湘南瑶岗仙钨矿床成矿流体地球化学

瑶岗仙钨矿区地处南岭中段，位于加里东隆起带与印支-燕山凹陷带的交汇地带。为了更深入地研究瑶岗仙钨矿成矿流体的性质和演化，在前人工作的基础上，本文结合流体包裹体的岩相学特征及其产出的构造特征，对瑶岗仙钨矿流体包裹体进行了显微测温和激光拉曼探针分析，从而确定了瑶岗仙钨矿成矿流体的性质，并进一步探讨了其成矿物质来源及成矿机制。 对瑶岗仙石英脉型钨矿床的石英、萤石和矽卡岩型钨矿床中石榴子石流体包裹体的岩相学特征研究表明，与成矿有关的包裹体主要有三类：富液相、富气相和含子晶多相包裹体。脉型钨矿床中石英的包裹体均一温度范围 180℃～300℃，盐度为 0.88～6.45 wt% NaCl；矽卡岩钨矿床中石榴子石包裹体均一温度范围为 190～300 ℃，盐度为 0.1～8.95 wt% NaCl，成矿溶液的密度为 0.70～1.05 g/cm3，说明形成两种类型矿床的流体均属中温、低密度、低盐度流体；两类矿床形成的压力为 32～38 MPa，成矿深度为 1～2 km，因此该矿床是在浅成、低压条件下形成的。激光拉曼探针测试表明，石榴石包裹体的气相成分以 H2O 为主，石英中包裹体的气相成分及其相对含量为 H2O＞CO2＞CH4＞N2＞H2S。由此说明，从矽卡岩型白钨矿阶段到石英脉型黑钨矿阶段，成矿流体中不断有 CH4、CO2和H2O 等挥发份的加入，此时的流体是一种介于岩浆与热液之间的过渡性流体，具有上部偏液、下部偏浆的特点。 根据前人的研究结果以及矿脉中花岗岩角砾的发现，泥盆系、寒武系岩层在花岗岩浆侵入过程中发生了混合岩化，成为成矿物质来源的基础，而真正的成矿母岩应该是深部的花岗岩体，由此推测“赋矿花岗岩并非成矿源岩”，很可能来自深部母岩浆中熔离出的流体。而 CH4 等还原组分的含量增多，推测也有可能来自相对是还原环境的地幔过渡带或软流圈中。

湘南瑶岗仙钨矿床成矿流体地球化学

瑶岗仙钨矿床位于湘东南后加里东隆起和湘、桂、粤北海西—印支坳陷带的交接部位，是南岭地区最典型的石英脉型钨矿床之一。为了深入研究瑶岗仙钨矿的成矿机制，本文在野外地质工作基础上，选取有代表性的样品，进行了氦、氩同位素以及碳、氧、硫稳定同位素研究，探讨了矿床成矿流体的来源，成岩成矿的关系，并初步讨论了矿床的成因模式。论文主要获得以下认识： （1）对瑶岗仙矿区不同硫化物中流体包裹体的氦、氩同位素系统测定表明，该矿床毒砂流体包裹体中3He/4He比值为0.58~2.60 Ra；黄铁矿和黄铜矿流体包裹体中3He/4He比值分别为0.41~1.26 Ra 和0.37~0.43 Ra，黑钨矿流体包裹体中氦同位素组成相对变化较大，其3He/4He比值为0.05~0.49 Ra，这些He同位素组成均明显高于地壳相应值；毒砂流体包裹体中的40Ar/36Ar变化范围在309.94~454.39；黄铁矿流体包裹体中的40Ar/36Ar变化范围在409.12~1822.31；黄铜矿和黑钨矿流体包裹体中的40Ar/36Ar变化范围分别为673~886和325~903，明显高于饱和大气雨水的40Ar/36Ar值。上述氦、氩同位素组成揭示瑶岗仙钨矿床中的成矿流体具有壳、幔两端元混合的特点。结合区域地质构造演化和成矿年代学的研究成果，本文认为瑶岗仙钨矿床的成矿流体是瑶岗仙花岗岩浆分异出的含有地幔He的岩浆流体与大气成因地下水二端元混合的产物。 （2）层解石和方解石的C、O同位素显示，该矿方解石的13CPDB和18OSMOW的变化范围为-2.2‰~ -7.0‰（均值为-4.8‰）和5.6‰~14.4‰（均值为11.3‰）；层解石的13CPDB和18OSMOW的变化范围为-5.5‰~ -6.3‰（均值为-5.8‰）和12.7‰~14.3‰（均值为13.8‰）；该矿方解石、层解石的C、O同位素组成与赣南西华山钨矿床非常类似。这些C、O同位素指示，该矿的成矿流体主要来自岩浆水，后期有少量大气降水的参与。 （3）对瑶岗仙矿区不同硫化物的硫同位素研究表明，该矿硫化物δ34S值的变化范围很窄，为-2.0‰~1.5‰之间，且具有明显的塔式分布。这些特征暗示，该矿的硫来源单一，主要来自岩浆。 （4）瑶岗仙花岗岩过去被视为典型的S型花岗岩，但本文研究发现该花岗岩普遍含有地幔He。结合区域构造背景的最新研究成果，本文认为，原来被认为“由地壳物质重熔形成的”瑶岗仙S型花岗岩体，实际上也是一种岩石圈伸展背景条件下壳幔相互作用的产物，地幔物质和能量的参与在该花岗岩的形成过程中发挥了重要作用。 （5）瑶岗仙钨矿床与矿区复式花岗岩体具有密切时空关系，而且该矿的主要成矿流体和成矿物质均来自矿区花岗岩，故两者亦应具成因联系。

The effect of tungsten additive on the surface characteristics of amorphous Ni-P alloy

The variation of surface compositions on amorphous Ni80.4W1.5P18.1 alloy by O-2 oxidation and H-2 reduction treatments have been studied by XPS, UPS and ISS. It shows that addition of tungsten in the amorphous Ni-P alloy leads to dramatic changes of the relating component distributions in the surface layers before and after these treatments. Oxidation of a Ni80.4W1.5P18.1 amorphous alloy in 1 bar of oxygen at 513 K caused a significant segregation of nickel in different oxide states at the surface. The subsequent reduction of the oxidized surface with I bar hydrogen at 553 K resulted in only a small portion of Ni and P being reduced into elemental states, while most of them was found to combine to form a kind of nickel phosphate compound. On the other hand, under the same conditions, the oxidation and reduction of a Ni80P20 alloy gave rise to metallic Ni and elemental P as the predominate species on the alloy surface. The addition of W in the amorphous alloy might act as nuclei for a favorable formation of the phosphate structure which was proposed to be an active species for hydrogen-relating catalytic reactions. (C) 1999 Elsevier Science B.V. All rights reserved.

Synthesis and structural characterization of (pyrazolyl)alkenyl Fischer carbene complexes of chromium and tungsten

Michael addition of substituted pyrazoles 2 to 1-alkynyl Fischer carbene complexes (CO)(5)M=C(OEt)(CdropCPh) (1) (a, M = Cr and b M = W) afforded (pyrazolyl)alkenyl Fischer carbene complexes (CO)(5)M=C(OEt)(CH=C(R(1)R(2)R(3)pz)Ph) (R(1)R(2)R(3)pz = pyrazolyl) 3 (M = Cr) and 4 (M = W), respectively, with an exclusive (E)-configuration in mild to excellent yields. The reaction of la and 3,5-dimethylpyrazole (2b) was monitored to demonstrate the formation and decomposition of complex 3b by H-1 NMR measurements in CDCl3 at 23degreesC. Complexes 3 and 4 were characterized with H-1, C-13{H-1} NMR, IR spectroscopies and elemental analysis. When the substituted pyrazoles were 3-methylpyrazole (2a) and 3,5-di-tert-butylpyrazole (2d), molecular structures of the corresponding (pyrazolyl)alkenyl Fischer carbene complexes 3a and 4d were characterized by X-ray crystallographic study. (C) 2004 Elsevier Ltd. All rights reserved.

Optimizing the operation of straight-grate iron-ore pellet induration systems using process models

Mathematical models of straight-grate pellet induration processes have been developed and carefully validated by a number of workers over the past two decades. However, the subsequent exploitation of these models in process optimization is less clear, but obviously requires a sound understanding of how the key factors control the operation. In this article, we show how a thermokinetic model of pellet induration, validated against operating data from one of the Iron Ore Company of Canada (IOCC) lines in Canada, can be exploited in process optimization from the perspective of fuel efficiency, production rate, and product quality. Most existing processes are restricted in the options available for process optimization. Here, we review the role of each of the drying (D), preheating (PH), firing (F), after-firing (AF), and cooling (C) phases of the induration process. We then use the induration process model to evaluate whether the first drying zone is best to use on the up- or down-draft gas-flow stream, and we optimize the on-gas temperature profile in the hood of the PH, F, and AF zones, to reduce the burner fuel by at least 10 pct over the long term. Finally, we consider how efficient and flexible the process could be if some of the structural constraints were removed (i.e., addressed at the design stage). The analysis suggests it should be possible to reduce the burner fuel lead by 35 pct, easily increase production by 5+ pct, and improve pellet quality.

LPCVD of tungsten by selective deposition on silicon

Beta-phase W, selectively grown at 440C had resistivity 20 micro-ohm cm and maximum layer thickness 100nm. Hydrogen passivation proved essential in this process. Higher deposition temperatures resulted in increased layer thickness but incorporated WSi2 and alpha- phase W. Self limiting W grown on polycrystalline and heavily doped silicon yielded reduced thickness. Boron is involved in the WF6 reduction reaction but phosphorus is not and becomes incorporated in the W layer. The paper establishes an optimised and novel CVD process suited to IC contact technology. A funded technology transfer contract with National Semiconductor Greenock (M Fallon) resulted from this work.

Tungsten Silicide Contacts to Polycrystalline Silicon and Silicon-Germanium Alloys

Novel CVD WSi2 technology with low series and contact resistance in SiGe HBTs was achieved. Specific contact resistance to Si1-xGex with 0