obtained show that in the E-N system an alternative metastable behavior of the forming boron nitride is observed in a wide p,T-range. And a considerable amount of the data obtained cannot be explained on the basis of the generally accepted view on the EN polymorphism.     

Mg3N2和Mg3B2N4触媒的研究

 本文由实验确定了常压下合成的Mg₃B₂N₄触媒和Mg₃N₂-BN体系在高温高压下都转变成相同的高压相Mg₃B₂N₄。本文还讨论了Mg₃B₂N₄和Mg₃N₂触媒的异同。认为用常压合成的Mg₃B₂N₄作为初始触媒对于合成立方氮化硼是有利的。     

Boron nitride phase diagram. State of the art

Abstract

From recent experimental data on BN thermodynamic propeties, the equilibrium phase diagram for boron nitride has been plotted, which differs from the generally accepted Bundy-Wentorfs one. At atmospheric pressure cubic boron niride has been shown to be a thermodynamically stable modification up to temperatures of 1600 K, which drastically changes the established notions of BN polymorphism, based on assumed analogy of phase diagrams for carbon and boron nitride. These studies have shown that according to the proposed equilibrium phase diagram the threshold pressure of cBN crystallization can be reduced from 4 down to 2 GPa with the supercritical fluids present, which opens new fields for developing methods for cBN low-pressure synthesis.     

用(C2H5)2O·BF3和Li3N苯热合成cBN机理探讨

 以(C₂H₅)₂O·BF₃和Li₃N为原料，于苯热条件下合成氮化硼并研究其相变机理。X射线粉末衍射和傅立叶变换红外吸收光谱分析证明，产物中不仅有hBN和cBN物相存在，而且还发现了正交氮化硼（oBN）和锂硼氮的常压相Li₃BN₂(O)及高压相Li₃BN₂(T)存在。分析了Li₃BN₂在高温高压条件下和在苯热条件下对合成cBN催化机制的差异，探讨了Li₃BN₂在以Li₃N和(C₂H₅)₂O·BF₃为原料合成BN的催化机制，提出常压相Li₃BN₂(O)和高压相Li₃BN₂(T)分别对生成cBN和oBN起催化作用的观点。     

掺氢、掺氮碳纳米线的合成及其焊接

利用一种有效而别致的双离子(N⁺和Ar⁺)辐照和热处理技术合成并焊接无定形碳纳米线(ACNWs).实验样品用高分辨透射电子显微镜(HRTEM)进行了表征证实,适当搭配的双离子辐照与热处理的结合将会引起多壁碳纳米管无定形化并导致相互交叉纳米线的焊接.此外碳结构相变中的原子演化也在目前已有的概念基础上进行了简单地讨论.关键词：无定形碳纳米线相变透射电子显微镜     

Thermodynamic stability of solid and fluid phases in the Si3B3N7 system

We investigate the thermodynamic properties of the ceramic material Si₃B₃N₇ which has so far only been synthesized as an amorphous compound. Using Monte Carlo simulations, we investigate the stability of both solid and fluid phases of Si₃B₃N₇, in order to gain insights into the proper synthetic conditions needed to generate the stable amorphous and crystalline phases of this compound. We study the ternary liquid–gas region of the phase diagram at temperatures above the theoretical glass transition in this system, and construct an approximate ‘metastable’ phase diagram of Si₃B₃N₇. In addition we study the stability of the amorphous and crystalline phases in the solid state against the decomposition into the binary phases h-BN and β-Si₃N₄ as a function of the size of the crystallites involved, and the stability of the melt against evolution of nitrogen as a function of nitrogen pressure.     

High pressure studies of viscosity effects on isomerization

Abstract

The viscosity dependence of the isomerization process with comparatively low potential barrier was studied as a model of one-dimensional barrier crossing.

We found that the ground-state isomerization of DODCI fails to fit the Kramers equation. We analyzed this non-Kramers behavior by means of an approach of frequency dependent friction.     

纳米结构超硬材料的机遇与挑战

经过几十年的研究和发展,纳米结构金刚石和立方氮化硼已相继被成功制备,其高硬度和强韧性充分表明纳米力学增强机制是制备超强超硬材料的有效途径。目前纳米结构超硬材料的研究仍处于起步阶段,高温高压相转变的路径与机制、复杂中间相的结构与产生的条件、热力学条件对晶粒生长和微结构(孪晶和堆垛层错等)形成的作用,以及超硬材料的纳米结构对力学性能和强化机制的影响等尚未完全揭示出来。为此,文章对近年来在相关领域的研究进行综述,总结了设计与寻找超硬材料的一般策略与原则,概括了典型的纳米微结构对超硬材料力学与热稳定性的影响,归纳了纳米结构超硬材料的高温高压相变与转化机制,并对当前的研究进展和潜在应用进行了归纳与展望。     

Polyamorphism in water

Water, the most common and important liquid, has peculiar properties like the density maximum at 4 °C. Such properties are thought to stem from complex changes in the bonding-network structure of water molecules. And yet we cannot understand water. The discovery of the high-density amorphous ice (HDA) in 1984 and the discovery of the apparently discontinuous change in volume of amorphous ice in 1985 indicated experimentally clearly the existence of two kinds of disordered structure (polyamorphism) in a one-component condensed-matter system. This fact has changed our viewpoint concerning water and provided a basis for a new explanation; when cooled under pressure, water would separate into two liquids. The peculiar properties of water would be explained by the existence of the separation point: the liquid-liquid critical point (LLCP). Presently, accumulating evidences support this hypothesis. Here, I describe the process of my experimental studies from the discovery of HDA to the search for LLCP together with my thoughts which induced these experiments.     

非晶态合金与氢相互作用的研究进展

非晶态合金在力学性能、耐磨耐蚀性、磁性等方面比传统晶态合金具有显著优势,是一类有优良应用前景的新型结构与功能材料.非晶态合金与氢相互作用可以产生很多有趣的物理化学现象和应用.本文从物理基础和材料应用两个方面评述非晶态合金和氢相互作用的研究进展,在物理基础研究方面,从氢在非晶态合金中的存在状态出发,讨论氢在非晶态合金中的溶解、分布、占位和扩散等相关物理问题,进而分析氢对非晶态合金的热稳定性、磁性、内耗、氢脆等的影响.在材料应用研究方面,对非晶态储氢合金、非晶态合金氢功能膜、吸氢改善非晶态合金的塑性和玻璃形成能力、氢致非晶化、利用非晶态合金制备纳米储氢材料等方面的研究进展进行评述.最后总结并展望有关非晶态合金与氢相互作用的研究和应用.     

高温高压条件下三氧化二硼相变过程的研究

详细考察了三氧化二硼在高温高压条件下的相变过程。研究结果表明,在高温高压条件下,三氧化二硼经历了从立方晶系向六方晶系、正交晶系和非晶相的相变。文中还比较详细地讨论了高温、高压两种因素对结构相变的影响,以及静高压熔态淬火方法在非晶态材料制备方面所具有的独到之处。     

单壁氮化硼纳米管的结构、对称性和晶格动力学

本文分析了氮化硼纳米管的结构对称性,并对其晶格振动模的对称性进行了分类。计算了单壁氮化硼纳米管的声子色散关系,给出了扶手椅管和锯齿管拉曼和红外活性模的频率随管径的变化规律。     

Surface properties of cubic boron nitride thin films

Studying the surface properties of cubic boron nitride (c-BN) thin films is very important to making it clear that its formation mechanism and application. In this paper, c-BN thin films were deposited on Si substrates by radio frequency sputter. The influence of working gas pressure on the formation of cBN thin film was studied. The surface of c-BN films was analyzed by X-ray photoelectron spectroscopy (XPS), and the results showed that the surface of c-BN thin films contained C and O elements besides B and N. Value of N/B of c-BN thin films that contained cubic phase of boron nitride was very close to 1. The calculation based on XPS showed that the thickness of hexagonal boron nitride (h-BN) on the surface of c-BN films is approximately 0.8 nm.