Nb,Mo,Ti,Ta,W掺杂硅化石墨扫描电镜研究

以硅粉的1％，2％－10％（wB）将Nb,Mo,Ti,Ta,W等5种金属粉掺入硅粉中，用液硅渗透法（LSP）制务出系列掺杂硅化石墨样品，这对些样品抗折，抗拉强测试结果：Nb(6%)－硅化石墨性能最优，抗拉强度提高了20％－27％，Mo(1%),Mo(5%)掺杂效果次之，而Ti(7%),Ta(3%),W(7%)等的杂反使材料强度降低。扫描电子显微镜（SEM）分析显示：Nb(6%）掺杂使抗担强增强的原因在于，新的铌与碳的间隙化合物相的生成，减小了硅化石墨显微结构的尺寸，且使材料外层及内核结构均匀，致密，统一，因而能有效分散应力集中，缓冲裂纹扩张，增大承载截面，从而提高材料力学性能。相反Ti(7%),Ta(3%)等掺杂后，尽管使材料外层结构致密，但内部结构疏松，晶粒，孔隙尺寸不大小不一，形态各异，外结构极不统一，导致材料性能下降。     

LSP法制备硅化石墨的主要影响因素

详细探讨了用LSP法制备硅化石墨的影响因素，结果表明，基料的热膨胀系数，石墨化与否，孔隙特征等物性以及温度、时间、真空度等硅化条件是决定基料硅化效果的关键因素。     

液硅渗透法制备硅化石墨工艺及性能初探

硅化石墨是由碳化硅、石墨、游离硅多相组成的复合材料，具有导电、导热、自润滑、耐腐蚀、耐高温、抗氧化、抗热震、高硬度等优异性能，广泛应用于工业部门及高科技领域，具有巨大的经济效益。利用国产代用设备和自制的渗硅浸渍坩锅。采用液硅渗透法制备出性能与日、美、俄产品相当的硅化石墨。其主要性能指标为：抗压强度３１９ＭＰａ，抗折强度１５１ＭＰａ，抗拉强度６０．１ＭＰａ，硬度７８９２ｋｇ／ｍｍ＾２，空气中耐温度〈     

磷块岩中的硅质组分和硅质岩

磷块岩中存在着大量硅质组分和硅质层。硅质矿物以自生石英、硅质条带、燧石结核、硅质胶结物和硅质交代物的形式产出。硅质胶结物有四种结构形式,在剖面和平面上与其它成分胶结物有一定的演变关系。硅化作用有众多的宏观和微观形态,硅化结果使P_2O_5含量大大下降。盆地型磷块岩硅化作用的硅源可能来自海底火山活动,台地型磷块岩硅化作用的硅源主要与陆源水的混合有关。     

湖南耒阳上堡花岗岩风化壳型铌钽矿床铌钽的赋存状态

湖南耒阳上堡花岗岩风化壳型铌钽矿床有三种类型铌钽矿石：钽铌铁矿矿石(类型Ⅰ)、铌金红石矿石(类型Ⅱ)和细晶石-钽铌铁矿矿石(类型Ⅲ)，铌钽矿床中的铌钽主要赋存在独立矿物钽铌铁矿、铌金红石、细晶石中，其次赋存在铁锂云母中。在Ⅰ类型矿石中铌钽矿物所含铌占有率为46．36％，钽为50．94％，在Ⅱ类型矿石中铌钽矿物所含铌占有率为43．37％，钽为56．44％，在Ⅲ类型矿石中铌钽矿物所含铌的占有率为48．81％，钽为66．37％。在云母中所含铌钽较高，铌占有率为5．71％～17．2％，钽为2．33％～12．52％。     

桩海地区下古生界潜山内新一类储层:硅化岩储层的发现及特征

通过对研究区下古生界取心井的岩心描述、镜下(包括偏光显微镜和扫描电镜)观察,并对目的层段声波时差、密度、自然伽马等测井参数进行分析,发现研究区下古生界硅岩段与原生硅岩的岩-电特征明显不同,本文称之为“硅化岩”,并总结了硅化岩段的特征.研究区下古生界硅化岩之原岩残留结构清晰、硅岩晶粒自形程度高;硅化岩段常出现热水矿物萤石、重晶石、黄铁矿、铁方解石、石英等的共生组合,且次生热水矿物的再次溶蚀特征显著;硅岩段孔隙极为发育,不但有角砾间溶洞、溶缝,次生矿物溶蚀也形成溶洞、裂缝等有效储集空间,另外,自形石英晶簇的晶间微孔隙也十分发育;与碳酸盐岩相比硅化岩段具有极低速度、较低密度特点,且其分布具有“穿层性”.通过与下古生界原生硅岩特征进行对比,认为桩海地区下古生界硅化岩为次生成因,其形成是埋藏溶蚀作用的结果.次生硅化岩为下古生界潜山中一种新的储层类型.这种新储层类型的发现不但对中国东部陆相盆地高成熟探区的油气挖潜具有重要的实际意义,而且对于进一步丰富硅岩理论、推动硅岩研究进展也具有一定的学术价值.      

溶胶—凝胶法在纳米材料制备中的应用

溶胶－凝胶法在纳米材料制备中的应用邢作云饶瑞孙国才（材料系，武汉４３００７４）（华中理工大学，武汉４３００７４）纳米材料是指由极细晶粒组成、特征维度尺寸在纳米数量级（１～１００ｎｍ）的固体材料．由于极细的晶粒和大量处于晶界和晶粒内缺陷中心的原子，纳米...     

石墨炉原子吸收法测定铝矾土中的硅

通过对照硅在热解石墨管、涂钼及涂钨石墨管中的原子化行为，选用涂钼石墨管和Ｌａ做基体改进剂，石墨炉原子吸收法测定铝矾土中的硅。经铝矾土管理样分析验证，方法可靠。实际样品分析结果与重量法和钼蓝法相符，对质量分数ｗ（ＳｉＯ２）在４％水平的铝矾土进行分析（ｎ＝５），其ＲＳＤ在１２％～１７％。     

纳米硅粉水泥土的强度特性及固化机理研究

将性能优异的纳米硅粉作为外掺剂应用于水泥土改性研究。通过室内试验，探讨了纳米硅粉水泥土的强度特性。试验表明，一定掺量下的纳米硅粉能够显著提高水泥土的各个龄期强度。结合试验测试和理论分析，探讨了纳米硅粉在水泥水化硬化过程中的作用以及纳米硅粉与土之间的作用，在此基础上，分析了纳米硅粉改性水泥土工程性状的机理，旨在为纳米硅粉应用于工程实践开展理论和试验研究探索。     

石墨合成金刚石的效果

石墨是合成金刚石的碳源,不同石墨材料合成金刚石的效果及其性能各有不同。石墨材料的种类、石墨化程度、纯度、晶粒尺寸与晶形、择优取向、密度、机械压强与杂质元素等是影响合成金刚石效果的一些重要因素。影响金刚石生长的因素是多方面的,在此仅就石墨材料影响合成金刚石的效果的因素进行讨论。     

Evidence for stable grain boundary melt films in experimentally deformed olivine-orthopyroxene rocks

The microstructure of olivine-olivine grain boundaries has been studied in experimentally deformed (1200–1227 °C, 300 MPa) partially molten olivine and olivine-orthopyroxene rocks. In-situ melting produced ∼1 vol% melt in all samples studied. Grain boundary analyses were carried out using a number of transmission electron microscopy techniques. The grain boundary chemistry in undeformed olivine-orthopyroxene starting material showed evidence for the presence of an intergranular phase along some, but not all, of the olivine-olivine boundaries. In the deformed samples, ultrathin Si-rich, Al- and Ca-bearing amorphous films have been observed along all investigated olivine-olivine grain boundaries. The chemistry of the grain boundaries, which is considered to be indicative for the presence of a thin film, was measured with energy-dispersive X-ray spectroscopy (EDX) and energy-filtering imaging. The amorphous nature of the films was confirmed with diffuse dark field imaging, Fresnel fringe imaging, and high-resolution electron microscopy. The films range in thickness from 0.6 to 3.0 nm, and EDX analyses show that the presence of Al and Ca is restricted to this ultrathin film along the grain boundaries. Because thin melt films have been observed in all the samples, they are thought to be stable features of the melt microstructure in deformed partially molten rocks. The transition from the occasional presence of films in the undeformed starting material to the general occurrence of the films in deformed materials suggests that deformation promotes the formation and distribution of the films. Alternatively, hot-pressing may be too short for films to develop along all grain boundaries. A difference in creep strength between the studied samples could not be attributed to grain boundary melt films, as these have been found in all deformed samples. However, a weakening effect of grain boundary melt films on olivine rheology could not be ruled out due to the lack of confirmed melt-film free experiments. Received: 13 April 1999 / Revised, accepted: 10 February 2000     

Development of a reconstituted brown coal material using cement as a binder

Like any other coal, the highly heterogeneous nature of brown coal can sometimes make it difficult to interpret the results of laboratory experiments. More homogeneous samples with properties reproducible in the laboratory would provide significant advantage, especially in understanding the effects of various factors in the properties of coal. An attempt was made to develop reconstituted coal (RC) samples in the laboratory through an extensive material development and laboratory testing programme. The latter consisted of mainly uniaxial compression tests. The main objective in developing the RC material is to use it in future research on CO₂ sequestration in unmineable coal seams. A highly homogeneous coal sample would make it much easier to identify, for example, the effect of CO₂ sorption on the mechanical, flow and transport properties of coal. Uniaxial compression tests were conducted on some brown coal samples to determine the approximate mechanical properties. The results revealed an average uniaxial compressive strength of 1.46 MPa, an average elastic modulus of 77.43 MPa and a Poisson’s ratio of 0.16. The measured properties were used as a reference for the development of RC samples. An extensive laboratory experimental programme was conducted to develop RC samples with the desirable mechanical properties. Portland cement was used as the cementing agent for the RC. Different variables such as percentage of cement, water content, compaction load and curing time were taken into account when developing RC samples. Uniaxial compression tests were carried out to ensure that the RC samples were reasonably homogeneous and the properties were similar to those of natural coal. Percentages of cement by weight of coal such as 4, 6 and 8% were attempted and a 4% cement mix with 50% water was considered most suitable for the RC samples. Average compressive strength of 0.8 MPa (28-day strength) and an average elastic modulus of 34 MPa were achieved for the RC samples. Further efforts at improvement would involve better matching of the uniaxial compressive strength and elastic modulus of RC samples with the natural coal samples.     

Nonstoichiometry and growth of some Fe carbides

Iron carbides containing from 31 to 17 atomic % carbon, with cohenite XRD structure and optical properties, were grown in experiments in Fe–Ni–S–C, Fe–Ni–C, and in Fe–C at 1, 6, and 7 GPa. X-ray cell volumes increase with C content. Compositions listed above vary considerably outside the nominal (Fe,Ni)₃C stoichiometry of cohenite/cementite. Cohenites coexisting with Fe–C liquid are carbon poor. The Eckstrom-Adcock carbide, nominally Fe₇C₃, was found to show compositions from 29 to 36 atomic % C at 7 GPa in Fe–C. Both these materials are better regarded as solutions than as stoichiometric compounds, and their properties such as volume have compositional dependencies, as do the iron oxides, sulfides, silicides, and hydrides. The fraction of C dissolved in cohenite-saturated alloy is found to become smaller between 1 and 7 GPa. If this trend continues at higher pressures, the deep mantle should be easier to saturate with carbide than the shallow mantle, whether or not carbide is metastable as at ambient pressure. At temperatures below the cohenite-graphite peritectic, cohenite may grow as a compositionally zoned layer between Fe and graphite. The Eckstrom-Adcock carbide joins the assemblage at 7 GPa. Phases appear between Fe and C in an order consistent with metasomatic interface growth between chemically incompatible feed stocks. Diffusion across the carbide layer is not the growth rate limiting step. Carbon transport along the grain boundaries of solid Fe source stock at 1 GPa, to form C-saturated Fe alloy, is observed to be orders of magnitude faster than the cohenite layer growth. Growth stagnates too rapidly to be consistent with diffusion control. Furthermore, lateral variations in carbide layer thickness, convoluted inert marker horizons, and variable compositional profiles within the layers suggest that there are local transport complexities not covered by one-dimensional diffusive metasomatic growth. In contrast to many transport phenomena which slow with pressure, at 7 GPa and 1,162 °C, carbide growth without open grain boundaries is faster than at 1 GPa with fast grain boundary channels, again suggesting C transport is less of a constraint on growth than C supply. C supply at 7 GPa is enhanced by graphite metastability and the absence of fast grain boundary channels to divert C into the Fe instead of growing carbide. At both 1 and 7 GPa, the growth rate of carbide is found to systematically vary depending on which of two stock pieces of graphite are used to form the growth couple, suggesting that some property of each specific graphite, like C release rate, possibly from amorphous binder material, may influence the cohenite growth process. At temperatures near and above the cohenite-graphite peritectic at 1–1.5 GPa, complex intergrowths involving Fe–C liquids and extensive thermal migration transport were encountered, eroding the organized spatial resolution, and the range of cohenite compositions found grown below this peritectic from growth couples of crystalline Fe and graphite. The migration of graphite to a position in the metasomatic sequence between liquid and cohenite demonstrates that the solubility of graphite in liquid increases with temperature above the peritectic, whereas the solubility of graphite in cohenite below the peritectic decreases with temperature. The variable solubility of graphite in cohenite, shown by thermal migration, emphasizes that cohenite does have compositional variations.     

Bolshetagninskoe Deposit Microcline-Pyrochlore Ore Process Mineralogy

Bolshetagninskoe deposit is one of the most important Russia niobium potential sources. It is confined to carbonatite complex of the same name that is situated in the Sayan Mountains, Eastern Siberia. In the result of VIMS exploration niobium ores reserves have been applied by Russian State Reserve Committee in 2012 year. Ores contain about 1% Nb2O5 and are unique in that the economic pyrochlore mineralization is concentrated in alkaline metasomatic rocks but not in carbonatites[1]. During exploration 47 borehole samples and 6 bulk samples were collected and studied by process mineralogy techniques (optic mineralogical analyze, optic image analyzer system, XRD, EPMA). 26 borehole samples and 2 bulk samples were tested by rougher floatation to define geometallurgical items and to understand the ore’s behavior. Four volumetric samples have been tested by commissioned flowsheet (radiometric separation → impact milling → selective floatation → pyrochlore leaching → ferroniobium). There are three ore types in the Bolshetagninskoe deposit: microcline-pyrochlore (MP), biotite-columbite-pyrochlore (BCP) and carbonate-pyrochlore (CP). MP type is the most important one. MP ore consists of microcline (59wt%–70wt%) with minor carbonates, apatite, sulfides, goethite. Pyrochlore, the essential Nb mineral (94% of ore Nb content), occurs as fine grains (weighted average grain size is 57 μn). Since pyrochlore grains are fine and friable, the ore preparation size and method is a main problem of its treatment. While primary ore processing is effective to remove about 30% waste material it is important to evaluate its influence on floatation feed grade.     

自由边界形状与近边界裂纹相互作用模型研究

大量的研究表明, 岩爆发生条件与岩石的力学性能有关。岩体中微裂纹的形成、扩展和汇合对岩体的力学性能产生显著影响,可以导致材料的逐渐劣化直至破坏。对于单轴压缩的岩石试件,其破坏型式主要是微裂纹的摩擦滑移、自相似平面扩展和弯折扩展。基于断裂力学机制,对单轴压缩荷载下3种不同边界形状,即直边、凸形、凹形情况下近边界原生斜裂纹的扩展进行了理论研究,并运用FLAC数值模拟技术,建立了基于Interface界面单元的裂纹扩展数值模型。近直边界及凸形边界情况的裂纹扩展使用梁渐近模型来解析薄片岩层的屈曲断裂问题,对于近凹形边界情况给予简化,提出了裂纹－圆－椭圆相互作用的修正模型并进行理论分析。研究结果表明,基于Interface界面单元的裂纹扩展的数值模型正确,解析解与数值解吻合较好,相应的梁渐近模型及裂纹-圆-椭圆模型可以合理地分析应力调整过程中裂纹的扩展和裂纹与不同洞室表面形状的相互作用问题,为岩爆工程及理论研究提出了新的理论依据。     

The equilibration of high-angle grain boundaries in dynamically recrystallized quartz: the effect of crystallography and temperature

Dynamically recrystallized and sutured quartz grains from metamorphic rocks with different strain intensities and temperature conditions ranging from ca. 350°C to ca. 700°C have been studied. Universal-stage measurements on quartz–quartz high-angle grain boundaries show that they are never curved but always consist of straight segments which preferentially occupy specific crystallographic orientations in relation to both neighboring crystals. With increasing temperature the segments preferentially concentrate in a decreasing number of orientations, mainly near the rhombohedral {101̄1} planes. The crystallographic data and the observations on grain boundary geometries suggest that: (i) grain boundary orientations are strongly crystallographically controlled, (ii) this control is the main factor on the textural equilibration of quartz–quartz grain boundaries in metamorphic rocks, and (iii) grain boundaries from dynamically recrystallized quartz should be regarded as annealed and equilibrated fabrics that are stable against subsequent annealing as long as the material is not re-deformed.     

Small-scale transport of trace elements Nb and Cr during growth of titanite: an experimental study at 600?°C, 0.4 GPa

Trace element distribution in titanite overgrowths on rutile has been investigated experimentally at 600?°C, 400?MPa and f_O2 near NiNiO buffer. Compositionally homogenous Cr- or Nb-doped synthetic rutile single crystals or Nb-containing natural rutile crystals were the source of Cr, Nb and Ti to synthesize titanite using the double-capsule technique. All element exchange with the source of Si, Ca and Al occurred via a NaCl–H₂O fluid. Titanite forms quickly and exclusively around the rutile crystals. The titanite overgrowth separates rutile from the bulk fluid, and all elements from rutile dissolution have to pass through the titanite rim. Trace element concentrations in titanite show a considerable scatter in experiments with and without Al, although the average concentrations of Cr or Nb of titanite around compositionally homogeneous synthetic rutile approach the expected values for closed system conditions. Variability of Al with Cr or Nb in the titanite is not correlated. The Al zoning is irregular and patchy, and also the distribution of trace elements does not show systematic trends in the spatial distribution. In experiments using zoned natural rutile, the concentrations of Nb in titanite are related to the Nb zoning in rutile, but the contents also vary unsystematically. Under the controlled conditions of the experiment, the explanation for the strongly irregular spatial distribution is most likely due to variations in elemental concentrations during transport from the rutile along the titanite grain boundaries. The transport pathway is complex because grain boundary migration is important during titanite growth. Such irregular element distribution is also found in a natural sample of titanite overgrowth on rutile from an eclogite with retrograde overprint in the amphibolite facies. Transport of Ti and trace elements was focused on grain boundaries and shielded from the rutile as a source of these elements. We conclude that this type of zoning is not related to changes in P–T or composition in an open system, but solely controlled by transport in and through the titanite rim.     

The migration of fluid-filled grain boundaries in recrystallizing synthetic bischofite: first results of in-situ high-pressure, high-temperature deformation experiments in transmitted light

The effect of fluids on recrystallization behaviour is well known; however, the detailed microscale distribution of fluid in grain boundaries and the influence of fluid on grain boundary migration are still unresolved. In this study, in‐situ deformation experiments in transmitted light microscopy were undertaken, as this allows continuous and direct observation of the whole range of processes involved in fluid‐assisted grain boundary migration. A new see‐through deformation apparatus was developed to enable the control of fluid pressure. Bischofite containing small amounts of aqueous fluid was deformed at temperatures between 50 and 90 °C, over a range of fluid pressure from 0.5 to 1 MPa, and strain rates of 5 × 10^?6 to 1 × 10^?4 s^?1. The rates of grain boundary migration were measured at different temperatures and strain rates. Detailed observations during and after the deformation illustrate the evolution of migrating fluid‐filled grain boundaries and show that the incorporation of fluids from inclusions as well as their pinch‐off is dependent on the grain boundary velocity, the thickness of the grain boundary and the size and shape of the inclusions. Direct evidence is presented for the contraction of the grain boundary fluids into isolated inclusions after equilibrium conditions are attained.     

掺入膨润土中的石墨最大粒径确定方法

核废料处置库缓冲层除要具备良好的隔离防渗外,还需要有卓越的导热性能。为此,论文以钠基膨润土为基础,混入高导热率天然石墨,配置兼具防渗-导热功能的缓冲材料。按照相同的石墨掺入率（20%,质量比）,把最大粒径为50目、100目、200目和325目的石墨分别掺入膨润土,形成均匀的石墨-膨润土混合物。开展膨润土-石墨混合物自由膨胀率、恒体积膨胀力和渗透等水-力特性试验,探讨石墨粒径对膨润土-石墨混合物水-力性能的影响。结果表明,相同石墨掺入率下,最大粒径100~200目的石墨和膨润土混合,可以形成更好的缓冲材料,其渗透系数最小,而膨胀力最大。究其原因,应与石墨-膨润土的接触方式相关。石墨呈扁平状结构,粒径较大时,石墨和膨润土被压实后,容易在扁平结构末端形成未被充填的孔隙;而石墨粒径较小时,石墨和膨润土颗粒接触面积增大,石墨属于憎水性材料,膨润土-石墨界面处提供了更多渗漏通道。研究结论为配置核废料处置库缓冲层材料提供了科学参考。