Fe-C-S系金刚石单晶的高温高压合成

在Fe-C体系中加入单质硫(S)作为添加剂,采用高温高压法合成金刚石单晶.研究表明:S在高温高压下与Fe发生了相互作用,影响了Fe的催化性能,进而对金刚石的自发成核产生抑制作用.S的添加能使纯Fe触媒合成六八面体晶体的温度区间变宽,从而提高合成六八面体的可控性;在显微镜下观察金刚石晶体形貌颜色为深黄,晶体完整,包裹体较...     

TiO_2薄膜对金刚石磨削性能的影响

采用溶胶-凝胶法在金刚石表面涂覆TiO_2薄膜.利用扫描电镜、能谱以及红外光谱等手段对涂膜后金刚石磨料表面形貌、结构和成键情况进行分析,研究在不同进刀量时TiO_2薄膜对金刚石磨削性能的影响.结果表明:磨料表面的TiO_2薄膜可以保护金刚石磨料在烧结过程中不受结合剂中碱金属氧化物的侵蚀,提高结合剂对金刚石的润湿性;在进刀量为5 μm/s时,与未涂膜金刚石砂轮相比,涂膜金刚石砂轮对硬质合金(WC,6%(质量分数)Co)的磨耗比提高121%.     

“限流环”对MPCVD法快速制备高质量金刚石膜的研究

为了提高金刚石膜的沉积速率和沉积质量,本文通过在5 kW微波等离子体化学气相沉积装置(MPCVD)的腔体内添加“限流环”,运用较高的微波功率(4700 W)以较高的沉积速率(25.0μm/h)得到了高质量的金刚石膜.添加“限流环”后,明显改变了工作气体在腔体中的流向.在高功率微波下,工作气体能尽可能多地流经高能等离子体...     

椭球形微波等离子体金刚石膜沉积装置与金刚石膜的制备

对椭球形谐振腔式微波等离子体(MPCVD)金刚石膜沉积装置的谐振腔进行了模拟,获得了谐振腔中的电场和等离子体分布。运用自行设计和建立的椭球形谐振腔式微波等离子体装置,沉积了纳米和微米尺度的金刚石膜。对金刚石膜的各种性能进行了检测。结果表明,所建成的椭球形谐振腔式的MPCVD金刚石膜沉积装置,可实现微米和纳米尺度不同品质金刚石膜的沉积。     

Residual stress distribution in thin diamond films and its effects on preparation of thick freestanding diamond films using DC arc plasma jet operated at gas recycling mode

Diamond films produced by chemical vapor deposition show excellent properties. The residual stress distribution of diamond thin films deposited by DC arc plasma jet at recycling mode was analyzed by line shifts of micro Raman spectroscopy. The results show that the compressive residual stress concentrates at the film's edge. The experimental observations show that cracks initiate at the edge of the diamond thick wafer and then propagate towards the center. The residual stress of diamond films increases with the increase of methane concentration and deposition temperature. The difference of adhesion in close area causes more shear stress and brings about the two sides of crack being not at same level. To suppress crack probability, it is favourable for increasing the film thickness and selecting a substrate with lower coefficient of thermal expansion and lower adhesion. The effects of the residual stress distribution on thick diamond films detachment were discussed.     

Experimental and gas phase modeling of nanocrystalline diamond films grown on titanium alloys for biomedical applications

For biomedical applications, it is highly desirable to be able to deposit smooth adherent diamond films on various complex-shaped substrates using the hot filament chemical vapor deposition technique (HFCVD). The properties of these films are affected profoundly by process parameters such as filament temperature, gas composition, and pressure. In this study, we present an insight into the gas phase chemistry involved in HFCVD of smooth nanocrystalline diamond films using Ar/CH₄/H₂ precursor mixtures. Experimental results on the growth, surface morphology, and crystalline structure are also presented. It is evident that the addition of a noble gas such as argon has a considerable effect on the gas surface chemistry. Notably at high concentrations of inert gas dilution (>90 vol.% argon) there are significant changes in diamond crystallinity ranging from polycrystalline through microcrystalline, and at argon concentrations >98 vol.%, nanocrystalline facets are observed. Modeling of the gas phase chemistry showed that the relative concentrations of CH₃ and C₂H alter significantly in this region, and these in turn influence surface morphology and crystallinity of the deposited films.     

高温高压下金刚石成核机制的研究

本文以国产六面顶压机作为人造金刚石的合成设备,采用金属粉末触媒技术,进行了金刚石晶体的合成.实验中,通过对生长工艺的调整,考察了金刚石在合成区间内的不同合成习性.实验结果表明:金刚石的合成区间可以根据能否自发成核而分为成核区与生长区.在生长区内,金刚石不能自发成核,但金刚石晶种可以在此区间稳定存在并长大.在生长区内金刚...     

人造金刚石磨料精密分级分选技术研究

金刚石磨粒的强度和破碎性能主要取决于其晶形及其规则程度和完整性、内部缺陷及杂质含量和分布形式等.要使磨粒在粒径、性能等方面尽可能一致,必须进行分级分选处理.本文论述人造金刚石磨料的基本性质和与其相关的基本性能特性;在采用振动选形技术的基础上,对应用磁分离技术、引入重液分离技术、探索浮选技术和应用选择性破碎原理及强化筛分分级几方面进行了探讨.提出了人造金刚石磨料精密分级分选的基本方法和一般原则.实践表明,这些方法是有效的和可行的.     

SiC衬底金刚石薄膜的制备与性能表征

用热丝CVD法,以丙酮和氢气为碳源,在SiC衬底上沉积金刚石薄膜,提出了分步变参数沉积法制备超细晶粒金刚石复合薄膜的新工艺.结果表明,合理控制工艺条件的新工艺,对金刚石薄膜质量、形貌和粗糙度、薄膜与衬底间的附着力以及薄膜的摩擦系数有显著影响,金刚石薄膜的平均晶粒尺寸从3 μm减小到0.3 μm,拉曼特征峰显示超细晶粒金刚石薄膜特征,涂层附着力好,超细晶粒金刚石薄膜的表面粗糙度和摩擦系数值显著下降,对获取实用化的SiC在基体上沉积高附着强度、低粗糙度金刚石薄膜的新技术具有重要的意义.     

CVD掺硅金刚石残余应力的X射线衍射和拉曼光谱分析(英文)

采用X射线衍射(XRD)和拉曼光谱2种方法测量了不同硅碳比的CVD掺硅金刚石薄膜的残余应力。采用偏压增强热丝化学气相沉积装置在硬质合金基底上制备了掺硅金刚石薄膜,将正硅酸乙酯以不同的体积比溶解在丙酮中以使得反应气体中的硅碳比从0.1%变化到1.4%,从而控制掺硅金刚石薄膜的掺杂浓度。SEM和XRD的表征结果显示,随着硅掺杂浓度的增加,金刚石薄膜的晶粒尺寸减小,而金刚石(110)的晶面则逐渐占优。XRD法是测量入射角从0°到45°变化时对应的金刚石(220)面XRD衍射峰,并采用sin2ψ方法计算掺硅金刚石薄膜的残余应力。拉曼谱法则是通过检测金刚石特征峰偏移1332cm1位置的偏移量来测量残余应力。2种方法测得的残余应力随着硅掺杂含量的升高显示出良好的一致性,所有的硅掺杂金刚石的残余应力均为压应力,Si/C摩尔比为0.1%的薄膜具有最高的残余应力,为~1.75GPa(拉曼谱法)或~2.3GPa(XRD法)。随着硅掺杂浓度的进一步升高,薄膜的残余应力则稳定在~1.3GPa左右。     

Fatigue strength of chromium coated elements and possibility of its improvement with slide diamond burnishing

Surface layer condition and fatigue strength of chromium coated elements were tested. Special shape samples cut out of chromium coated shafts were symmetrically deflected on electrodynamic vibrator at sample frequency oscillations in the 1000 Hz order. They were 42CrMo4 and 41Cr4 steel samples with a 25 and 50 μm chromium coat finished by slide diamond burnishing and polishing. Surface topology parametres, surface microhardness and residual stresses in the surface layer were checked and fatigue strength was tested. Before the coating was applied, the roller surfaces of the samples were ground and band polished. It was found that chromium electroplating causes detrimental, tensile stresses in the surface layer and worsens the fatigue strength limit. Slide burnishing of chromium coatings produces advantageous, compressive stress in the surface layer and the oscillatory bending fatigue strength of elements with burnished coatings can be improved up to 40%, which completely reduces the detrimental chromium plating effects. It can also be stated that slide burnishing of coatings does not create bigger technical problems and gives better results than band polishing.     

Understanding of the shape-controlled synthesis of strip shape diamond under high pressure and high temperature conditions

We present the shape-controlled synthesis of strip shape diamond with stretched crystal faces along {100} or {111} direction and larger length-to-radius ratio than the conventional diamond in the designed NiFe-C system at high pressures and high temperatures (HPHT). A series of synthetic experimental results on the strip shape diamonds were obtained at different pressures and temperatures. Under the constant pressure condition, the morphology of the strip shape diamond varied with the increase of temperature obviously. Fourier transform infrared (FTIR) micro spectroscopy and Raman spectroscopy revealed that the various locations of crystal face have different nitrogen impurity concentration, and internal strain and defects in these strip shape crystals. According to these results, it can be concluded that the difference of growth rates at various crystal faces results in different crystal morphologies. Based on the growth characteristics, we suggest that composition segregation of the metal film around the growing crystal induces the formation of strip shape diamond.     

Nucleation and growth of combustion flame deposited diamond on silicon nitride

The effect of substrate temperature (T_s) on the nucleation and growth of diamond on silicon nitride (Si₃N₄) based substrates deposited via the oxy-acetylene combustion flame technique was investigated. The diamond deposits were characterized via scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The nucleation density of the resulting deposits, which was of the order 10⁵ nuclei/cm², was used to approximate the activation energy for heterogeneous nucleation of diamond as32 – 40 kcal/mol. An Arrhenius plot of particle growth rate was used to calculate the activation energy for diamond growth as9.4 and 8.3 kcal/mol in the center and outside annulus of the deposit, respectively. These results suggest that the heterogeneous nucleation of diamond is a highly energetic process and may in fact be responsible for the observed low nucleation density of diamond on Si₃N₄. Thermodynamic analysis of gas/substrate reactions under conventional process conditions predicted that SiC formation, which is known to be a necessary precursor to diamond nucleation on Si, is energetically forbidden. Via kinetic and thermodynamic considerations, a patented in situ multistage deposition technique was developed which yielded continuous diamond coatings on Si₃N₄ substrates without extensive substrate preparation.     

Fe-B-C体系金刚石单晶的高温高压制备与表征

在国产六面顶高温高压设备上,利用低价纯铁粉末为触媒开展含硼金刚石的制备研究。研究发现:无定型硼的掺入会导致金刚石合成条件(温度和压力)不断提高;晶体颜色由浅黄色逐渐变为黑色,晶体主要以八面体为主。利用扫描电镜(SEM)分析含硼金刚石的微观形貌,发现:硼添加后金刚石{111}晶面上存在微米尺寸的圆形凹坑。通过Raman光谱研究发现:随着硼掺入量的增加,金刚石特征峰发生蓝移,其半峰宽变大、晶体质量下降。通过红外光谱可以发现较强的Ⅱb型金刚石存在2 800 cm-1处的 B-C键特征峰。在纯铁触媒体系中,硼的质量分数在0.2%～0.8%时,均能合成出优质含硼金刚石。      

沉积温度及其变化对金刚石膜内黑色缺陷产生过程的影响

用高功率直流电弧等离子体喷射方法研究金刚石膜沉积温度稳定性对膜中黑色缺陷产生的影响。结果表明,在温度稳定条件下制备的金刚石膜中,黑色缺陷的密度较低;当沉积温度大幅度变化时,在膜中产生大量黑色缺陷。形成大量黑色缺陷的原因是:沉积温度变化时,在金刚石晶粒的表面形成贯穿型孪晶,而在随后的生长过程中,这些孪晶的长大将抑制金刚石膜局部生长环境中活化的反应气体与其下晶界位置的金刚石组织接触,导致其生长缓慢并保留在金刚石膜中,从而形成大量黑色缺陷。     

Machinability of ultrafine-grained copper using tungsten carbide and polycrystalline diamond tools

Equal channel angular extrusion (ECAE) is an effective process to produce bulk ultrafine-grained (UFG) materials from regular coarse-grained materials. Such ECAE-processed materials typically excel in strength, wear resistance, ductility, and high strain-rate superplasticity, with promising applications in lightweight transportation and medical industries. Precision machining work is generally indispensable for further applications after bulk materials are produced by ECAE. To effectively and efficiently machine such ECAE-processed materials for further broad applications, machining issues such as machinability and tool material selection should be considered. This study was undertaken to investigate the machinability of ECAE-processed pure copper using both tungsten carbide (WC) and polycrystalline diamond (PCD) cutting tools in order to facilitate broad applications of ECAE-processed UFG coppers. It is found that despite its higher cost, PCD is favored to machine UFG copper based on this study since it has better wear resistance, gives lower cutting forces, yields a better workpiece surface finish, and results in no smearing on the workpiece. In machining UFG copper, depth of cut notching was observed as the wear pattern and abrasion as the wear mechanism for the WC tool, while flank wear was observed as the wear pattern and diffusion as the wear mechanism for the PCD tool.     

真空微蒸发镀覆工艺参数对镀层质量及金刚石性能的影响

本文通过对金刚石镀Ti过程中镀层形成的演化过程的测试观察，研究了镀覆温度、时间等工艺参数的改变对镀层厚度控制及其随后的性能变化等。用扫描电镜观察了镀覆处理后金刚石的表面形貌，同时测定了镀覆处理后金刚石颗粒的静压强度和冲击韧性。结果表明，当镀覆温度高于100℃时镀层将由于厚度增加和应力过大，使其局部脱落，达到1100℃时脱落率达到60％；镀覆温度在900-1000℃范围内，对质量较好的金刚石静压强度和冲击强度达到最高，继续升高温度导致其强度数值下降；本文研究证明，对于石墨模具、含Fe40％的Cu—w基结合剂、1100℃／10min条件下热压烧结，镀覆温度为900—1000℃／60min保温所获得的Ti镀层具有最佳使用效果。     

Effect of pretreatment, seeding and interlayer on nucleation and growth of HFCVD diamond films on cemented carbide tools

The direct deposition of diamond on carbide tools is difficult because formation of graphitization and thus leading to poor adhesion, due to presence of cobalt on the surface. Various methods were adopted to suppress the effect of cobalt during deposition. One of them was by putting an interlayer. In this study, carbide substrates with coatings of Ti, TiN and TiC were used. Ti coating has a strong tendency to form intermediate carbide leading to the highest nucleation density of diamond. A comparison was made on nucleation and growth of diamond crystals on various interlayers by hot filament CVD method. At the same time, the variations of diamond film growth morphology have been studied on unseeded and seeded carbide inserts. The SEM pictures revealed that among interlayer, Ti coating gave highest nucleation density compared to TiN and TiC coatings. At the same time, diamond seeded inserts, pretreated by Treat 1 [HCl + HNO₃ + H₂O (1:1:1)] for 15 min ultrasonically resulted in the highest nucleation density, compared to Treat 2 [K₃[Fe(CN)₆] + KOH + H₂O] solution in (1:1:10) for 15 min, at constant process parameters.     

型面约束下的真空钎焊金刚石工艺及其等高性分析

在真空炉中采用石墨阴模对金刚石进行适当约束的方法开展钎焊试验,实现了金刚石与钢基体之间的高强度连接及磨粒等高性的有效控制. 采用SEM对钎焊试样和金刚石表面形貌进行观察,采用EDS对金刚石表面定点和微区成分进行分析,使用超景深三维显微镜对磨粒等高性进行测量. 结果表明,液相Cu70Sn20Ti10钎料在毛细作用下可润湿包裹在石墨阴模上粘接的金刚石,且两者界面上形成TiC反应物,由此可获得钢基体对金刚石高的把持力. 钎焊过程银胶不与金刚石发生反应,同时由于银胶能够始终保持对金刚石的粘接及约束作用,所以钎焊后的磨粒等高性好.     

Effect of pressure on nanocrystalline diamond films deposition by hot filament CVD technique from CH4/H2 gas mixture

The effect of pressure on the deposition of nanocrystalline diamond (NCD) films in a hot filament chemical vapor deposition (HFCVD) system was investigated employing a 1% CH₄ in H₂ gas mixture. With decreasing the growth pressure from 5.0 to 0.125 kPa, a gradual reduction of the diamond grain sizes from sub-micrometer to nanometer scale was observed, accompanied by the decline of surface roughness and the evolution of film cross-sectional morphologies changing from columnar to grainy structures. The pressure also exerted prominent influence on the film growth rate. At 2.8 kPa the growth rate featured a maximum, while decreasing to higher and lower pressures. Such pressure dependence of the diamond growth rate was suggested to result from two competing effects of pressure on the concentration of reactive species near the diamond growth surface. Further, the mechanism for the NCD film formation under low deposition pressures was discussed in light of the high secondary nucleation rate.