金刚石中氢的研究及其意义

含氢对于天然与高温高压合成金刚石体内而言是固有的，但是对CVD金刚石来说并非固有。氢可以稳定存在于晶格位、键心、反键心及四面体空隙等金刚石的结构属性中，也可以存在于显微流体包裹体中。即便是在 1473K下淬火，氢在金刚石中也并不发生迁移或扩散，表明氢在金刚石结构中是自陷的。金刚石中的氢的研究对于地幔矿物学及材料科学等均有重要理论意义和实际意义。     

氢在金刚石结构中的自陷模型

氢在金刚石结构中是自陷的。可以稳定存在的自陷形式有成键氢、反键心氢、键心氢及四面体空隙氢四种模型，而且氢在其中的相对稳定程度依上述顺序渐次递减。     

金刚石中水的研究

根据红外光谱定量分析的原理，利用吸收峰位之间的相关性，判别出金刚石中结构水(-OH)的伸缩振动频率为3760cm^-1；水分子的反对称伸缩与对称伸缩振动频率分别为3630cm^-1和3200cm^-1。在分别垂直于金刚石(100)、(110)及(111)方向上的定向显微红外光谱研究表明：-OH、H2O及C-C键在不同方向上所测得的浓度是不相同的；样品本身存在晶格畸变；-OH和H2O共有的OH基团在金刚石中的取向并不相同；-OH和H2O并没有进入金刚石的晶格，更多的可能是存在于金刚石的空隙中。     

天然金刚石的定向红外光谱研究

本文对天然金刚石在垂直于（100）、（110）和（111）三个方向上定向红外光谱进行了定量比较分析，指出C－H键和C－C键在以上三个方向上的浓度不相同，引起C－C键和C－C键在不同方向上的浓度差异是由于氢具有优先取代垂直于（111）方向上C－C键中碳原子的倾向。     

基于红外光谱-拉曼光谱研究山东郯城砂矿的金刚石及包裹体类型

对山东郯城砂矿中的金刚石开展了傅里叶红外光谱和显微激光拉曼光谱的测试,结果显示,红外光谱均可见C—C的本征峰;绝大多数可见氮的吸收峰:双氮的吸收峰、聚合氮的吸收峰和氮片晶的吸收峰;部分可见氢的吸收峰:C—H的吸收峰、C—N的吸收峰和H2O的吸收峰.郯城金刚石以Ⅰa型金刚石为主,有ⅠaA、ⅠaB、ⅠaAB型,而Ⅱa型仅1粒;氮类型包括双氮(A心)、聚合氮(B心)及氮片晶(B'心),说明金刚石中的孤氮(C心)已经转化为双原子氮,但部分双原子氮未完成进一步的聚形.金刚石拉曼峰值集中在1131 cm–1,拉曼位移漂移程度较小,说明金刚石内部应力发生小幅的变化.在郯城金刚石中首次发现柯石英包裹体,出现139 cm–1、152 cm–1、212 cm–1、272 cm–1、328 cm–1、356 cm–1、428 cm–1和529 cm–1左右的拉曼峰值.在1粒金刚石中柯石英包裹体数量多达十余个,直径几μm至几十μm,呈针状、哑铃状、浑圆状和短柱状等多种形态.郯城金刚石中柯石英包裹体的出现,可作为郯城地区存在榴辉岩型金刚石的可靠标志,也佐证了该地部分金刚石的来源可能和洋壳循环或者俯冲过程有关.镁橄榄石包裹体上覆分散的黑色石墨斑点,与山东蒙阴、辽宁和湖南金刚石中的镁橄榄石等不同种类包裹体具有相似特征,推测这些石墨斑点是晶体包裹体形成后,由于外部环境温压条件的变化产生.     

关于Fe-C(H)系高温高压合成金刚石多晶形成机制的一些思考

Fe-C(H)系高温高压金刚石多晶在合成片上呈成堆聚集状、不均匀分布.多晶中的金刚石晶粒多为八面体晶形、随机定向、大小无规律,表面发育"锯齿状"生长台阶,普遍发育塑性形变等缺陷.多晶中的金刚石晶粒间接触界线清晰、呈突变状.无论是利用品体成核、还是晶体长大理论都只能解释多晶中存在的部分现象.利用碳原子配位四面体生长基元模型分析多晶的形成机制值得探索.深入分析Fe-C(H)系高温高压合成金刚石多晶的形成机制不但有利于改善金刚石合成的工艺、提高合成金刚石多晶的品级.而且有利于为人们探讨天然金刚石多晶的形成机制及其深部意义提供科学线索.     

湖南发现天然产出的Ⅰb型金刚石

正金刚石结构是由两个面心立方点阵沿立方晶胞的体对角线偏移1/4单位嵌套而成的晶体结构。按N含量和N聚集类型,金刚石一般分为Ⅰa型、Ⅰb型、Ⅱa型和Ⅱb型(含B元素)。研究证实,金刚石形成时杂质N主要以孤N(C中心)形式存在,在一定条件下,孤N逐渐转变为双原子N(A中心),这一转变过程所需时间较短,因而在自然界中Ⅰb型金刚石较少见。Ⅰb型金刚石以孤原子氮的存在形式被作为合成金刚石的证据。目前,华北和扬子地区金刚石矿产调查二级项目组在湖南发现了8粒Ⅰb型金刚石,     

尼日利亚石—塔菲石—黑铝镁铁矿及相关系列矿物的晶体结构构筑原理

从氧原子最紧密堆积以及阳离子充填四面体和八面体空隙原理出发 ,以简单氧化物矿物最紧密堆积结构类型金绿宝石、尖晶石、铁钒矿为基础 ,深入讨论了复杂氧化物矿物最紧密堆积结构类型彭志忠石、尼日利亚石、塔菲石、黑铝镁铁 (钛 )矿等晶体结构构筑原理。以O表示全部为阳离子八面体配位的层 ;以T层表示阳离子八面体配位与阳离子四面体配位的混合层 ,其中T1表示阳离子八面体配位与一种方向阳离子四面体配位的混合层 ,T2 表示阳离子八面体配位与两种方向阳离子四面体配位的混合层。这类矿物晶体结构可用O、T1、T2 堆积方式表征 ,O层与T层交替排列。如 :彭志忠石 ( 6H)的晶体结构表示为…OT2 OT1OT1… ,塔菲石 ( 8H)的晶体结构表示为…OT2 OT1OT2 OT1… ,尼日利亚石 ( 2 4R)的晶体结构表示为…OT1OT2 OT2 OT1…× 3 ,等等 ;它们的晶体结构中既有尖晶石的…OT2 OT2 …晶体结构单位 ,又有铁钒矿的…OT1OT1…晶体结构单位。     

金刚石的微区显微红外光谱分析及其意义

金刚石的微区显微红外光谱分析表明：金刚石的形成是一个结晶物化条件变异，原始物质变换的复杂而又漫长的过程；杂质N、H等在其中的分布不均匀；同一晶体的中心部位其氮聚合态的转变时间与边缘相差约602Ma；金刚石中的成键氢以对应－CH3的C－H键形式存在要比对应于＞C＝CH2的C－H键形式存在更为广泛。利用红外光谱研究晶化固态物质必须强调定向及微区研究的意义。     

ТДН——К1型岩心钻具

目前,在裂隙大的岩层和矿体中钻进时,采用T?-2型和T?H-4型的双管岩心钻具,配以59毫米或76毫米的金刚石钻头,岩心和矿心采取率应不低于70%.但是,采用这种钻具进行钻进,不是经常能够达到高指标,以致降低了工程质量.因此,为了能在极复杂的条件下进行钻进,试制了一种配备有正常胎体厚度的金刚石钻头的T?H-K1型岩心钻具(图1).T?H-K1型钻具可以在9～12级裂隙大或裂隙小的岩层和矿体中采取岩心和矿心.钻具是由外管     

金刚石中的成键氢

金刚石中杂质相的研究一直倍受关注,但大多集中在B、N两种杂质的研究上,而对于氢在其中的赋存状态研究则刚刚开始。从振动谱学（IR、Raman）的角度对氢在金刚石中的一种赋存状态--成键氢进行的研究表明,成键氢在金刚石中可以以碳氢键、H2及 O-H键的形式存在。     

Water incorporation in synthetic and natural MgAl2O4 spinel

The solubility and incorporation mechanisms of water in synthetic and natural MgAl₂O₄ spinel have been investigated in a series of high-pressure/temperature annealing experiments. In contrast to most other nominally anhydrous minerals, natural spinel appears to be completely anhydrous. On the other hand, non-stoichiometric Al-rich synthetic (defect) spinel can accommodate several hundred ppm water in the form of structurally-incorporated hydrogen. Infrared (IR) spectra of hydrated defect spinel contain one main O-H stretching band at 3343-3352 cm⁻¹ and a doublet consisting of two distinct O-H bands at 3505-3517 cm⁻¹ and 3557-3566 cm⁻¹. IR spectra and structural refinements based on single-crystal X-ray data are consistent with hydrogen incorporation in defect spinel onto both octahedral and tetrahedral O-O edges. Fine structure of O-H bands in IR spectra can be explained by partial coupling of interstitial hydrogen with cation vacancies, or by the effects of Mg-Al disorder on the tetrahedral site. The concentration of cation vacancies in defect spinel is a major control on hydrogen affinity. The commercial availability of large single crystals of defect spinel coupled with high water solubility and similarities in water incorporation mechanisms between hydrous defect spinel and hydrous ringwoodite (Mg₂SiO₄) suggests that synthetic defect spinel may be a useful low-pressure analogue material for investigating the causes and consequences of water incorporation in the lower part of Earth’s mantle transition zone.     

绿柱石中铁离子的晶格占位及致色作用

绿柱石族宝石颜色丰富,一直是市场上重要的宝石品种。几十年来,国内外学者对不同颜色绿柱石的致色机理及改色工艺开展了广泛的研究。铁离子作为重要的致色过渡金属离子之一,其价态调控是绿柱石改色工艺的关键,所以铁离子的价态、晶格占位和对应的致色作用也一直是绿柱石研究的焦点。铁离子被认为可能存在于绿柱石中的铝氧八面体Al³⁺格位、硅氧四面体Si⁴⁺格位、铍氧四面体Be²⁺格位、结构通道2a或2b位和晶格间隙6g位等位置,是蓝、绿或黄等颜色绿柱石的主要致色元素。本文通过对绿柱石的晶体结构、铁离子的核外电子排布和晶格占位等方面文献资料的梳理及综合分析,认为Fe²⁺和Fe³⁺分别对蓝色和黄色绿柱石的呈色起着主导作用。当Fe²⁺和Fe³⁺处于晶格中不同位置时致色作用的具体差异,仍有待于进一步研究。     

Rotation and dilation deformation mechanisms for auxetic behaviour in the α-cristobalite tetrahedral framework structure

 Analytical expressions are derived for the Poisson's ratios associated with a three-dimensional network of regular, corner-sharing tetrahedra in which: (1) the tetrahedra are assumed to be rigid and free to rotate relative to each other; (2) the tetrahedra are assumed to maintain shape and orientation but are free to change size (dilate); (3) tetrahedral rotation and dilation are assumed to act concurrently. The structure has a primitive unit cell containing four tetrahedra and is analogous to the molecular structure of α-cristobalite. Strain-dependent variations in Poisson's ratio are also predicted by the models. For deformation due to tetrahedral rotation the network is found to exhibit negative Poisson's ratios in each of the three principal directions, with the magnitude of the Poisson's ratio being dependent on the angle of rotation of the tetrahedra. The behaviour of the Poisson's ratio is isotropic in the transverse plane, but anisotropic elsewhere. In the dilation model negative Poisson's ratios equal to −1 are observed for uniaxial loading in any of the principal directions, with the value being constant irrespective of tetrahedral size. The model for concurrent tetrahedral rotation and dilation allows positive as well as negative Poisson's ratios, with the values determined by the framework geometry and relative strengths of the two mechanisms. The concurrent model also offers a design route to materials and structures having ultrahigh Young's moduli. Received: 15 February 2000 / Accepted: 1 October 2000     

Bonding in silicates: an assessment of bonding in orthopyroxene

The molecular orbital and crystal field theories are compared and their applicabilities to bonding in silicates are discussed, A molecular orbital bonding model is favoured for orthopyroxene since bonding in both tetrahedral and non-tetrahedral sites within the crystal structure can be described and accommodated by the theory. It is suggested that Fe located in M₂ sites has more electron delocalisation (or covalence) associated with it than Fe located in the M₁ site. Order-disorder phenomena in orthopyroxene are discussed in relationship to Mueller's (1970) two-step exchange mechanism, whereby the first step corresponds to vacancy activation and the second step to exchange of Fe between an ‘octahedral’ site and a vacancy.     

Effect of the Si/Al ordering on structural parameters and the energetic stabilization of vermiculites – a theoretical study

The effect of the Si/Al distribution in the tetrahedral sheets of the vermiculite mineral has been investigated employing density functional theory. The structures of six models for vermiculite with the structural formula (Mg₄)(Mg₁₂)(Si₈Al₈)O₄₀(OH)₈·24(H₂O) per unit cell were fully optimized. The models differ by the T···Mg²⁺···T coordination of the interlayer Mg²⁺ cations by two central cations from the adjacent tetrahedral sheets of the 2:1 vermiculite layers (T,T=Si,Al). We observed the formation of very strong hydrogen bonds between water molecules solvating the interlayer Mg²⁺ cations and the surface basal oxygen atoms of the 2:1 layers. The directionality of hydrogen bonds is the major factor determining the layer stacking in the vermiculite structure. Results showed that the most stable model is that where only silicon atoms in the tetrahedral sheets coordinate all interlayer Mg²⁺ cations.