Valance electron structure of carbide-diamond interface and catalytic mechanism for diamond synthesis under high-pressure and high-temperature

The metallic films surrounding a synthetic diamond formed under high-pressure and high-temperature (HPHT) in the presence of Fe-based and Ni-based catalysts were studied by scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM). It was showed that the carbide was the primary carbon source for the nucleation and growth of diamond. Based on the EET (empirical electron theory in solid and molecules) theory, the valence electron structure of interface between carbide (Fe₃C, Ni₃C, (Fe, Ni)₃C) and diamond was calculated using the bonding length difference (BLD) method. The boundary criterion of Thomas-Fermi-Dirac-Cheng (TFDC): “the electron density being equal on the contacting surfaces of atoms” was applied to analyze the valence structure of carbide-diamond interface. The result based on the calculation valance electron structure is in good accordance with the experimental result. This study is very helpful to reveal the catalytic mechanism of diamond nucleation and growth and design the new catalyst for diamond synthesis.     

Study on growth of coarse grains of diamond with high quality under HPHT

The growth of coarse grains of diamond was observed with graphite as carbon source and Fe₈₀Ni₂₀ alloy powder as catalyst at HPHT in a China-type SPD 6×1670T cubic high-pressure apparatus with highly exact control system. To synthesize coarse grains of diamond crystal with high quality, advanced indirect heat assembly, powder catalyst technology and catalyst with optimal granularity were used. Especially the nucleation of diamond and the growth rate were strictly controlled by the optimized synthesis craft. At last, diamond crystals (about 0.85 mm) in the perfect hex-octahedron shape were successfully synthesized at ~5.4 GPa and ~1360℃ in 60 min. The characteristic of crystal growth with powder catalyst technology under HPHT was discussed. The results and techniques might be useful for production of coarse grains of diamond.     

Mechanism of diamond-to-graphite transformation at diamond-stable conditions

The diamond-to-graphite transformation at diamond-stable conditions is studied by temperature gradient method （TGM） under high pressure and high temperature （HPHT）, although it is unreasonable from the view of thermodynamic considerations. It is found that, at diamond-stable conditions, for example, at 5.5 GPa and 1550 K, with fine diamond grits as carbon source and NiMnCo alloy as metal solvent assisted, not only large diamond crystals, but metastable regrown graphite crystals would be grown by layer growth mechanism, and the abundance of carbon source in the higher temperature region is indispensable for the presence of metastable regrown graphite crystals. From this transformation, it is concluded that, with metal solvent assisted, although the mechanism of crystal growth could be understood by the macro-mechanism of solubility difference between diamond and graphite in metal solvents, from the point of micro-mechanism, the minimum growth units for diamond or graphite crystals should be at atomic level and unrelated to the kinds of carbon source （diamond or graphite）, which could be accumulated free-selectively on the graphite with Sp2Tr or diamond crystals with sp3 bond structure.     

Effect of additive boron on type-Ib gem diamond single crystals synthesized under HPHT

The boron-doped type-Ib gem diamond crystals were synthesized successfully by adding amorphous boron into a system of graphite and Kovar catalyst under high pressure and high temperature (HPHT).The effect of additive boron on type-Ib gem diamond was extensively studied including the growth characteristic,morphology and nitrogen concentration.The synthesized boron-doped type-Ib gem diamond crystals were characterized by optical microscope (OM),scanning electron microscope (SEM) and infrared spectrometer (IR)...     

电镀晶种法合成金刚石单晶实验研究

目的寻求一种合成金刚石大单晶的有效方法。方法采用在金刚石单晶上面电镀一层金属镍膜作为触媒,镀有镍膜的金刚石晶种被规则地放在石墨片上预先刻好的洞中,每两个洞之间保持相等的间距,然后与其他石墨片交替组装在高温高压下进行实验合成。结果实验结果表明,在合成压力、温度和时间分别~5.8 GPa、~1 460℃和14 min的条件下,合成后的单晶尺寸约是原晶种的3倍。与传统的合成工艺相比较,合成后的金刚石单晶具有较好的形貌与质量。结论采用电镀晶种法合成对高品级金刚石大单晶的合成具有一定参考意义。     

Synthesis of boron-doped diamond with laser heated diamond anvil cell

Boron-doped diamond has been synthesized from graphite mixed with different ratio of B₄C at high pressure high temperature (HPHT) using laser heated diamond anvil cell. The starting composition was transformed to diamond compound at pressure ∼9 GPa, 2300–2400 K as indicated by the in-situ X-ray diffraction pattern with synchrotron radiation source. Raman spectrum of the recovered specimen from HPHT state confirmed that boron has been doped into diamond lattice.     

Microstructures of metallic film and diamond growth from Fe-Ni-C system

The microstructures of metallic film surrounding diamond have been systemically studied using the transmission electron microscopy (TEM) and the atom force microscopy (AFM). The film can be divided into three layers (inner layer near diamond, external layer near graphite and middle layer). The graphite cannot be directly transformed into diamond in the film at HTHP; there exists a parallel relationship between (−111) of γ-(Fe,Ni) and (110) of Fe₃C in the inner layer; the sawtooth-like step morphology found by AFM on the film is similar to that of corresponding diamond surface. A new model for diamond growth at HPHT is proposed from the parallel relationship and sawtooth-like step morphology. It is believed that Fe₃C may be a transitional phase in the course of diamond growth, γ-(Fe,Ni) in the inner layer can absorb carbon atom groups with lamella structure from Fe₃C, and then the carbon groups stack on growing diamond.     

Study on the HPHT synthetic diamond crystal from Fe-C（H） system and its significance

Investigations of crystal habit, micro-topographic imaging, micro-composition and micro-structural analysis of HPHT synthetic diamonds from the Fe-C（H） system indicate that most of them have an octahedral habit. The crystals grow mainly layer-to-layer from center to periphery. HPHT synthetic diamond is smaller in size than natural diamond because it only goes through nucleation and growth in the early stage. In the middle and late stages, due to the coalescence of diamond grains related to differences of surface energy, the growth of HPHT synthetic diamond is limited. The active energy （E） of transforming single nitrogen into a nitrogen-pair is lowered and the time of transforming single nitrogen into a nitrOgen-pair is shortened because of the existence of hydrogen. Therefore, aggregate nitrogen （A-centers） may exist in synthetic diamond from HPHT and explosive detonation processes. It needs further discussion on a worldwide view that the time of natural diamond formation extracted from nitrogen aggregation is some hundred million years. Consideration of the way in which surface energy influences the growth of diamond can help to understand some of the remaining issues （e.g. growth mechanism, etc.） in the HPHT synthetic process and effectively explain the formation of natural diamond in terms of HPHT thermodynamic theory. Especially, it is important to pay more attention to the influence of hydrogen on surface energy in that hydrogen may be a ＂bridge＂ for explaining the formation of HPHT synthetic and natural diamond.     

Growth and characterization of large, high quality cubic diamond crystals

High quality cubic diamond crystals were grown using the temperature gradient method at high pressure and high temperature(HPHT),in a new FeNi alloy as solvent.The crystals were grown at relatively low temperatures suitable for the growth of {100} faces.An increase in the radial growth rate,and inhibition of the axial growth caused the growth of large,high quality cubic diamond single crystals at high growth rates.For example,over 33 h,the radial growth rate was 0.22 mm/h,while the axial growth rate was only 0.08 mm/h;the growth rate by weight was also increased to 7.3 mg/h.The yellow color of our crystal samples was more uniform than samples from Sumitomo Corporation of Japan and Element Six Corp.The Raman FWHW of the 1332 cm 1 peak in our diamond sample was smaller than the Element Six Corp.sample,but larger than that of the Sumitomo Corp.sample.The nitrogen content of our diamond samples was 240 ppm,which was much higher than the Sumitomo and Element Six samples because of the higher growth rate of our diamond samples.     

火焰法沉积金刚石薄膜的组织结构

用透射电镜（ＴＥＭ）对大气中火焰法沉积（ＣＦＤ）金刚石薄膜的组织结构进行了分析研究。结果表明，所沉积的金刚石晶体中（１１１）面上存在着大量层错及显微孪晶，在（１１１）面上晶粒边界处的位错密度较低，此外，在金刚石薄膜中还观察到存在于金刚石颗粒间的非金刚石型碳（Ｃ），即无定形碳及微晶石墨。     

TiB2粒子细化铝合金的电子理论分析

利用固体分子经验电子理论对在铝合金细化过程中起主要作用的TiB2 粒子的价电子结构进行了分析和计算。结果表明 ,TiB2 中的共价电子主要集中在最强的B B键上 ,其晶体中的B B键可形成稳固的六边形结构。大量弥散分布的TiB2 粒子在铝熔体中形成了与石墨类似的连续网状结构 ,为TiAl3 在其上成核提供了平面衬底。TiB2与TiAl3 之间的润湿角较小 ,使成核所需的能量较低。加之TiAl3 与α Al之间具有良好的晶格对应关系 ,从而形成了大量的异质晶核 ,使铝合金得到细化。     

Effects of Ti additive on HPHT diamond synthesis in Fe-Ni-C system

Diamond crystals with low nitrogen concentration were synthesized from the Fe-Ni-C system with Ti additive at high pressure and high temperature （HPHT） in a china-type cubic high pressure apparatus （CHPA）. The synthesis pressure range was 4.8-5.2 GPa, and the temperature range was 1420-1600 K. The lowest synthesis pressure for diamond fell first and then rose with the increase of Ti additive. The color, shape, surface morphology and nitrogen impurity concentration of the synthesized diamond crystals were characterized using optical microscopy （OM）, scanning electron microscopy （SEM） and micro Fourier transform infrared （FTIR） spectrometry. The results show that the Ti additive has significant effects on color, growth rate, crystal shape, surface morphology and nitrogen impurity con- centration of the synthesized diamond crystals. The color of diamond crystals synthesized without Ti additive is yellow, while that with Ti additive becomes light and nearly colorless. The growth rate without Ti additive is higher than that with Ti additive. The crystal shapes of as-grown diamond crystals vary with the increase of Ti additive. The {111} crystal faces become dominant and some {311} crystal faces appear with the increase of Ti additive. The concentration of nitrogen impurity in diamond crystals without Ti additive is higher than that with Ti additive.     

CH4／CO2体系化学气相淀积金刚石的非平衡定态相图计算

用非平衡热力学耦合模型首次获得了由ＣＨ４／ＣＯ２体系化学气相淀积金刚石的相图。该相图与用经典平衡热力学得 结果不同,相图中出现了１个金刚石的生长区,相图中的金刚石生长区是实现金刚石气相生长的热力学基础,它的存在体现了超平衡氢原子等激活粒子对石墨的激活和对金刚石的稳定作用。     

Cu-Ni-Si合金的价电子结构分析

基于固体与分子经验电子理论(EET),对纯金属晶体Cu以及合金固溶体Cu-Ni、Cu-Si和Cu-Ni-Si进行价电子结构分析,建立相空间价电子结构计算模型和方法,从相空间价电子结构角度探讨合金元素的合金化行为。计算结果表明:Cu处于第15杂阶,Ni处于第8杂阶,Si处于第2杂阶,Cu-Ni-Si晶胞的最强键上共价电子数达到了0.45722,这说明合金元素Ni和Si的溶入,能够提高纯铜晶胞的原子键引力,强化铜基体。     

CVD金刚石膜场发射机制的探讨

通过分析CVD金刚石膜的结构,对CVD金刚石膜的场发射机制进行了研究,结果表明金刚石膜内含有一定数量的石墨,当电子通过石墨时从石墨的电场中获得能量增大了电子隧穿金刚石晶粒的系数,据此提出了金刚石膜内石墨相增强电子隧穿金刚石颗粒以增强金刚石膜场电子发射的机制,并且根据该机制解释了一些实验现象。     

人工合成金刚石技术比较

静压法是当前工业合成金刚石的主要的合成手段,合成工业用金刚石主要采用静压法中的静压触媒法,合成宝石级金刚石主要采用静压晶种触媒法生产,通过静压法中的直接变换法,纯净的多晶石墨棒可以在短时间内转化为多晶金刚石,二十世纪八十年代还出现了一种在低压下生长金刚石的新方法——化学气相沉积法(CVD),目前只能用于制备金刚石薄膜,本文通过总结比较各种金刚石合成技术,提出了利用激光控制金刚石生长的设想,使用这种方法将提高金刚石的质量,     

余氏理论中原子平均共价电子密度研究

在价电子理论中提出了原子平均共价电子密度的概念 ,计算了马氏体中典型结构单元内各晶面上的原子平均共价电子密度 .研究表明 :在相邻晶面上的原子平均共价电子密度应连续是不同结构类型单元相邻的必要条件 ,把此条件应用于余氏理论的价电子结构计算中 ,可以消除或减少多重解 .     

Fe-Si-C体系合成金刚石的生长特性

研究高温高压下掺Si合成金刚石, 并与Fe-C体系合成的金刚石进行比较. 实验结果表明, 体系中掺入Si, 合成的晶体颜色比Fe-C体系合成的晶体颜色浅, 在相同的合成时间内, Fe-Si-C体系合成金刚石的粒度比Fe-C体系合成金刚石的粒度小; 通过X射线衍射(XRD)可见, 该体系产生FeSi和Fe₃C两种新物质.      

干摩擦条件下金刚石复合膜摩擦学性能

在干摩擦条件下利用 SRV磨损试验机比较了在硬质合金基体上金刚石薄膜、石墨 /金刚石复合膜以及硬质合金 3种试样的摩擦学性能。利用扫描电子显微镜观察了试样和磨痕的表面形貌。利用表面形貌仪测试了磨损体积。研究了振动频率对试样的摩擦学性能影响。结果表明 ,在干摩擦条件下 ,金刚石薄膜与石墨 /金刚石复合膜的摩擦学性能差别不大 ,二者的磨损机理均为微断裂磨损。在干摩擦条件下 ,高频时金刚石薄膜的耐磨性是硬质合金耐磨性的 8～ 10倍 ,其原因是硬质合金的磨损机理存在着从粘着磨损到微断裂磨损的转变     

爆轰过程中游离碳的状态研究

目的 研究高密度负氧平衡炸药爆轰过程中游离碳的状态。方法 结合爆轰合成纳米金刚石数值结果以及对固相爆轰产物的实验研究,对爆轰过程中游离碳的状态进行讨论。用具有明确物理意义和纯石墨,金刚石,超微金刚石和类液碳的状态方程对多种炸药的爆速进行计算。结果与结论 用超微金刚石和类液碳的状态方程比用纯石墨和金刚石的状态方程预报的炸药爆轰参数更接近实验值,证明高密度负氧平衡炸药爆轰时ＣＪ点上游离碳主要是以液态或