Phase Diagrams and Synthesis of Diamond

For reasons of phase equilibria, the lowest temperatures T min , above which at high pressures the diamond crystallization from melt solutions is allowable in terms of thermodynamics, have been found for a number of metal-carbon systems. In the Ta-C and Nb-C systems, the diamond synthesis is possible at temperatures below T min , while to synthesize diamond in the Mg-Zn-C system, the temperatures much higher than T min , are required because of the necessity to overcome the kinetic difficulties.     

Ib型金刚石大单晶的限形生长

金刚石的限形生长有利于其后续加工.对于磨料级金刚石限形生长的研究已经比较透彻,但金刚石大单晶的限形生长尚缺乏全面系统的研究.本文以Fe Ni(64wt%:36wt%)合金为触媒,利用高温高压下的温度梯度法在5.6 GPa时对不同温度下分别沿(100)面和(111)面生长的Ib型金刚石大单晶的晶形进行了研究.研究表明:随着温度的升高,沿(100)晶面生长的金刚石大单晶的晶形分别为板状、塔状直至尖塔状,而沿(111)面生长的金刚石大单晶的晶形则分别为塔状和板状;分析了不同温度下分别沿(100)面和(111)面生长金刚石大单晶不同晶形高径比的变化情况.利用不同压力和温度下的金刚石大单晶合成实验绘制了沿(100)和(111)面生长金刚石大单晶的晶形在V形生长区域内的分布示意图,表明沿(111)面生长的金刚石大单晶V形区温度下限明显比以(100)面生长的高,而沿这两面生长金刚石大单晶的V形区温度上限差别并不明显.对不同生长面V形区温度上下限的差别进行了解释,据此实现了Ib型金刚石大单晶的限形生长.     

高压熔渗生长法制备金刚石聚晶中碳的转化机制研究

在6 GPa和1500 ℃的压力和温度范围内, 利用高压熔渗生长法制备了纯金刚石聚晶, 深入研究了高温高压下金刚石聚晶生长过程中碳的转化机制. 利用光学显微镜、X-射线衍射、场发射扫描电子显微镜检测, 发现在熔渗过程中金刚石层出现了石墨化现象, 在烧结过程中金刚石颗粒表面形貌发生了变化. 根据实验现象分析, 在制备过程中存在三种碳的转化机制: 1)金属熔渗阶段金刚石颗粒表面石墨化产生石墨; 2)产生的石墨在烧结阶段很快转变为填充空隙的金刚石碳; 3)金刚石直接溶解在金属溶液中, 以金刚石形式在颗粒间析出, 填充空隙. 本文研究碳的转化机制为在高温高压金属溶剂法合成金刚石的条件下(6 GPa和1500 ℃的压力和温度范围内)工业批量化制备无添加剂、无空隙的纯金刚石聚晶提供了重要的理论指导.     

Transformation of Carbon Nanotubes to Diamond at High Pressure and High Temperature

The synthesis of diamond at high pressure and high temperature and the discovery of fullerenes and carbon nanotubes are among the most important achievements in carbon science. In the present work, we report the synthesis of diamond from carbon nanotubes at 4.5 GPa and 1300°C. Under these conditions, no diamond crystals were obtained when graphite was used as the starting material. The detailed investigation shows that at high pressure and high temperature carbon nanotubes first transform into quasi-spherical onion-like structures and then into diamond crystals. Our work suggests that carbon nanotubes can be used for the synthesis of high-quality diamond crystals at lower pressure and temperature.     

温度对Ib型和IIa型金刚石大单晶(100)表面特征的影响

本文在5.6 GPa, 1250–1340 ℃的条件下, 利用温度梯度法, 以FeNiMnCo 合金为触媒, 沿籽晶的(100)晶面成功合成了不同晶形的优质Ib型和IIa型金刚石大单晶. 利用激光拉曼附件显微镜, 分别对上述不同温度下合成的两类金刚石样品上表面(100)面的中心区域及棱角区域进行观察分析. 研究发现, Ib型和IIa型金刚石大单晶(100)晶面上从中心到棱角处黑色纹路的分布逐渐变黑变密集; 另外, 随着金刚石合成温度的升高, Ib型金刚石大单晶(100)面上黑色纹路由稀疏逐渐变稠密, 而IIa型金刚石大单晶的黑色纹路较为稀疏; Ib型金刚石大单晶的形貌特征表现为从低温晶体的不规则分布过渡到中温、高温晶体的典型树枝状分布. IIa型金刚石大单晶(100)面特征随温度变化规律与Ib型的类似. 这两类金刚石大单晶表面特征的差异可能是由于IIa 型金刚石具有比Ib型更小的生长速度和更少的氮含量. 最后, 对两类塔状金刚石大单晶进行拉曼光谱测试分析, 结果表明IIa型金刚石大单晶的品质较Ib型金刚石大单晶好.     

Effect of deuterium on phase transformations in fullerenes at high temperatures and high pressures

The effect deuterium has on phase transformations is studied for amorphous and crystalline fullerenes C₆₀ and C₇₀ at high temperatures of up to 1300°C and high pressures (2–8 GPa). Amorphous fullerene phases are obtained via long grinding in a planetary mill. Structure is studied by means of neutron diffraction. In all cases, amorphous graphite (nanographite) forms in the temperature range of 800–1100°C. This material has different diffraction spectra distinguished by the heights of the halos observed on the graphite diffraction maxima and their relative intensities. These spectra (the structure of nanographite) are affected by preliminary amorphization, the number of carbon atoms in the fullerenes (C60 or C70), and the introduction of deuterium atoms. The different spectra of amorphous (disordered) graphite testify to its varying structure.     

Currently available methods of industrial nanodiamond synthesis

The main theoretical aspects of detonation decomposition of powerful mixed explosives with a negative oxygen balance accompanied by the formation of nanodiamonds (ultrafine-dispersed diamonds, UDDs) are described. The basic UDD synthesis parameters are considered, and the expediency of using trotyl-hexogen alloys is shown. The conditions of diamond phase conservation in the detonation products are specified. Various versions of industrial detonation synthesis of UDDs are considered. The most efficient technology of chemical cleaning of UDDs (with nitric acid at high temperatures and pressures) for producing UDDs with the highest purity is described.

     

Diamond anvil cell, 50th birthday

The year 2008 marked the fiftieth birthday of the diamond anvil cell. Its birth took place when Alvin Van Valkenburg, while working with his colleagues, Charles E. Weir, Ellis R. Lippincott, and Elmer N. Bunting, first realized that he could look right through one of the diamond anvils and see a sample while it was at high pressure. In the following years, these scientists and many others adapted the diamond anvil cell to a wide variety of analytical techniques that have provided an impressive amount of information about materials at high pressures and high temperatures. But, virtually all of those techniques start with looking into the diamond anvil cell.     

Dry mixing of diamond and n-layered graphene powders substantially different in density and particle size

In this paper, the two-stage process of the uniform distribution of n-layer graphenes in a mixture for sintering polycrystalline diamond at high pressures and temperatures is described. Due to the preliminary deposition of a nanopowder layer on the surface of diamond crystals, at the second stage of mixing the uniform application of a layer of the n-layer graphenes powder on the prepared surface and mixture uniform in the properties are achieved. This approach ultimately makes it possible to produce diamond polycrystals stable in properties. In particular, the current-conducting diamond polycrystals are obtained.     

压力对纳米金刚石膜生长的影响

纳米金刚石膜具有高耐磨能力和低摩擦系数,在多个领域有广阔的应用前景。纳米金刚石膜可通过热丝化学气相沉积方法进行制备。其中,系统压力是关键的参数,适当的压力下可生长纳米金刚石膜,而改变压力则金刚石膜的表面形态将发生变化。实验通过不同压力下制备金刚石膜,采用扫描电镜进行形貌观察,并通过拉曼光谱确定纳米金刚石结构。实验表明,金刚石膜形态随压力变化而改变,一定压力下生长出纳米金刚石膜,降低压力则晶体颗粒变粗。分析其原因是与氢原子的运动密切相关。     

Single crystal x-ray diffraction with a synchrotron source in a mdac at low temperature

Abstract

A new diamond anvil cell and a helium flow cryostat have been developed for x-ray diffraction on single crystals at low temperatures and high pressures using the white radiation of a synchrotron beam. This novel instrument especially enables continuous change of sample temperature and pressure without any adjustment of alignment. A minimum temperature of 46 K has been reached.

Presented at the IUCr Workshop on ‘Synchrotron Radiation Instrumentation for High Pressure Crystallography’, Daresbury Laboratory 20-21 July 1991     

Enhanced hardness of CVD diamond after high pressure and high-temperature treatments

The diamond thick layers prepared using chemical vapor deposition (CVD) methods have been treated at high pressures and high temperatures (HP-HT). It was found that the Vickers hardness of the HP-HT treated bulks was nearly two times as high as that of the starting CVD diamond samples. The hardness of the samples treated at 8?GPa and 1800°C is ～80?GPa at a loading force of 49?N, close to that of the single-crystal diamond (～100?GPa). In addition, the oxidation resistance of CVD diamond samples was also enhanced greatly after HP-HT treatments, and the diamondization of sp² bonded carbon in the CVD diamond samples could occur at 7–8?GPa and 1600–1800°C. The HP-HT conditions of diamondization in our works are much lower than the case of the graphite-to-diamond direct transformation without the presence of catalyst (>15?GPa and 2000°C).     

离子辐照与碳纳米结构体的合成

阐述了在离子辐照下生成各种碳纳米结构体研究的发展现状,探讨了相应的生长机制和一些相变机理 ,提出了一些有待解决的问题 ,并对其发展方向作了展望. The synthesis of carbon nanostructures, such as fullerenes, nanotubes, onions and diamond, by using ion irradiation, has been reviewed and the growth mechanisms of these carbon nanostructures as well as their phase transitions are simply discussed. It shows that high density plasma engendered by ion irradiation plays an important role in the growing of carbon nanostructures. In addition, it indicates that ion irradiation, due to its great flexibility of experimental parameters, is enormously convenient in...     

不同添加剂对超细晶粒度金刚石烧结体组织和性能的影响

 本文研究了形成强碳化物的元素，和触媒金属镍作添加剂得到的超细晶粒度金刚石烧结体在显微组织上的差异。讨论了两种不同类型添加剂在超高压高温下烧结所起的作用。对含不同类型添加剂的金刚石烧结体进行了耐磨性、抗氧化性等性能的测定。     

金属包裹体的变化及对人造金刚石强度的影响

 当温度超过1 000 ℃时，人造金刚石中的金属触媒包裹体，在形态、结构和成份上都将发生改变，并且这种变化会在金刚石晶格内造成尺寸更大的缺陷区域，因此在表面氧化不起决定性作用的情况下，金属触媒包裹体的这种变化，就成了导致金刚石强度下降的最直接的原因。我们对在氩气保护下、不同温度处理的一系列人造金刚石样品进行了强度测量，并用SEM、X射线衍射及光学显微镜等手段观测了金刚石断裂表面上的包裹体及其形态变化。我们的实验结果证实了上述结论。我们还发现，金属触媒包裹体的存在极大地影响着金刚石的热稳定性，它们使金刚石在1 000 ℃左右即可向石墨转化。     

Gold under high pressure

Abstract

First principle predictions for the equation of state of gold using solid and liquid state theories are compared up to combined pressures and temperatures of 600 GPa and 17 000 K with static diamond anvil cell compression, ultrasonic measurements and shock Hugoniot data which include a recent laser driven shock Hugoniot points at 600 GPa. Excellent agreement between theoretical and experimental data is observed. The theoretically estimated 300 K isotherm agrees to within 2 GPa with the isotherm that has been measured to 70 GPa using the diamond anvil cell. The structural energy estimates show that the normal f.c.c. phase remains stable under pressure. The estimate of the shock Hugoniot temperature of gold at 600 GPa based on a liquid state model is consistent with the measurements of laser induced shock luminescence, which in fact provides an experimental determination of the temperature of gold above its Hugoniot melting point. The powerful means provided by theory in the prediction of material properties of gold at ultra high pressures and temperatures is significant because gold is an efficient converter of laser energy into soft X-rays and is a potential candidate as a standard for high pressure, high temperature work.     

Large single crystal diamond grown in FeNiMnCo-S-C system under high pressure and high temperature conditions

Large diamonds have successfully been synthesized from FeNiMnCo-S-C system at temperatures of 1255-1393 ℃and pressures of 5.3-5.5 GPa.Because of the presence of sulfur additive,the morphology and color of the large diamond crystals change obviously.The content and shape of inclusions change with increasing sulfur additive.It is found that the pressure and temperature conditions required for the synthesis decrease to some extent with the increase of S additive,which results in left down of the V-shape region.The Raman spectra show that the introduction of additive sulfur reduces the quality of the large diamond crystals.The x-ray photoelectron spectroscopy(XPS) spectra show the presence of S in the diamonds.Furthermore,the electrical properties of the large diamond crystals are tested by a four-point probe and the Hall effect method.When sulfur in the cell of diamond is up to 4.0 wt.%,the resistance of the diamond is 9.628×10~5 Ω·cm.It is shown that the large single crystal samples are n type semiconductors.This work is helpful for the further research and application of sulfur-doped semiconductor large diamond.     

Plasma etching of cavities into diamond anvils for experiments at high pressures and high temperatures

We describe a method for precisely etching small cavities into the culets of diamond anvils for the purpose of providing thermal insulation for samples in experiments at high pressures and high temperatures. The cavities were fabricated using highly directional oxygen plasma to reactively etch into the diamond surface. The lateral extent of the etch was precisely controlled to micron accuracy by etching the diamond through a lithographically fabricated tungsten mask. The performance of the etched cavities in high-temperature experiments in which the samples were either laser heated or electrically heated is discussed.     

The formation of a diamond layer on a carbide substrate during diamond interaction with Si,WC and Co

Abstract

A diamond layer was formed on a carbide substrate in an irregular temperature field at high pressures (HP). A gradient scheme of HP cell set-up has been developed, which provides for a simultaneous impregnation of opposite planes of a diamond layer by components that differ in melting temperature. The cell temperature field has been calculated and physico-mechanical properties of the obtained composite material have been studied.     

用表面生长CVD金刚石的石墨合成高压金刚石

 用热灯丝CVD方法在多晶石墨衬底表面制备CVD金刚石颗粒，并用这种石墨在高温高压条件下采用六面顶压机合成出高压金刚石。初步实验结果表明：采用其表面生长CVD金刚石颗粒的石墨合成高压金刚石，可以提高金刚石的转化率和降低合成压力。