Innovation in diamond

 This historical review of the progress of innovation in diamond research is discussed comparing it with the history of other materials. The innovation steps in current diamond technology are shaped by the fact that diamond is a functional material. This series of innovations was mainly brought about by the discovery of CVD methods of synthesizing diamond from the gas phase. Many kinds of expected applications have been proposed. Success in demonstrating diamond electronic devices has been achieved, and atomic scale observations on diamond growth are reported. Thus, even atomic scale control in synthesizing diamond looks quite realistic in the near future. Although such new data enhance the applications of diamond, most industrial applications of diamond still rely on its hardness. Innovation with diamond will be accelerated when a product using diamond as a functional material is used widely. Received: 2 January 1997 / Accepted: 27 March 1997     

改性金刚石膜的形貌、结构和附着性能

为了提高金刚石膜/基附着力,通过氧辅助使高温钨丝蒸发,在基底表面与碳氢基团反应生成纳米碳化钨,从而得到金刚石和纳米碳化钨混合的改性金刚石膜.用扫描电子显微镜、X射线衍射仪和压痕法研究了改性金刚石膜的形貌、结构和附着力性能.结果表明,碳钨化合物以纳米相存在于改性金刚石膜中.碳钨化合物的存在使改性金刚石膜的硬度下降,但是适当的碳钨化合物能使膜/基附着力性能得到较大提高.当氧气通入量为1.2sccm时,膜/基附着力性能最好.     

The oxygenated phenomena of the undoped large-grain and small-grain polycrystalline diamond films

The polycrystalline diamond films in this research were deposited using a methane/hydrogen gas mixture in a microwave plasma assisted chemical vapor deposition system. Large-grain, several μm size crystallite, diamond films and small-grain, sub-micron size crystallite, diamond films were prepared by diamond paste and diamond powder nucleation method, respectively. It is found that there is no oxygen incorporated into the diamond films during the microwave plasma chemical vapor deposition process at the synthesis temperature between 900°C and 1000°C. However, the oxygenated phenomena did appear for both of the large-grain and the small-grain polycrystalline diamond films after the films were exposed to air for a period of time. It was shown that the large-grain diamond films are oxygenated more than the small-grain diamond films as the samples were exposed to air for a period of time and also after the chemical cleaning treatment. It is indicated that the oxygenated phenomena of the diamond films come from two contributors, the diamond crystallite surfaces and the diamond grain boundaries. The reaction between the diamond grain boundaries and the air is fast and the oxidized dangling bonds are hard to remove. However, the oxidized dangling bonds on the diamond crystallite surfaces are gradually formed and are easily etched away by the hydrogen plasma.     

表面活性剂对金刚石在树脂中悬浮性及与树脂结合性的影响

用KH550硅烷偶联剂和聚电解质型表面活性剂聚乙烯亚胺(PEI)分别对金刚石进行表面改性,研究了KH550和PEI对金刚石表面电性、金刚石在聚酰胺酰亚胺树脂液中的悬浮性及与树脂结合性的影响.结果表明:改性后金刚石表面的电性能发生显著变化,在酸性条件下,zeta电位绝对值明显提高,颗粒间的静电斥力增强,改善了金刚石在树脂液中的悬浮稳定性;改善了树脂对金刚石表面润湿性及其界面结合性,提高了线锯的切割性能;KH550对金刚石的改性效果优于PEI的改性效果.     

静电纺丝制备金刚石/聚丙烯腈杂化复合纤维

为了改善金刚石在聚合物中的均匀分散性,并提高导热性能,以不同粒度的金刚石和聚丙烯腈（PAN）共聚物为原料,采用静电纺丝方法制备得到金刚石/PAN杂化复合纤维。通过改变纺丝溶液中金刚石的添加量,研究了不同金刚石含量及不同粒度的金刚石对金刚石/PAN杂化复合纤维形态和热性能的影响。研究结果表明,静电纺丝可以有效解决微米级金刚石在PAN聚合物中的分散问题,金刚石的粒度对纺丝的稳定性和连续性影响很大,粒度为0.5~1 μm的金刚石经过纺丝可以有效地包覆在纤维中。当金刚石的粒度大于1~2 μm时,纺丝时稳定性差,纤维中很少或几乎没有包覆金刚石颗粒。当金刚石粒度为0.5~1 μm、实际质量分数为38.5wt%时,金刚石/PAN杂化复合纤维热导率最高,达到1.923 W/（m·K）。     

Characteristics of diamond regrowth in a synthetic diamond compact

A transmission electron microscopic study of a commercial sintered diamond compact is reported that identifies and characterizes the diamond that has regrown between the grains of the original diamond powder during the high-pressure, high-temperature manufacturing process of the compact. The majority of the original grains are strongly deformed whereas the regrown diamond shows little or no plastic deformation. The dislocations in diamond regrown between the original grains occur in low-angle boundaries and other configurations typical of grown-in dislocations in crystals. The manufacturing process involves infiltrating the diamond aggregate by molten cobalt, and the regrown diamond is characterized by the presence of cobalt inclusions in sizes ranging from a few tenths of a micrometre down to a few nanometres, possessing the same orientation and lattice parameter as the diamond host. Graphite inclusions also occur in regrown diamond, few in comparison with cobalt inclusions and in random orientation. The graphite crystals exhibit axial ratios, (c/a), lowered by several per cent due to the containment pressure exerted by the diamond host.     

The formation and characterization of diamond crystallites by microwave plasma enhanced chemical vapor deposition – a comparison of gaseous and solid carbon sources as precursors

Commercial diamond powders are in irregular shapes and have been used as seeds for growing well crystallized fine diamond grits in this study. The surfaces of irregular diamond particles would serve as the seed for the subsequent growth of the diamond crystallites using microwave enhanced chemical vapor deposition (MPECVD). Both gaseous and solid carbon sources were used to transform the irregular shaped diamond seeds with sharp edges and corners along with the increase in size to the final equilibrium form of diamond crystallites. In case of gaseous carbon source, the effect of increasing methane content and applying negative dc bias voltage on the formation of diamond crystallites was significant. While in case of solid carbon source, well-faceted diamond crystallites can he extracted from the molten metal-carbon-hydrogen (M-C-H) system. Surface etch pits are numerous; especially noticeable after long exposure in hydrogen plasma. Both growth rates of diamond crystallite irrespective of the carbon sources tend to be parabolic at the later stage of growth. Electronic Publication     

CVD金刚石材料在高性能刀具上的应用

介绍了在激发氢气和碳氢混合气体的“活化”发光状态下使金刚石沉积的CVD金刚石制造工艺原理和“厚膜”CVD金刚石的新工艺。由于CVD金刚石的聚晶结构使其具有超过天然金刚石断裂韧性的优异特点,因此可作为切削刀具材料使用。介绍了其在高性能切削刀具和修整刀具上的实际应用情况。     

Nanosecond pulsed excimer laser machining of chemical vapour deposited diamond and highly oriented pyrolytic graphite: Part I An experimental investigation

A laser beam offers the benefits of high precision, contamination-free, high speed, and low bulk temperature for machining of chemically vapour deposited (CVD) diamond thin films that in turn enable ultrafine finishing of diamond coated cutting tool inserts and drills, and for finishing and drilling of diamond coated multichip module applications. In this work, laser hole drilling and polishing of CVD diamond (free-standing diamond and coated tool inserts) and HOPG (highly oriented pyrolytic graphite) using a 248 nm wavelength, 23 ns pulsed excimer laser were conducted. The threshold energy fluence required for ablation of diamond and graphite was nearly the same but the material removal rate rapidly increases with the energy fluence for the graphite compared to diamond. At an energy fluence of 10 J cm^-2, the depth removed per pulse was 0.05 μm and 0.30 μm for diamond and graphite respectively. Raman microprobe analysis indicates that the laser machining induced the transformation of diamond to disordered forms of carbon in CVD diamond and some transformation of graphite to diamond in HOPG. The experimental data indicates that the transformation of diamond to graphite requires an energy input of 1.44 × 10⁷ J per mole. For a given set of laser parameters, the depth per pulse was substantially higher for diamond coated tool inserts compared to the free-standing diamond. The surface roughness of CVD diamond was reduced by 0.25 μm per pulse at an energy fluence of 16 J cm^-2 This revised version was published online in November 2006 with corrections to the Cover Date.     

Effect of activators on the properties of nickel coated diamond composite powders

Nickel coated diamond composite powders were fabricated via a newly developed direct electrodeposition technique. The effects of activators on the coating of diamond were firstly investigated and diamond grinding wheels were then prepared from Ni-coated diamond composite powders with different activators. The microstructural characterizations of this composite powders were finally conducted by scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction, and the mechanical and tribological properties of as-prepared diamond grinding wheels were also measured. There are changes in microstructures and properties of the composite powders with activators. The activator concentration also has an influence on the morphologies and phase structures of the Ni coating on diamond particles.The composite powders with more compact coating of nickel can be prepared by adding 1 g dm~(-3) or more AgNO_3 as an activator to electrodeposit nickel on diamond. The mechanical and tribological properties of diamond grinding wheels were significantly improved when the coating phase structure of Ni crystal grew with(111) plane orientation on the surface of diamond particles. The wheels made from nickel coated diamond composite powders possessed the advantages of easy preparation and outstanding tribological properties. Therefore, Ni coated diamond composite powders exhibit a great potential to be extensively applied in diamond cutting and grinding tools.     

The effective chemical vapour deposition rate of diamond

The effective chemical vapour deposition (CVD) rate of diamond, defined as the total thickness of diamond or as the mass of diamond deposited per unit time, may be increased by orders of magnitude by increasing the substrate area per unit volume. To obtain these high deposition rates, novel substrate designs are proposed that exploit three-dimensional arrays of small diameter wires or fibres. The analysis suggests that the increased diamond output should be achieved with no increase in the net gas flow or power consumption, which could lead to the more economic production of solid diamond shapes and of composites containing continuous or short diamond fibres, or particulate diamond. Estimates for the cost of CVD diamond made by the fibre array technique are compared with reported current and predicted costs for CVD diamond and estimates for the cost of CVD SiC.     

Nucleation and growth mechanism of diamond during hot-filament chemical vapour deposition

High-resolution transmission electron microscopy (HRTEM) was employed to study the nucleation and subsequent growth mechanism of crystalline diamond grown on copper TEM grids by the hot-filament chemical vapour deposition process. The HRTEM revealed direct evidence for the formation of a diamond-like amorphous carbon layer 8–14 nm thick, in which small diamond microcrystallites about 2–5 nm across were embedded. These diamond microcrystallites were formed as a result of direct transformation of the diamond-like carbon into diamond. Large diamond crystallites were observed to grow from these microcrystallites. The diamond surface was found to be non-uniform. It is envisaged that the diamond microcrystallites present in the amorphous, diamond-like carbon layer provide nucleation sites on which the large diamond crystallites grew. A mechanism of diamond growth has been proposed, based on the experimental findings, and is consistent with available theoretical models and numerous experimental observations reported in the literature.     

3D Printing of Diamond Tools for Dental Ceramics Processing

This paper is focused on preparing diamond tools with orderly arranged abrasive particles for dental ceramics processing via 3D printing. This allows one to overcome such drawbacks of the existing methods of dental ceramics processing as weak bonding strength, short service life, and irregular diamond distribution in diamond tools. Firstly, the CAD model of the dental diamond tool is constructed using 3D cartographic software, with level‐scan‐path geometry information generated via hierarchcal slicing. Then, using Ni–Cr alloy powder and diamond as raw materials, the dental ceramics processing diamond tool with orderly arranged diamond particles is prepared via a 3D printer. Next, an X‐ray diffractometer, energy dispersive spectrometer, and scanning electron microscope are used to analyze the microstructure of the Ni–Cr alloy and diamond particle interfaces, resulting in the identification of their bonding mechanism. Finally, the diamond grinding wheel produced by 3D printing is subjected to dental zirconia ceramics grinding performance tests. The results obtained confirm that diamond particles experience normal wear, while no abrasive falling off occurs on the 3D printed diamond tool surface.

     

金刚石薄膜的空间应用

总结了四种主要的制备金刚石膜的方法。介绍了金刚石膜的最新发展水平。概括了它们在空间光学，摩擦润滑，空间电子装置的热管理和环境探测方面的一些应用．指出了金刚石膜在航天工业中的重要住、相互关系和前景。     

大气下火焰法合成金刚石薄膜

本文介绍了用氧-乙炔火焰法在大气下合成金刚石薄膜的实验结果,初步研究了基板温度对金刚石晶体生长速度、结晶习性的影响,指出了在金刚石(111)及(100)晶面上外延单晶金刚石膜的温度范围,还探讨了氧对薄膜的质量均匀性的影响。     

用纳米石墨作碳源在高温高压下合成条形金刚石

在国产 6× 12 0 0吨铰链式六面顶压机上 ,选用 Fe55Ni2 9Co16粉末触媒和 Ni70 Mn2 5Co5粉末触媒 ,在 5.1GPa和 1350 K的条件下 ,首次用纳米石墨进行了金刚石的合成实验。实验结果表明 :纳米石墨在 Fe55Ni2 9Co16粉末触媒和高温高压条件下生成大小在 2 0 μm左右的条形金刚石 ;在Ni70 Mn2 5Co5粉末触媒和高温高压条件下生成大小在 5～ 2 0 μm左右的、呈六一八面体的金刚石。两种金刚石都是透明的。初步分析了条形金刚石的形成原因。     

Investigation into polishing process of CVD diamond films

A new technique used for polishing chemical vapor deposition (CVD) diamond films has been investigated, by which rough polishing of the CVD diamond films can be achieved efficiently. A CVD diamond film is coated with a thin layer of electrically conductive material in advance, and then electro-discharge machining (EDM) is used to machine the coated surface. As a result, peaks on the surface of the diamond film are removed rapidly. During machining, graphitization of diamond enables the EDM process to continue. The single pulse discharge shows that the material of the coated layer evidently affects removal behavior of the CVD diamond films. Compared with the machining of ordinary metal materials, the process of EDM CVD diamond films possesses a quite different characteristic. The removal mechanism of the CVD diamond films is discussed.     

大面积印刷纳米金刚石薄膜的场致发射的研究

研制了特定比例的纳米金刚石浆料,采用了丝网印刷工艺在石墨衬底上大面积印制了纳米金刚石场发射薄膜,实验探索了石墨衬底纳米金刚石薄膜的烧结工艺和后处理过程,利用扫描电镜(SEM)观察了纳米金刚石膜的表面形貌,经后处理的薄膜中纳米金刚石露出薄膜表面,纳米金刚石的棱角是天然的发射体.采用本课题组研制的多功能场发射测试台在10-6Pa的真空条件下进行了场发射特性的测试,结果发现石墨上低成本大面积印刷的纳米金刚石薄膜具有均匀稳定的场发射特性,作为电子器件的理想冷阴极发射,可在宇宙飞船、原子反应堆等恶劣条件下工作的平面显示器中得到应用.     

AFM Study on Interface of HTHP As-grown Diamond Single Crystal and Metallic Film

The study for the interface of as-grown diamond and metallic film surrounding diamond is an attractive way for understanding diamond growth mechanism at high temperature and high pressure (HTHP), because it is that through the interface carbon atom groups from the molten film are transported to growing diamond surface. It is of great interest to perform atomic force microscopy (AFM) experiment; which provides a unique technique different from that of normal optical and electron microscopy studies, to observe the interface morphology. In the present paper,we report first that the morphologies obtained by AFM on the film are similar to those of corresponding diamondsurface, and they are the remaining traces after the carbon groups moving from the film to growing diamond. The fine particles and a terrace structure with homogeneous average step height are respectively found on the diamond(100) and (111) surface. Diamond growth conditions show that its growth rates and the temperature gradients inthe boundary layer of the molten film at HTHP result in the differences of surface morphologies on diamond planes,being rough on (100) plane and even on the (111) plane. The diamond growth on the (100) surface at HPHT could be considered as a process of unification of these diamond fine particles or of carbon atom groups recombination on the growing diamond crystal surface. Successive growth layer steps directly suggest the layer growth mechanism of the diamond (111) plane. The sources of the layer steps might be two-dimensional nuclei and dislocations.     

Photoluminescence of Diamond Films and Ultrafine Diamond under UV Laser Excitation

Time-resolved photoluminescence spectra of diamond films and synthetic diamond powders are measured under pulsed UV laser excitation at time delays in the range 0–50 ns. The results are compared with the photoluminescence spectra of synthetic and natural diamond single crystals. The luminescence decay time is determined for the diamond films and ultrafine diamond.