拉丝成品模用生长型多晶金刚石

人造多晶金刚石是研制大颗粒人造金刚石的一种重要途径,它制作方便,易于直接成型.目前在高温高压下有两种研制方法:一是由石墨合成金刚石,再由金刚石微粉烧结成多晶金刚石,即烧结型多晶金刚石(也称烧结型聚晶);另一就是由石墨直接一次生长成多晶金刚石,即生长型多晶金刚石(也称生长型聚晶). 人造多晶金刚石已在机械、地质、冶金、石油工业中广泛应用.近几年在电线、电缆行业中,也开始以人造金刚石拉丝模代替天然金刚石拉丝模和硬质合金模。天然金刚石模价格贵,资源少.硬质合金模耐磨性差,使用寿命短.所以,人造多晶金刚石拉丝模有着广阔的应…     

压力、温度以及时间对金刚石烧结体性能的影响

 采用熔渗法研究了烧结压力、烧结温度以及烧结时间对金属添加剂金刚石烧结体性能的影响;在1 400 ℃、5.8 GPa、12 min的烧结条件下,烧结出磨耗比为285×10³、金刚石颗粒未出现异常长大的金刚石烧结体;分析了烧结方法对烧结效果的影响。     

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。     

类球状微米金刚石聚晶膜场发射的稳定性

在覆盖金属钛层的陶瓷上,利用微波等离子体化学气相沉积(MPCVD)法制备出类球状微米金刚石聚晶膜。通过二极管结构测试了聚晶膜的场致电子发射特性,利用扫描电子显微镜、拉曼光谱、XRD分析了场发射前后薄膜的结构和表面形貌的变化。发现在高场、大电流密度的场发射中,对类球状微米金刚石聚晶薄膜中的金刚石聚晶颗粒影响很小,而对金刚石聚晶颗粒间的非晶碳层影响很大。对类球状微米金刚石聚晶变化机理进行了研究。     

亚微米级聚晶金刚石的高温高压合成

聚晶金刚石作为超硬材料具有很广泛的应用,常用于油气钻探、切削刀具、耐磨零件等领域。目前,工业上合成聚晶金刚石的内部晶粒尺寸一般都在微米量级以上,而合成微米级以下的聚晶金刚石则要面临很多困难。本工作使用熔渗法在高温高压的条件下合成了亚微米级聚晶金刚石,并对合成的样品进行了X射线衍射、扫描电子显微镜、电子背散射衍射、能谱、硬度等分析测试,结果表明:在5.5GPa、1 500℃、保温15min的情况下成功合成了维氏硬度高达57.0GPa的亚微米级聚晶金刚石;分层组装的方法可以使Co均匀地分散在聚晶金刚石样品中,呈现出圆孔状,从而保证样品具备均匀、优异的性能。同时,通过对烧结工艺的探索发现,温度和保温时间在亚微米级聚晶金刚石的合成过程中起着非常重要的作用。     

多晶金刚石烧结中晶粒表面石墨化的实验研究

 利用X射线微区衍射，X射线光电子谱（XPS）及激光拉曼光谱等分析，对高温高压下以金刚石微粉为原料的多晶金刚石烧结过程中，金刚石晶粒表面石墨化现象进行了考察。结果表明，虽经历了烧结过程，但在没有掺杂剂作用的区域内，没有发现金刚石晶粒表面的石墨化。晶粒表面石墨化的高峰期，处于掺杂剂刚开始液化，但尚未饱和充填金刚石晶粒间空隙的烧结初期阶段，随着液相掺杂剂的饱和充填作用，金刚石晶粒表面的石墨消失，并最终完成多晶金刚石的烧结。     

拉丝成品模用生长型多晶金刚石

天然多晶金刚石极其稀少,而人造大颗粒单晶金刚石的制备又很困难.这样,研制人造多晶金刚石就成为人们研制大颗粒人造金刚石的重要途径.与制备人造大颗粒单晶金刚石比较,人造多晶金刚石的制作工艺简单,易于成型,成本低.目前,在超高压、高温下研制人造多晶金刚石有两种方法:一种是由石墨加金属触媒合成出金刚石微粉,再由金刚石微粉加金属粘结剂烧结成多晶金刚石块.这种方法称为烧结法;另一种是石墨在触媒金属的作用下,一次快速生长成多晶金刚石,这种方法称为生长法.从表面上看生长法不需要经过两次高温、高压过程.但由于需要完成由石墨到金刚…     

高温高压下碳的状态方程及相变理论研究

 研究了高温高压下三相碳（石墨、金刚石、液相碳）的状态方程，包括高压下石墨到金刚石的固-固相变以及高温下石墨和金刚石的熔解曲线。计算所得到的金刚石熔解曲线具有正的斜率，石墨-金刚石-液相三相点为4 400 K，14 GPa左右。     

用过剩压法生长金刚石过程中石墨再结晶现象的研究

描述了在过剩压驱动下金刚石晶种外延生长过程中，大量伴生的石墨再结晶现象，再结晶石墨抑制了金刚石的自发成核，它们分布于合成腔触媒金属的低温区，结晶数量多，晶粒片状分层，尺寸大，但出现乱层晶体结构，同时产生一定数量的无定形碳，分析认为，这与长时间的低过剩压驱动，触媒金属内有足够的碳源供给，并具备在高温高压下石墨分充结晶但又达不到完全石墨化条件有关，还讨论了在低过剩压驱动下，促进金刚石晶体外延生长的碳本     

大块高纯Fe3C的高温高压合成

Fe_3C(渗碳体)是一种用途广泛、力学和磁学性能优良的材料,因而其制备方法一直受到人们的关注。通过高温高压下铁和碳的固相反应,成功制备出大块、致密、高纯的Fe_3C样品,探索了原料种类、颗粒大小、合成温度、合成压力、保温时间等因素对烧结样品的影响。结果表明:当Fe粉粒径为9,石墨粒径为1.3,在4 GPa、1000℃条件下烧结的Fe_3C最为致密。     

Effects of additive NaN_3 on the HPHT synthesis of large single crystal diamond grown by TGM

In this paper,large single crystal diamond with perfect shape and high nitrogen concentration approximately 1671-1742 ppm was successfully synthesized by temperature gradient method (TGM) under high pressure and high temperature (HPHT).The HPHT synthesis conditions were about 5.5 GPa and 1500-1550 K.Sodium azide (NaN3) with different amount was added as the source of nitrogen into the synthesis system of high pure graphite and kovar alloy.The effects of additive NaN3 on crystal growth habit were investigated in detail.The crystal morphology,nitrogen concentration and existing form in synthetic diamond were characterized by means of scanning electron microscope (SEM) and infrared (IR) absorption spectra,respectively.The results show that with an increase of the content of NaN3 added in the synthesis system,the region of synthesis temperature for high-quality diamond becomes narrow,and crystal growth rate is restricted,whereas the nitrogen concentration in synthetic diamond increases.Nitrogen exists in diamond mainly in dispersed form (C-centers) and partially aggregated form (A-centers).The defects occur more frequently on crystal surface when excessive NaN3 is added in the synthesis system.     

A relation between a metallic film covering on diamond formed during growth and nanosized inclusions in HPHT as-grown diamond single crystals

One of the most important characteristics and basic phenomena during diamond growth from liquid metal catalyst solutions saturated with carbon at high temperature–high pressure (HPHT) is that there exists a thin metallic film covering on the growing diamond, through which carbon-atom clusters are delivered to the surface of the growing diamond by diffusion. A study of microstructures of such a metallic film and a relation between the thin metallic film and the inclusions trapped in HPHT as-grown diamond single crystals may be helpful to obtain high-purity diamond single crystals. It was found that both the metallic film and the HPHT as-grown diamond single crystals contain some nanostructured regions. Examination by transmission electron microscopy suggests that the microstructure of the thin metallic film is in accordance with nanosized particles contained in HPHT as-grown diamond single crystals. The nanosized particles with several to several tens of nanometers in dimension distribute homogeneously in the metallic film and in the diamond matrix. Generally, the size of the particles in the thin metallic film is relatively larger than that within the diamond matrix. Selected area electron diffraction patterns suggest that the nanosized particles in the metallic film and nanometer inclusions within the diamond are mainly composed of f.c.c. (FeNi)₂₃C₆, hexagonal graphite and cubic γ-(FeNi). The formation of the nanosized inclusions within the diamond single crystals is thought not only to relate to the growth process and rapid quenching from high temperature after diamond synthesis, but also to be associated with large amounts of defects in the diamond, because the free energy in these defect areas is very high. The critical size of carbide, γ-(FeNi)and graphite particles within the diamond matrix should decrease and not increase according to thermodynamic theory during quenching from HPHT to room temperature and ambient pressure. Received: 13 September 2001 / Accepted: 12 June 2002 / Published online: 17 December 2002 RID="*" ID="*"Corresponding author. Fax: +86-0531/295-5081; E-mail: yinlw@sdu.edu.cn     

金刚石和石墨之间相转变几率的研究

 以势垒渡越模型为基础，对石墨和金刚石的相转变几率在压强-温度（p-T）图上的分布进行了研究。从理论上得到了金刚石和石墨的亚稳态相区边界，理论计算得到的相转变几率分布与文献报道的相转变速率的实验结果具有相同的规律。高温高压法合成金刚石的p-T特征程序可以用相转变几率的分布来解释。     

多次冲击石墨合成聚晶金刚石的实验研究

 利用高能炸药爆轰产物驱动金属飞片，碰撞“硬”回收包套以输入平面冲击波，在24~37 GPa的压力范围内，对纯石墨进行1~4次的冲击压缩实验，合成出了纯度很高、形貌良好的立方型聚晶金刚石。随着冲击次数的增加，金刚石的转化率和粒度有增大的趋势。但是，当金刚石粒度较大时（约100 μm以上），如果冲击温度较低（约1 000 K以下），同时冲击压力又较高（约20 GPa以上），金刚石颗粒就容易被冲击波破碎。     

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.     

Transformation of Carbon Nanotubes to Diamond at High Pressure and High Temperature

The synthesis of diamond at high pressure and high temperature and the discovery of fullerenes and carbon nanotubes are among the most important achievements in carbon science. In the present work, we report the synthesis of diamond from carbon nanotubes at 4.5 GPa and 1300°C. Under these conditions, no diamond crystals were obtained when graphite was used as the starting material. The detailed investigation shows that at high pressure and high temperature carbon nanotubes first transform into quasi-spherical onion-like structures and then into diamond crystals. Our work suggests that carbon nanotubes can be used for the synthesis of high-quality diamond crystals at lower pressure and temperature.     

HPHT preparation and Micro-Raman characterization of polycrystalline diamond compact with low residual stress

High quality grown polycrystalline diamond compact (PDC) with low residual stress was prepared using the infiltration method with nickel based alloys as the solvent under high temperature and high pressure (HPHT). Scanning electron microscopy (SEM) was used to observe the micro morphology of the diamond layer and the diamond/WC substrate interface. It was found that dense and interlaced microstructure with diamond-diamond (D-D) direct bonding formed in the diamond layer of PDC. Micro-Raman spectroscopy was used to measure the Raman shift of diamonds in the polycrystalline diamond (PCD) layer and the residual stress was calculated based on the Raman shift of diamonds. Experimental results show that the residual stress of PCD layer is compressive stress, and the range of the residual stress is from 0.075 to 0.250 GPa in the whole PCD layer, much lower than that of other reports (up to 1.400 GPa). Moreover, the distribution of the residual stress from the diamond surface layer to the inner cross-section is homogeneous.     

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。     

高温高压下碳纳米管的相转变及金刚石的合成

 利用透射电子显微镜（TEM）和扫描电子显微镜（SEM）研究了碳纳米管在高压高温下的相转变。研究发现在高压高温条件下碳纳米管是不稳定的,在5.5 GPa压力下,770 ℃到950 ℃间退火时碳纳米管趋向形成碳纳米葱。在5 GPa、1 000 ℃条件下合成了金刚石。