温度梯度法宝石级金刚石的合成及表征

利用温度梯度法,在5．0—5．7GPa,1250---1600℃条件下,研究了FeNiMnCo触媒合成宝石级金刚石的温度和压力区间,给出了P-T相图．基于有限元法的温度场模拟及碳素浓度梯度拟合结果表明,I型温度场只适合生长大尺寸优质板状及小尺寸塔状金刚石单晶;II型温度场可以合成出大尺寸优质板状或塔状金刚石单晶．该结论被Ib型及掺硼宝石级金刚石晶体生长实验所证实．提出碳素浓度梯度是决定晶体生长速度及合成晶体品质的关键因素．研究得到了只有触媒中温度场分布与晶体尺寸、形貌相匹配时,才能合成出优质宝石级金刚石单晶的晶体生长规律．揭示了{110},和{113}高指数晶面在Ib型金刚石“V”形区内的分布规律．通过傅里叶红外光谱检测发现,FeNiMnCo触媒合成金刚石的氮含量较低,较低的氮含量是由铁会降低金刚石氮含量所致．氮含量低有利于金刚石的光谱透过性．     

硼掺入量对含硼金刚石单晶热稳定性的影响

 在铁基触媒原材料中添加不同含量的六方氮化硼,采用粉末冶金方法制备片状触媒,在六面顶压机上合成出含硼金刚石单晶。用体视显微镜对金刚石单晶的结构、形貌进行观察,并用电子探针（EPMA）和波谱仪（WDS）分析了金刚石（111）晶面的硼含量,发现金刚石表面有硼元素存在,且其含量随着触媒中掺硼量的增加而变化。在测定了含硼金刚石单晶的静压强度的基础上,采用冲击韧性测定仪和差热分析仪对不同掺硼量触媒合成出的金刚石单晶在空气中的热稳定性进行了系统的对比研究。结果表明,触媒掺硼量对金刚石的机械强度和热稳定性有重要影响,随着掺硼量的变化,其机械强度和热稳定性均存在一个最佳值。     

触媒组分对高温高压金刚石大单晶生长及裂纹缺陷的影响

本文利用六面顶压机,在5.6 GPa, 1250—1450℃的高压高温条件下,分别选用FeNiCo和NiMnCo触媒合金开展了金刚石大单晶的生长实验,系统地考察了触媒组分对金刚石单晶裂纹缺陷的影响.首先,通过对两种组分触媒晶体生长实验对比发现,金刚石大单晶裂纹缺陷出现的概率与触媒组分相关联.同NiMnCo触媒相比, FeNiCo触媒生长的金刚石单晶更容易出现生长裂纹.我们认为,这与FeNiCo触媒黏度高、流动性差、碳素输运能力差、生长中晶体比表面积大,进而导致其对生长条件稳定性的要求较高有关.其次,两种触媒极限增重速度和生长时间的关系曲线表明,相同生长时间条件下, NiMnCo触媒生长金刚石单晶的极限增重速度相对较大.再次,扫描电子显微镜测试结果表明,裂纹缺陷的出现与否同晶体表面平整度的高低无必然联系,表面平整度高的金刚石单晶内部也可能存在裂纹缺陷.最后,经对金刚石单晶傅里叶微区红外测试结果进行分析,得出了氮杂质含量的高低与金刚石单晶裂纹缺陷的出现与否无内在关联性的研究结论.     

Ni-Mn粉末触媒中固溶碳的作用效果和机理初探

 在国产DS6×800A型六面顶压机上，对比研究了含与不含固溶碳的Ni-Mn粉末触媒，采用直热式静压触媒法合成金刚石的差异。实验表明：Ni-Mn粉末触媒中固溶碳的存在，不仅可以提高金刚石的合成单产、细化金刚石晶粒，而且在同工艺条件下，能得到晶形完整度较高的金刚石单晶。     

添加Fe(C5H5)2合成氢掺杂金刚石大单晶及其表征

在Ni₇₀Mn₂₅Co₅-C体系中添加含氢化合物Fe(C₅H₅)₂作为新型氢源, 利用温度梯度法, 在压力为5.5-6.0 GPa、温度为1280-1400 ℃的条件下, 成功合成出氢掺杂的宝石级金刚石大单晶. 通过傅里叶显微红外光谱发现, 随着Fe(C₅H₅)₂添加量的增加, 合成晶体中与氢相关的对应于sp³杂化C-H键的对称伸缩振动和反对称伸缩振动的红外特征峰2850和2920 cm^-1逐渐增强, 而晶体中氮含量却逐渐减少. 通过合成晶体的拉曼光谱分析发现, 金刚石的拉曼峰伴随Fe(C₅H₅)₂的添加向高频偏移, 这表明氢的进入在金刚石内部产生了压应力. 观察扫描电子显微镜图像发现, 在低含量Fe(C₅H₅)₂添加时晶体表面平滑, 而高含量添加时晶体表面缺陷增多, 且呈现出气孔状. 使用新的添加剂Fe(C₅H₅)₂作为氢源, 合成出含氢宝石级金刚石单晶, 丰富了金刚石单晶中对氢的研究内容, 也可为理解天然金刚石的形成机理提供帮助.     

温度对Ib型和IIa型金刚石大单晶(100)表面特征的影响

本文在5.6 GPa, 1250–1340 ℃的条件下, 利用温度梯度法, 以FeNiMnCo 合金为触媒, 沿籽晶的(100)晶面成功合成了不同晶形的优质Ib型和IIa型金刚石大单晶. 利用激光拉曼附件显微镜, 分别对上述不同温度下合成的两类金刚石样品上表面(100)面的中心区域及棱角区域进行观察分析. 研究发现, Ib型和IIa型金刚石大单晶(100)晶面上从中心到棱角处黑色纹路的分布逐渐变黑变密集; 另外, 随着金刚石合成温度的升高, Ib型金刚石大单晶(100)面上黑色纹路由稀疏逐渐变稠密, 而IIa型金刚石大单晶的黑色纹路较为稀疏; Ib型金刚石大单晶的形貌特征表现为从低温晶体的不规则分布过渡到中温、高温晶体的典型树枝状分布. IIa型金刚石大单晶(100)面特征随温度变化规律与Ib型的类似. 这两类金刚石大单晶表面特征的差异可能是由于IIa 型金刚石具有比Ib型更小的生长速度和更少的氮含量. 最后, 对两类塔状金刚石大单晶进行拉曼光谱测试分析, 结果表明IIa型金刚石大单晶的品质较Ib型金刚石大单晶好.     

人造金刚石合成中黑色低磁金刚石的研究

 通过对合成金刚石的原材料和合成产物——石墨、Ni₇₀Mn₂₅Co₅触媒、普通人造金刚石、黑色人造金刚石、NiMnCoC熔体的磁化率测试，以及对黑色人造金刚石和普通人造金刚石破碎断面扫描电镜的对比分析，认为黑色人造金刚石形成低磁性的原因是由于合成过程中温度偏高、压力偏低，生长的金刚石质量差、裂纹多。晶体内夹杂了很多石墨与触媒包裹体，同时金刚石表面与金刚石晶体内的触媒包裹体之间形成贯穿性的裂纹。在金刚石化学提纯处理过程中，金刚石晶体内的铁磁性触媒包裹体杂质被通过裂纹进入的酸除去。因而在检测金刚石磁性时，黑色金刚石的磁性很小，呈弱磁性。     

籽晶{100}面形状对高温高压合成金刚石大单晶的影响

选用不同形状的{100}金刚石籽晶面,以NiMnCo合金为触媒,利用温度梯度法在压力为5.5 GPa、温度为1260～1300℃的条件下,合成Ib型金刚石大单晶。通过光学显微镜和电子显微镜对晶体的形貌进行表征。研究发现,将合成籽晶的{100}晶面切割成不同形状,只会令晶体的长宽比发生改变,晶体并不会因籽晶形状的改变而偏离{100}晶体的正常形貌。晶体的合成质量受到籽晶长宽比的影响:在籽晶长宽比较小的情况下,晶体的合成质量能够得到保证;但当籽晶长宽比过大时,合成晶体的下表面出现较多缺陷。关于籽晶形状对晶体生长情况影响的研究,揭示了籽晶形状与合成晶体形貌之间的关系,有利于更深入理解晶体的生长过程和外延生长机理,对于今后合成不同形貌的金刚石具有借鉴意义。同时此项研究有助于扩大籽晶的选取范围,降低籽晶的选择难度,提升工业级金刚石的利用率,为合成金刚石大单晶的籽晶选取提供了技术支持。     

国产六面顶压机多晶种法合成宝石级金刚石单晶

对国产六面顶压机平台下使用多晶种法合成宝石级金刚石单晶进行了系统的研究. 通过合理调整温度梯度法的合成腔体组装, 采用多晶种法, 探索多晶种法金刚石合成的压力和温度区间, 在单个合成腔体内放置3–5颗金刚石晶种, 成功合成出多颗(3–5)优质Ib型宝石级金刚石单晶. 多颗晶种的引入, 单次实验合成的多个金刚石晶体晶形及品质一致; 同时, 晶体的整体生长速度也有明显的增大. 多晶种法金刚石单晶合成的研究, 可以有效地利用腔体空间、提高单次金刚石单晶合成的效率, 解决压机大型化下高温高压资源利用率低的问题; 同时, 为宝石级金刚石单晶商业化生产提供重要的依据. 关键词： 金刚石 国产六面顶 多晶种 温度梯度法     

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。     

Synthesis of industrial diamonds using FeNi alloy powder as catalyst

Synthesis of diamond single crystals in Fe80Ni20 C system was carried out in a cubic anvil high-pressure and high-temperature apparatus. This paper reports that the surface morphology and inclusion distribution of the grown diamonds had been observed. It finds that the inclusions in cubic and octahedral diamonds radiated along certain crystal orientation, while the inclusion distribution in cubo-octahedral diamond seemed independent of crystal orientation. By using scanning electron microscope, the surface morphology of the three shapes of diamonds was observed. The results of Mossbauer spectrum indicated that there were iron-inclusions FeaC and Fe-Ni alloy in the diamonds. According to the Fe-C phase diagram, FeaC should have formed during the quenching process. Nickel might have an inhibitory effect on the formation of Fe3C.     

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     

ESR studies of diamond powders

The ESR spectrum of two defect centres were observed in finely ground diamond powders (0.5 to 30 μm size). The one centre has been seen before in irradiated and annealed single crystals of natural diamonds (the O₁ centre) while the second one has only been seen in synthetic diamonds grown from a nickel-iron melt and is only observable below 250 K. From the study of the variation of the intensity of these lines with size of particles it could be concluded that the O₁ centre lies just beneath the surface of these particles and the S centre at least 0.5 μm below the surface.     

The correlation of doping ions to holographic storage properties of Mg:Mn:Fe:LiNbO3 crystals

The congruent Mn(0.1 wt%):Fe(0.03 wt%):LiNbO₃ crystals doped with different concentration of MgO(0,1,3,6 mol%) have been grown by Czochralski method in air atmosphere. Some crystal samples were reduced in Li₂CO₃ powder. The defects and doping ions location in crystals were investigated by UV-Vis. absorption spectrum as well as infrared transmittance spectrum analysis. In two wave coupling experiments we determined the writing time, maximum diffraction efficiency and the erasure time of four crystal samples with He-Ne laser at 633 nm. The results indicated that Mg(3 mol%):Fe:Mn:LiNbO₃ was the most proper holographic recording media material among four crystals in the paper.     

Growth of gem-grade nitrogen-doped diamond crystals heavily doped with the addition of Ba（N3）2

Additive Ba(N 3) 2 as a source of nitrogen is heavily doped into the graphite-Fe-based alloy system to grow nitrogendoped diamond crystals under a relatively high pressure (about 6.0 GPa) by employing the temperature gradient method.Gem-grade diamond crystal with a size of around 5 mm and a nitrogen concentration of about 1173 ppm is successfully synthesised for the first time under high pressure and high temperature in a China-type cubic anvil highpressure apparatus.The growth habit of diamond crystal under the environment with high degree of nitrogen doping is investigated.It is found that the morphologies of heavily nitrogen-doped diamond crystals are all of octahedral shape dominated by {111} facets.The effects of temperature and duration on nitrogen concentration and form are explored by infrared absorption spectra.The results indicate that nitrogen impurity is present in diamond predominantly in the dispersed form accompanied by aggregated form,and the aggregated nitrogen concentration in diamond increases with temperature and duration.In addition,it is indicated that nitrogen donors are more easily incorporated into growing crystals at higher temperature.Strains in nitrogen-doped diamond crystal are characterized by micro-Raman spectroscopy.Measurement results demonstrate that the undoped diamond crystals exhibit the compressive stress,whereas diamond crystals heavily doped with the addition of Ba(N 3) 2 display the tensile stress.     

LiNbO3:Fe晶体的光折变对喇曼光谱的影响

我们观察到了LiNbO₃:Fe晶体中某些几何配置下十分异常的喇曼光谱现象。这一现象是与该晶体光折变后出现的异常光散射现象相联系的。 关键词：     

Electronic configuration of iron in diamond

CNDO molecular orbital calculations have been performed for Fe on both substitutional and interstitial sites in diamond, as well as Fe adjacent to a vacancy. Different charge states of the defects have also been studied, this dramatically influencing the relative occupancies of the Fe(3d) and Fe(4s) shells. It is this effect which is particularly sensitive to the environment of the Fe atom that in fact influences the Mössbauer spectrum. Conjectures as to the origin of the Mössbauer spectrum of Fe in diamond are made in the light of the present calculations.     

Diamond-graphite phase transition in ultradisperse-diamond clusters

A systematic study of the diamond-graphite structural phase transition in ultradisperse-diamond clusters obtained by the detonation technique is reported. Samples of two types, differing in the kinetics of detonation-product cooling, were investigated. The phase transition was achieved under heating in an inert atmosphere in the temperature range 720–1400 K. The transition was identified by Raman scattering and x-ray diffraction data. Raman and x-ray characterization showed the ultradisperse diamond, irrespective of the cooling rate used, to be cluster material possessing diamond structure with a characteristic nanocrystal size of 43 Å. The diamond-graphite phase transition in ultradisperse diamond is shown to start from the cluster surface inwards at T _pt≈1200 K, i.e. at substantially lower temperatures than is the case with bulk diamond single crystals.     

Pt插层对铁磁/反铁磁界面交换耦合的影响

在铁磁层(FM)/反铁磁层(FeMn)耦合体系中插入Pt 插层或对靠近FM/FeMn界面处的FeMn掺杂Pt元素,研究了体系的交换偏置场 H_ex及矫顽力H_c随Pt插层深度 d_Pt与Pt掺杂层厚度t_PtFeMn的变化关系. 实验结果表明,引入Pt插层后NiFe/FeMn(d_Pt)/Pt/FeMn体系的未补偿磁矩(UCS)的数量得到很大的提高,从而对H_ex与H_c 起到增强的作用; 同时, 从实验结果可以推测FeMn层内部UCS的分布深度约为1.3 nm. 另外,对靠近FM/FeMn界面处的FeMn掺杂Pt元素,发现掺入Pt元素后体系的H_ex 得到有效增强, 这是因为掺入Pt元素后体系UCS的数量也得到很大的提高.     

The effect of high pressure treatments on the stability of Fe-C/H2O compounds dispersed in graphite

Small amounts of⁵⁷ Fe were dispersed in graphite, with concentration of about 0.3 at% Fe. The sample was heat treated in a not anhydrous environment, under a pressure of 40 kbar and at a temperature of 1600°C (close to graphite-diamond equilibrium line). The Mössbauer spectrum showed the presence of Fe-C/H₂O compounds. These compounds did not disappear under subsequent heat treatment until about 1000°C. Thermal treatments at atmospheric pressure on the same kind of sample yields basically the same result. However, the stability of the compounds formed under high pressure was much higher. This fact was attributed to the formation of clusters of compounds inside the graphite, isolated from the surface. The formation and stabilization of those compounds under high pressure can explain the harmful effect of water on the diamond synthesis and its dependence on the type of graphite.