粉末触媒合成金刚石体系的温度稳定性问题

就不同粉末触媒、石墨粉配比体系的金刚石单晶在高温高压条件下生长过程中,合成腔体内温度场的变化进行分析,指出合理的粉末触媒合成金刚石体系的粉末触媒及石墨粉的分布状态。     

不同粒度NiMnCo粉末触媒催化特性及其影响因素的研究

采用扫描电干显微镜(SEM)、X射线光电子能谱(XPS)、差热分析(DAT)研究了不同粒度NiMnCo触媒合成空刚石的催化特性及熔化特性、微观形貌、表面化学状态对其影响，结果表明：320／500目触媒适宜粗颗粒金刚石的合成，150／200目粉末触媒合成的SMD系列金刚石比例较高；比表面积、表面状态和熔化特性直接影响其合成金刚石的效果，比表面积增大，有利于提高空刚石的合成单产；熔化温度降低．可以减少连聚晶的发生；控制粉末触媒表面的氧含量是提高其催化活性的关键。     

高温高压合成含硼金刚石单晶制备工艺初探

本文以掺入不同含量硼铁的铁基合金为触媒,以石墨为碳源,在高温高压条件下合成了含硼金刚石单晶体.利用扫描电镜(SEM)观察了金刚石及触媒的组织形貌;利用金相显微镜观察了金刚石颗粒的颜色和形态;利用拉曼光谱仪(RS)确认了人造金刚石单晶体中硼的存在;利用低温电阻测量仪验证了合成的含硼金刚石单晶颗粒具有半导体性能.实验结果表明,在金刚石的合成中,触媒中硼铁含量为2wt%的合成效果相对最好.     

微晶石墨对Ⅱa型宝石级金刚石单晶生长的影响

将除氮剂Ti(Cu)添加到FeNiCo合金触媒中在高温高压下合成出优质Ⅱa型宝石级金刚石单晶.在压力5.4GPa、温度1600K的条件下沿{111)面合成Ⅱa型宝石级金刚石过程中伴随有黑色粉末析出.采用X射线衍射(XRD)和扫描电子显微镜(SEM)对该黑色石墨粉末的测试表明其为微晶石墨.随着生长时间的延长,这种微晶石墨...     

Fe-Ni-C体系高温高压生长金刚石单晶的碳源供给

在Fe-Ni-C体系中高温高压生长金刚石单晶,通过对触媒和金属包覆膜的物相结构表征、相图分析以及热力学计算等方法探讨金刚石形核长大的碳源供给。研究发现:在金刚石形核的初期,由于石墨的不断熔入,触媒熔体会迅速形成对碳的过饱和溶液,并析出初生渗碳体。金刚石单晶合成之后触媒和金属包覆膜的组织与物相均以渗碳体为主。相图分析发现,金刚石的形核长大伴随有渗碳体的分解。热力学计算表明,在金刚石稳定生长区域,渗碳体向金刚石转变的相变自由能比石墨-金刚石的相变自由能更负。由此说明,Fe-Ni-C体系高温高压生长金刚石单晶的直接碳源并非石墨,而是渗碳体,即金刚石单晶来源于渗碳体高温高压的金刚石化而不是石墨的直接转化。     

合成金刚石用触媒合金粉末的开发应用

粉末法合成人造金刚石相比片状合成的相同体积的金刚石来说，产量、质量均有大幅度提高，而材料消耗大幅度降低，用触媒合金粉末材料合成人造金刚石已经得到国内各生产厂家的认同，合成高品级人造金刚石用的触媒合金粉末材料正处于方兴未艾的阶段，触媒合金粉末材料的需求量呈快速增长的趋势。     

触媒合金渗硼对合成人造金刚石性能的影响

本文研究了触媒合金渗硼对合成人造金刚石性能的影响。结果表明，采用渗硼触媒合成金刚石，可提高金刚石的抗压强度、耐热性和优质粗晶粒百分比，但却使金刚石的单次合成产量降低。     

测定含硼金刚石单晶颗粒电阻的方法

以铁基舍金掺杂FeB或B4C为触媒、石墨为碳源，在高温高压条件下合成了含硼金刚石单晶。测定了金刚石单晶颗粒在不同温度下的电阻并绘制出两参数之间的变化曲线。结果表明，当金刚石单晶中掺入硼时，其电阻大幅度降低，且电阻随温度的升高而下降，即存在负的电阻温度系数，表现出半导体材料的特性。     

铁基触媒的组织结构对合成金刚石的影响

采用粉末冶金铁基触媒在六面顶压机上高温高压合成金刚石.使用高性能金相显微镜,扫描电子显微镜和X射线衍射仪对合成之后触媒的组织结构进行系统的表征.试验发现,触媒组织主要由粗大的板条状初生渗碳体和细密的共晶莱氏体构成;金刚石生长效果不好时,触媒组织中夹杂有团絮状石墨.分析认为,初生渗碳体极有可能就是金刚石生长的直接碳源,即高温高压下溶解于触媒熔体的石墨首先与触媒合金形成碳化物,在触媒的催化作用下,碳原子自渗碳体脱溶,沉积到金刚石表面,完成金刚石的生长.     

铁镍碳体系中触媒含量的不同对金刚石晶体生长的影响

本文以高纯鳞片石墨为碳源,以Fe_(80)Ni_(20)合金触媒粉为触媒,在国产JHY-Ⅲ型六面顶液压机上进行金刚石的合成实验。在设定相同压力及加热功率的条件下研究了触媒粉与石墨粉分别按3:7、4:6、5:5、6:4和7:3混合时对金刚石合成的影响规律,得出了500秒合成时间内最佳石墨触媒混合比为4:6的结论。     

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。     

Electrodes from diamond and diamond-like materials for electrochemical applications

Generalized results are given of the investigation into the electrochemical behavior of electrodes made from monocrystals of dielectric and semiconducting synthetic diamonds, polycrystalline diamond films, amorphous carbon and hydrogenated amorphous carbon films, as well as of compacts from nano-and microdispersed diamond powders in aqueous solutions. It is shown that the decisive role in the use of these electrodes is played by the value and type of electroconductivity of diamond materials, quality (continuity) of films and their resistance to corrosion. Our findings have shown that the use of the studied materials in electrochemical processes has considerable promise.     

Effects of added diamond powder on the reaction sintering behaviour of diamond in the graphite-nickel system

Polycrystalline diamond sintered compact was prepared under high pressure and temperature conditions (7 GPa, 1700°C, 10 to 30min) from the starting material with the composition of the system 50 wt% carbon (diamond + graphitized pitch coke (GPC))-50 wt% Ni. The effects of added diamond powder on the microstructure of the sintered compact and reaction sintering behaviour were investigated. The grain size of diamond in the sintered compact decreased remarkably from 20 to 40m to 2 to 3m on addition of 10 to 20 wt% diamond powder (grain size: 1m) to the GPC-Ni system. The grain size can be controlled by that of the added diamond powder. A sufficient supply of carbon from GPC plays an important role in the formation of a covalently bonded compact of diamond. The grain growth of the formed diamond is depressed by the coexistence of diamond powder, which controls the solubility of carbon in the metal-carbon system and also the grain growth process by solution-reprecipitation.     

Investigation on defects in HPHT-grown diamond single crystals

In the diamond single crystals synthesized at high temperature and high pressure using FeNi as catalyst, there are usually supersaturated vacancies and inclusions formed during the diamond crystal growth and rapid cooling from high temperature. Some defects such as prismatic dislocation loops, stacking faults and array of dislocations are closely related to such supersaturated vacancies and inclusions. The supersaturated vacancies agglomerate into discs on the (111) close-packed planes, subsequent collapse of the discs forms the dislocation loops and stacking faults. The thermal internal stresses, which are caused by the difference of thermal contraction between the diamond and the inclusions due to the difference of thermal coefficients between them as the diamond is cooled from high temperature, may be relieved by the formation of array of dislocations. In the present paper, these defects in the diamond single crystals were directly examined by transmission electron microscopy (TEM). The characteristics and formation process of these defects were analyzed briefly.     

Analysis of the Phenomena of Diamond Synthesis by Seeding with Diamond

Synthesizing diamond single crystal by diamond seed particles which were electroplated with nickel film as catalyst under high pressure and high temperature （HPHT） was described. The microstructure of nickel film after synthesis and morphology of grown diamond were investigated by means of X-ray diffraction （XRD） and scanning electron microscopy （SEM）, respectively. The phase structure in nickel film were graphite, NiC, Ni, and diamond structure hadn＇t been found. A lot of recrystallized graphite pits appear in interface between the inner surface of nickel film and the surface diamond. It is shown that the new-grown diamond was developed epitaxially on the crystal planes of seeds. Also, the new-grown diamond grew by two-dimensional nucleation and by a layer growth mechanism. The growth process of crystal was microaggregate→step→expansion→new crystal layers, and the flat growth interface transformed into a cellular interface at the same time.     

Growth of diamond microcrystals by the oriented attachment mechanism at high pressure and high temperature

For the first time it has been experimentally shown that a powder of detonation nanodiamonds (DND) and a saturated acyclic hydrocarbon, mono- or dibasic alcohol, used as the reaction mixture after treatment at high pressures (5–8 GPa) and high temperatures (1300–1800°C) results in the formation of diamond single crystals up to 15 micron in size. The Raman spectrum indicates that the diamonds have a perfect of crystal structure. It has been suggested that the oriented attachment mechanism is responsible for growth of micrometer-size diamond single crystals out of DND particles with sizes of about 5 nm under these technological conditions.     

两段成长法改善微波电浆辅助化学气相沉积多晶金刚石之品质

以化学气相沉积法成长多晶金刚石薄膜时,薄膜的品质会受到成长时间、成长压力、反应气体比例、偏压与否及成核的机制等因素影响.研究采用微波电浆辅助化学气相沉积(MPECVD)法,以甲烷(CH4)和氢气(H2)作为反应气体原料,在P型(111)硅基板沉积多晶金刚石薄膜.典型沉积多晶金刚石薄膜的制程可分为四个阶段:抛蚀表面阶段、渗碳阶段、偏压增强成核(BEN)阶段及成长阶段.研究将成长阶段划分为两个阶段,第一阶段压力较低(成长Ⅰ阶段),第二阶段压力较高(成长Ⅱ阶段).结果表明:第一阶段可大大改善金刚石薄膜的品质,所获多晶金刚石薄膜的晶粒具有明确的颗粒边界、较低的碳化物或缺陷,电导率急剧降低,显现出本徵金刚石半绝缘的性质.可以认为金刚石薄膜品质的改善完全为低压成长所致.实验发现在成长Ⅰ阶段或成长Ⅱ阶段施加偏压时,只会降低多晶金刚石薄膜的品质.     

添加剂LiF对FeNi粉末触媒合成金刚石的影响

研究了添加剂LiF对FeNi粉末触媒合成金刚石的影响.实验中将一定比例的无定形LiF、粉末直接添加到FeNi-C粉末体系中并均匀混合,利用高温高压条件,进行掺LiF合成金刚石的研究.实验结果表明,由于体系中LiF的掺入,对金刚石的合成条件没有明显的影响;借助X衍射测试发现,在高温高压下,体系中LiF的成份并没有发生变化;借助于光学显微镜发现,FeNi-LiF-C体系合成出的晶体晶形完整,但透明度变的很差且表面变得很粗糙,包裹体增多;通过扫描电子显微镜(SEM),对两种体系所合成金刚石表面的形貌进行了观察,发现FeNi-LiF-C体系所合成的晶体表面有凹坑出现.     

Growth and characterization of diamond particles,diamond films,and CNT-diamond composite films deposited simultaneously by hot filament CVD

It is important to understand the growth of CNT-diamond composite films in order to improve the inter-link between two carbon allotropes, and, in turn, their physical properties for field emission and other applications. Isolated diamond particles, continuous diamond thin films, and thin films of carbon nanotubes (CNTs) having non-uniformly distributed diamond particles (CNT-diamond composite films) were simultaneously grown on unseeded, seeded, and catalyst pre-treated substrates, respectively, using a large-area multi-wafer-scale hot filament chemical vapor deposition. Films were deposited for four different growth durations at a given deposition condition. The changes in surface morphology and growth behavior of diamond particles with growth duration were investigated ex situ using field emission scanning electron microscopy and 2D confocal Raman depth spectral imaging, respectively. A surface morphological transition from faceted microcrystalline nature to nanocrystalline nature was observed as a function of growth duration in the case of isolated diamond particles grown on both unseeded and catalyst pre-treated substrates. However, such a morphological transition was not observed on the simultaneously grown continuous diamond thin films on seeded substrates. 2D confocal Raman depth spectral imaging of diamond particles showed that the local growth of CNTs did not affect the growth behavior of neighboring diamond particles on catalyst pre-treated substrates. These observations emphasize the importance of surface chemical reactions at the growth site in deciding sp² or sp³ carbon growth and the final grain size of the diamond films.