Melting behaviors of carbon underhigh pressures

Abstract

The melting behaviors of graphite and diamond were investigated at pressures up to 25 GPa using flash-heating method. By rapid heating, the metastable graphite was melted in the diamond stable P-T field, competing with its conversion to diamond in the rate of reaction. For the diamond the pressure dependence of inserted energy required to reach the molten state suggested that the melting temperature of diamond increases with pressure.     

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。     

Bulk diamond formation from graphite in the presence of C-O-H fluid under high pressure

Abstract

C-O-H fluids have been successfully applied as catalysts for bulk diamond formation under high pressure. New insight into C-O-H fluids extends the understanding of the origin of natural diamond, which is presently of interest in materials and geological sciences. This review presents current literature data concerning the synthesis and characterization of bulk diamond formation assisted by C-O-H fluids at high pressure and high temperature. Based on a general survey of this subject, the pressure-temperature regime for diamonds formed in these fluids was established and the mechanism of conversion from graphite to diamond is discussed. Finally, a few questions are put forward that may be useful for the continued development of this research area.     

Novel techniques for the prepartion of synthetic diamond

Abstract

The objectives of this work are two fold: (1) to study the effect of using oxygen-acetylene flame grown synthetic diamond as seed crystals for the high pressure-high temperature conversion of graphite into diamond and (2) to demonstrate the ability to produce small crystallites of diamond by a simple, electron beam evaporation technique. In each case, the production of diamond from graphite was confirmed.     

合成金刚石与合成体系之关系

 通过各种材料的试验和压机设备因素的测定，总结了金刚石生长过程的特性：金刚石晶体是在石墨（G）-触媒（Me）界面上生长；因电阻R_(G)>R_(Me)、温度T_(G)>T_(Me)以及与外界热交换等原因，使合成腔内产生压力、温度梯度，成为金刚石生长之驱动力。梯度过大过小对金刚石生长均不利；金刚石晶体在G-Me界面两侧是非对称性生长；每个晶粒表面有一特殊结构约20 μm左右厚的金属薄膜，它起到运载碳源和催化的双重作用。要合成粗粒高强金刚石，需要有一个稳定的合成体系。本文分析了该体系状态的性质及稳定的必要性与稳定的具体方法。     

高温高压下纳米金刚石粉的特性研究

 研究了炸药爆轰合成的纳米金刚石粉在高温（约1 600 K）、高压（5.2 GPa）条件下的行为。将纳米金刚石粉与粉末合金（Ni₇₀Mn₂₅Co₅、100^#）混合、压制成圆片,与合金片 （Ni₇₀Mn₂₅Co₅）和人造石墨片一起交替放入高温高压合成腔体内,进行高温高压实验。实验结果表明：在高温高压条件下,纳米金刚石粉不能长大,反而石墨化了;在相同的高压和保温时间条件下,随着温度的降低,纳米金刚石粉的石墨化程度减弱,纳米金刚石粉的纳米颗粒长大,可长成0.1 mm尺寸的金刚石颗粒（温度为1 070 K左右）。而在此条件下,人造石墨不能合成金刚石,一般金刚石晶体要变成石墨相。这进一步表明,纳米金刚石颗粒表面的活性使得它可以在较低的温度下长成较大颗粒的金刚石。     

纯铁触媒合成磨料级金刚石及表征

本文报道了高温高压下纯铁触媒与石墨体系合成磨料级金刚石的过程,并给出了P-T相图.在此基础上,通过调整工艺参数,控制再结晶石墨量与金刚石生长速度,合成出无色透明的金刚石样品,解决了纯铁触媒合成的金刚石透明度较差及包裹体较多的问题.采用穆斯堡尔谱仪和傅里叶红外光谱仪等测试手段,对金刚石样品内部包裹体以及氮元素含量进行了表征,在揭示包裹体形成机理的基础上提出了减少包裹体的方法,同时阐明了纯铁触媒合成的金刚石样品颜色变浅的原因. 关键词： 铁触媒 金刚石 生长速度 高温高压     

Nano-polycrystalline diamond synthesized through the decomposition of stearic acid

ABSTRACT

Here we report a novel route for synthesizing nano-polycrystalline diamond (NPD) using stearic acid (C₁₈H₃₆O₂) as a starting material under high pressure and high temperature. The obtained NPD shows a transparent dark-yellowish color similar to the standard NPD synthesized from graphite and consists of extremely fine diamond grains (～10?nm). The temperature required for the present synthesis of pure transparent NPD is as low as 1000°C at 13 and 17?GPa, which is surprisingly lower than that for conventional NPD synthesis (1800–2000°C). The amorphous-like, extremely poorly crystalline graphite produced by the thermal decomposition of stearic acid likely provides preferential nucleation sites for diamond and significantly lower the activation energy. The removal of volatile components such as H₂O generated through the decomposition from the system is a key to obtain pore-free transparent NPD. Magnesite, MgCO₃ and periclase, MgO can be used as an efficient H₂O remover through the hydration reaction.     

Synthesis of nano-polycrystalline diamond from glassy carbon at pressures up to 25 GPa

ABSTRACT

Nano-polycrystalline diamond (NPD) with various grain sizes has been synthesized from glassy carbon at pressures 15–25?GPa and temperatures 1700–2300°C using multianvil apparatus. The minimum temperature for the synthesis of pure NPD, below which a small amount of compressed graphite was formed, significantly increased with pressure from ～1700°C at 15?GPa to ～1900°C at 25?GPa. The NPD having grain sizes less than ～50?nm was synthesized at temperatures below ～2000°C at 15?GPa and ～2300°C at 25?GPa, above which significant grain growth was observed. The grain size of NPD decreases with increasing pressure and decreasing temperature, and the pure NPD with grain sizes less than 10?nm is obtained in a limited temperature range around 1800–2000°C, depending on pressure. The pure NPD from glassy carbon is highly transparent and exhibits a granular nano-texture, whose grain size is tunable by selecting adequate pressure and temperature conditions.     

高温高压触媒法金刚石生长的热力学分析

 利用热力学中经典的ΔG<0判定法,探讨了Fe基触媒合成金刚石晶体生长中的碳源问题,在计算中考虑了各物相的体积随温度和压力的变化。结果表明：在金刚石形成之前,就有大量Fe₃C形成,而在触媒法合成金刚石的温度和压力范围内,Fe₃C→C(金刚石)+3γ-Fe反应自由能和石墨→金刚石相变自由能均为负值,但前者比后者的绝对值更大,这说明前者更容易发生。因此,从热力学角度看,Fe₃C的形成降低了石墨转变为金刚石所要越过的势垒,使用Fe基触媒合成金刚石单晶的生长来源于Fe₃C的分解而不是石墨的直接转化。同时推导出在1200 K以上石墨-金刚石的平衡p-T关系：p_eq(GPa)=1.036+0.00236T (K),与F.P.Bundy的平衡线非常接近,证明了本热力学计算方法的可行性。     

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.     

高温高压条件下石墨的再结晶与金刚石单晶的生长

 用电子显微镜观察到了在高温高压条件下再结晶石墨的形状随温度变化而改变的规律。实验表明：从石墨向金刚石的转变，与石墨在催化剂——溶剂合金中的再结晶状态有关，类球形再结晶石墨是转变成金刚石小单元的基础。金刚石晶体的不同形态及其多样化的表面结构表明金刚石单晶的生长具有比较复杂的过程。研究了具有一定规则形状由类球形再结晶石墨晶粒组成的聚合体，这种聚合体将在适当温度压力下转变成金刚石颗粒。本研究给出了生长粗颗粒、晶形完整的金刚石单晶的原则办法。     

Growth of diamond thin film on tool materials from a gas phase

Abstract

In the present paper, diamond films have been synthesized on tungsten carbide, sintered diamond and high pressure diamond by hot filament chemical vapour deposition method from the mixture gas of methane and hydrogen, and growth features of diamond were studied.     

Strength and plastic deformation of polycrystalline diamond composites

ABSTRACT

The use of nanopolycrystalline diamond has allowed a systematic study on deformation of polycrystalline diamond composites (PCDCs). Bulk PCDCs samples containing either Co or SiC as a binding agent were deformed under high pressure and temperature to strains up to 18% at strain rates ～10^?5?s^?1. All samples exhibit strong work hardening. The strength of PCDCs depends on the amount and type of binding agents and is consistently weaker than that of diamond single crystals. The weakening may be due to the binder materials, which play an important role in affecting grain boundary structures. In SiC-based PCDC, significant grain fragmentation occurs. Nearly all grain boundaries are wetted by SiC after large deformation, resulting in lower strength. In Co-based PCDC, the microstructure is dominated by dislocations, deformation twins, and separated grain boundaries. The density of deformation twins increases significantly with strain, with the twin domain width reaching as low as 10–20?nm at 14% strain.     

从碳化硅和铁体系合成金刚石

 为了探明从SiC生成金刚石这一过程中触媒作用的机理，有必要调查SiC加不同金属在高压高温下的行为。在本工作中，以16重量比混合的SiC和铁粉经5.4~6.0 GPa的高压力和1 300~1 500 ℃的高温处理20 min后，样品的X射线衍射分析表明：所有实验条件下SiC都发生了分解，并分别生成了Fe₃Si和Fe₃C；温度越高，SiC分解得越彻底，在温度高于1 375 ℃的样品中，伴随Fe₃C减少，有金刚石和石墨明显析出。扫描电镜观察表明：6.0 GPa、1 500 ℃下所得的金刚石晶体具有完整的八面体晶形，平均粒度约50 μm。     

模板对异构体选择性生长的动力学控制作用与化学气相沉积金刚石的生长机理

阐述了模板的动力学控制作用对大尺度有序结构特别是亚稳相的生长，对自由能相差很小的异构体的选择生长所具有的重要作用.汲取现有金刚石生长理论的合理思想，以模板概念为基础给出了对化学气相沉积(CVD)过程的动力学热力学综合描述：1)碳原子在碳氢化合物中的化学势高于固相碳，气相碳氢化合物的碳原子有可能落到化学势较低的固态碳的各种异构体.2)气相碳通过表面反应实现向固相碳的转化.3)表面的模板作用是控制气相碳原子转换方式的主要动力学因素，不同的表面(石墨各种取向的表面及金刚石不同取向的表面)选择了落入其上的碳原子的结构方式及能量状态.4)因此,衬底的不同区域可发生几种不同的独立的表面反应过程,这些反应对应于不同表面的生长.5）而这些表面反应的方向性及速度受表面临域热力学因素的影响，反应的方向性决定了某种晶面是生长或刻蚀，在特定的温度、压强及各种气体分压下可以实现金刚石的生长和石墨的刻蚀.6)衬底局域晶格结构及键价结构和衬底表面气相的温度、压强及各种气体分压等热力学条件共同决定了成核的临界条件.7）与外界有能量和物质交换的等离子体系统，以及气相中发生的一系列化学反应，仅起到了维持某种固相表面生长所需要的非平衡热力学条件和化学条件的作用.金刚石和石墨表面具有的模板动力学控制作用，在特定热力学条件下主导自身外延层的生长方式；异质衬底的某些局域微观结构可以作为新相生长成核的局域模板；不同材料、不同的处理方法、及不同的化学环境下的衬底具有不同的局域微观结构，从而决定了多晶薄膜的取向优势. 关键词： 模板 异构体 选择性生长 金刚石薄膜     

Growth of gem-grade nitrogen-doped diamond crystals heavily doped with the addition of Ba（N3）2

Additive Ba(N 3) 2 as a source of nitrogen is heavily doped into the graphite-Fe-based alloy system to grow nitrogendoped diamond crystals under a relatively high pressure (about 6.0 GPa) by employing the temperature gradient method.Gem-grade diamond crystal with a size of around 5 mm and a nitrogen concentration of about 1173 ppm is successfully synthesised for the first time under high pressure and high temperature in a China-type cubic anvil highpressure apparatus.The growth habit of diamond crystal under the environment with high degree of nitrogen doping is investigated.It is found that the morphologies of heavily nitrogen-doped diamond crystals are all of octahedral shape dominated by {111} facets.The effects of temperature and duration on nitrogen concentration and form are explored by infrared absorption spectra.The results indicate that nitrogen impurity is present in diamond predominantly in the dispersed form accompanied by aggregated form,and the aggregated nitrogen concentration in diamond increases with temperature and duration.In addition,it is indicated that nitrogen donors are more easily incorporated into growing crystals at higher temperature.Strains in nitrogen-doped diamond crystal are characterized by micro-Raman spectroscopy.Measurement results demonstrate that the undoped diamond crystals exhibit the compressive stress,whereas diamond crystals heavily doped with the addition of Ba(N 3) 2 display the tensile stress.     

FEM simulations and experimental studies of the temperature field in a large diamond crystal growth cell

We investigate the temperature field variation in the growth region of a diamond crystal in a sealed cell during the whole process of crystal growth by using the temperature gradient method (TGM) at high pressure and high temperature (HPHT). We employ both the finite element method (FEM) and in situ experiments. Simulation results show that the temperature in the center area of the growth cell continues to decrease during the process of large diamond crystal growth. These results are in good agreement with our experimental data, which demonstrates that the finite element model can successfully predict the temperature field variations in the growth cell. The FEM simulation will be useful to grow larger high-quality diamond crystal by using the TGM. Furthermore, this method will be helpful in designing better cells and improving the growth process of gem-quality diamond crystal.     

Peculiarities of phase transitions when synthesizing diamond in high pressure apparatus of various types

Abstract

The influence of P, T-parmeters and duration of heat when synthesizing diamond in high pressure apparatus both of recessed anvil-type and cylindrical type (belt-type) on properties of diamond powders was studied. The dependence of pressure in reaction cells on temperature of force elements of apparatus in initial state and on efficiency of high pressure production in a reaction cell before heating was shown.     

D-D结合型金刚石聚晶的高压合成研究

 为了探索功能金刚石聚晶的高压合成，使其具有优异的透红外和散热性能，我们采取了提高合成压力、温度和尽量减少结合剂的办法进行试验。首先探索如何使合成的金刚石聚晶具有D-D型结合，然后尽量减少结合剂，以合成出高密度的D-D型金刚石聚晶。为了尽量减少结合剂含量，不用粉末混合法，而是分别采用7~14 μm和63~80 μm粒度的金刚石为原料，与纯Ni或Ni₇₀Mn₂₅Co₅合金为基底积层组装，通过高温高压下触媒金属向金刚石晶粒间渗透进行烧结生长。在6.3 GPa的压力和1 440~1 650 ℃的不同温度下分别保持3~40 min。所得到的金刚石聚晶在触媒金属渗透得充分的区域形成了D-D结合型结构，而没有发现碳化物生成及金刚石表面石墨化等现象。