不同反应参数下纤蛇纹石纳米管的水热合成研究

以活性MgO和纳米SiO2为原料,在仿地质作用的碱性水热环境下控制不同反应参数合成了多个系列的纤蛇纹石样品。利用XRD和IR分析系统地研究了不同反应参数对纤蛇纹石特征的影响。结果表明,活性MgO和纳米SiO2在水热环境中很容易转变成纤蛇纹石相,但形成完善纳米管结构须严格控制水热反应条件;pH值、反应温度和反应时间的提高均有利于水热合成结晶度及管状结构更加完善的纤蛇纹石,最佳水热反应条件为pH=13.8,200℃,反应60h,此条件下无其它杂质产物生成,合成温度较前人采用的300℃有所降低。利用SEM和AFM对最佳反应条件下合成的纤蛇纹石纳米管的形貌进行了观察,发现其为短柱状,准直性较高,表面光洁无杂质,直径均一,约50nm,长度多为400～500nm。     

碱度对水热合成纤蛇纹石纳米管的影响研究

为克服天然纤蛇纹石纳米管在量子组装应用上存在的不易提纯、易被伴生矿物堵塞、管径不均等缺点,以活性MgO和纳米SiO2为原料,采用水热法在不同碱度下合成了系列纤蛇纹石样品.时合成样品的X射线衍射(XRD)、傅立叶红外光谱(FTIR)以及扫描电镜(SEM)分析表明,在200℃.pH值大于13的条件下反应60 h以上能够合成结晶度比较完善的纤蛇纹石;碱度的提高有利于纤蛇纹石氢氧镁石层和硅氧四面体层的生长,并促使两者结合更为紧密,晶胞参数b0值增大,结构层更易卷曲,纤蛇纹石的纤维管状结构更加完善,结晶度提高,纤维的晶体轮廓更加清晰,直径更为均一,长度增加;最后确认在200℃.pH 13.8,反应60 h条件下合成纤蛇纹石纳米管的直径约50 nm.长度多在600nm以上,长度上优于前人的合成.     

纤蛇纹石纳米管的水热合成与表征

采用水热法进行了纤维蛇纹石的合成研究,通过改变反应温度、反应体系pH值合成了多个样品,并利用X射线衍射仪、透射电子显微镜、扫描电子显微镜和红外光谱仪等手段对合成样品的物相、结构和形貌进行表征,分析表明在180℃～220℃、pH值为10.39～13的水热体系中均能够合成纤蛇纹石结构纤维;在220℃、pH值为13的条件下合成晶型最好、纤维最长的纤蛇纹石纳米管,其内径约6 nm～8 nm、外径约30 nm～35nm,长约200 nm～400 nm。     

皂石的异相水热合成及其影响因素

与均相水热反应相比,异相水热反应不仅可以提供一个骨架离子的适度过饱和环境,而且其新相成核所需逾越的能垒较低,更有利于晶体的形成和生长。本文采用异相水热法合成在皂石,即固定初始物料中氧化镁的添加量与硅、铝的添加量之和的摩尔比为一定值,n(Mg)/n(Si+Al)=3∶4],在不同的合成温度和时间条件下合成了一系列不同Si/Al比的样品。所有样品的XRD图均呈现层状硅酸盐矿物的特征衍射峰,且d(060)≥0.153 nm,说明合成的是皂石矿物。其中,当n(Si)/n(Al)=5.43~7.89时,皂石的结晶度较好。实验表明,延长时间、提高合成温度有利于皂石晶体生长。在较低温度(160℃)下,样品中的杂相主要为水镁石和方沸石。水镁石相的存在主要归因于氧化镁在碱性条件下的快速水合及水镁石的慢速溶解,而方沸石则是由于Mg2+释放缓慢,导致溶液中Si4+及Al3+相对过剩而形成。这两种杂相均会随着反应时间的延长而逐渐消失。在较高温度(300℃)下,皂石的结晶度明显升高,并由于Mg2+的快速释放导致Mg2+的局部过剩,因而形成了少量1∶1型的纤蛇纹石。     

四川石棉县石棉矿床的蛇纹石化及成矿地球化学作用

超基性岩体(橄榄岩)已经完全蛇纹石化.主要的蛇纹石结构的网状结构,砂钟结构等.渐进蛇纹石化作用的发育对纤蛇纹石石棉的形成是有利的。矿区蛇纹石化的特征之一是叶蛇纹石广泛发育,而且是在石棉主要矿化期中或之前的中温条件下形成的.蛇纹石化过程中,主要元素均显示活动性.部分Si是从相对富Si岩石带入蛇纹岩的.Mg和Al从围岩蛇纹石向蛇纹石脉迁移。Ca和Fe从原生矿物迁出,分别形成碳酸盐矿物和磁铁矿。     

灼烧处理对纤蛇纹石反应活性的影响

    使用可循环的NH4Cl 溶液作为中间媒介获取Mg2+用于CO2 矿物封存是一种新兴工艺,但是纤蛇纹石在NH4Cl 溶液中较 低的Mg2+浸出率却是这项工艺发展的瓶颈。针对这一问题,本文采用灼烧处理对纤蛇纹石进行改性。结果表明, 灼烧处理 可以有效改变纤蛇纹石中Mg2+反应活性。在600℃灼烧后,所得产物与NH4Cl 反应的转化率达到55.64%,比灼烧前提高了 约43%。600℃灼烧处理脱除了纤蛇纹石外羟基,增大了矿物的反应表面积和具反应活性的Mg2+的量,促进了其与NH4Cl 的 反应 ;脱除内羟基后,具反应活性Mg2+减少,与NH4Cl 反应的转化率降低。     

物理化学条件对合成Mg／Al-LDH结晶度和结构的影响

采用共沉淀法在不同物理条件下合成了一系列镁铝层状双氢氧化物(LDH),用化学分析、XRD和红外光谱对产物的组成与结构进行了表征,并探讨了初始溶液Mg/Al比、平衡pH值、水热反应温度、干燥温度等因素对合成LDH产物的结晶度、Mg/Al比、结构以及镁铝水解率的影响。结果表明,在实验条件范围内,最佳的合成条件为:初始Mg/Al比为2∶1,pH值为10,合成温度50℃,在此条件下固体产物为单一LDH物相,合成LDH的Mg/Al比为2∶1,镁铝水解率分别为99.21%和98.97%,结晶度高,可以实现在较低的温度下水热合成LDH。由于在LDH结构中Al3 替代Mg2 的量不同,导致X衍射分析d值和晶胞参数呈规律性变化。     

斜纤蛇纹石的管道水特征研究

河北涞源斜纤蛇纹石为较小的中孔纳米管材料,通过氮吸脱附法、差热和热重曲线分析法、差示扫描量热分析法和红外光谱分析法,主要分析了其纳米管中管道水特征,明确了管道水作为有效加速剂和载体的作用,对以及对抗拉强度和介电常数的影响。研究表明斜纤蛇纹石纳米管中存在管道水(属于吸附水),去除温度在240℃±,内径为2nm～3nm的纳米管中管道水含量最高,管道水含量与纳米管分散度成反比。     

合成纤蛇纹石纳米管组装ZnS的实验研究

采用超声化学法在合成纤蛇纹石纳米管内进行了组装ZnS量子点的研究。利用X射线衍射仪(XRD)、透射电镜(TEM)及紫外-可见光谱仪对组装样品进行了表征。TEM观察发现在纤蛇纹石纳米管中组装了ZnS;XRD分析表明组装的ZnS量子点为β-ZnS结构,其平均晶粒度为4.2nm;紫外-可见吸收光谱研究表明ZnS量子点的吸收边红移5nm。     

吉林蛇纹石玉特征初步研究

对产自吉林省白山市抚松县沿江乡的蛇纹石玉样品分别从地质背景、激光诱导离解光谱、X射线粉末衍射和红外吸收光谱等方面进行了研究,并与辽宁岫玉样品进行了对比。结果表明,吉林蛇纹石玉样品的主要颜色为深浅不一的绿色,主要含Si,Al,Cr,Fe,Mn,Mg,Ca,Sr和Na等元素,其中Ca与Mg的谱线较强,Al,Mn与Sr的质量分数少;X射线粉末衍射结果显示,样品的主要矿物组成为纤蛇纹石,红外光谱结果也显示了其具有纤蛇纹石峰值的特征。     

An experimental study on the hydrothermal preparation of tochilinite nanotubes and tochilinite-serpentine-intergrowth nanotubes from metal particles

Tochilinite and tochilinite-serpentine-intergrowth (TSI) phases, including their nanotubes, are major components of CM carbonaceous chondrites. The laboratory synthesis of tochilinite and TSI phases, particularly their nanotubular forms, has rarely been reported. In this article, we show that FeMgAl tochilinite nanotubes and TSI nanotubes can be hydrothermally prepared from heat-treated metal particle mixtures below 200 °C under reducing and basic conditions. The metal particles used in the preparation of FeMgAl tochilinite were Fe, Mg and Al and those used for the preparation of TSI were Fe, Mg, Al, Si, Cr and Ni. FE-SEM, TEM, HRTEM, ED, EDX and XRD were used to characterize the reaction products. The yield of FeMgAl tochilinite and TSI was generally low and the FeMgAl tochilinite and TSI samples were very heterogeneous. Both the FeMgAl tochilinite and TSI crystallites existed in two forms, i.e. flakes and nanotubes. They generally had micrometer to sub-micrometer sizes and low crystallinity, and they were extremely sensitive to the electron beam. The FeMgAl tochilinite showed various structural modifications; however, the chemical compositions of these structural modifications were similar. The same phenomenon existed for TSI. The structural modifications of FeMgAl tochilinite and TSI may originate mainly from their mixed-layer structures, two-dimensional incommensurability of their sub-structures and the synthetic conditions. Some of the FeMgAl tochilinite nanotubes and the TSI nanotubes were likely to have been formed by curling of the corresponding flakes. The curling process appears to be delicate, requiring a quiet reaction environment with stable temperature and pressure and without vibrations. Our synthetic FeMgAl tochilinite and TSI showed remarkable similarities to natural tochilinite and TSI, respectively. Therefore, meteoritic tochilinite and TSI probably formed by reaction of metal particles with S²⁻ bearing water at temperatures of around 50-100 °C.     

尖晶石中的Si含量及其存在形式

自然岩石及简单和复杂体系中实验合成或经重新平衡的尖晶石化学成分显示，在中－低压条件下，与橄榄石共存的尖晶石可含一定量的Ｓｉ，其含量随温度和压力的升高而增大。用最小二乘法对简单体系中 实验数据的热力学模拟发现，Ｓｉ在铬尖晶石中以硅酸盐尖晶石（Ｍｇ２ＳｉＯ４）形式存在，Ｍｇ２ＳｉＯ４组份在铬尖晶石中的活度ａＳＤＭＧ２ＳｉＯ４＝（ＮＳＰＭＧ／２）２＊（ＮＳＰＳｉ）２（ＮＳＰＳｉ代表以４个氧为基础的单位尖     

Experimental study of incongruent evaporation kinetics of enstatite in vacuum and in hydrogen gas

Variations in bulk Mg/Si ratios in the various groups of chondritic meteorites indicate that Mg/Si fractionation occurred in the primitive solar nebula. Enstatite (MgSiO₃) evaporates incongruently forming forsterite (Mg₂SiO₄) as an evaporation residue; therefore, evaporation of enstatite produces Mg/Si variations in solid (Mg-rich) and gas (Si-rich) and must be considered as a probable process responsible for Mg/Si fractionation recorded in chondrites. To understand the evaporation kinetics of enstatite, incongruent evaporation experiments on enstatite single crystals have been carried out in vacuum and in hydrogen gas at temperatures of 1300 to 1500°C. A polycrystalline forsterite layer is formed on the surface of enstatite by preferential evaporation of the SiO₂ component, both in vacuum and in hydrogen gas. The thickness of the forsterite layer in vacuum increases with time in the early stage of evaporation and later the thickness of the forsterite layer remains constant (several microns). This is due to the change in the rate limiting process from surface reaction plus nucleation and growth to diffusion in the surface forsterite layer. The activation energy of the diffusion-controlled evaporation rate constant of enstatite is 457 (±58) kJ/mol. A thinner forsterite layer is formed on the surface of enstatite in hydrogen gas than in vacuum. Evaporation of enstatite in hydrogen gas is also considered to be controlled by diffusion of ions through the forsterite layer. The thin forsterite layer formed in hydrogen gas is ascribed to the enhanced evaporation rate of forsterite in the presence of hydrogen gas.The results are applied to incongruent evaporation under the solar nebular conditions. The steady thickness of the forsterite of nebular pressure-temperature conditions is estimated to be submicron because of the enhanced evaporation rate of forsterite under hydrogen-rich nebular conditions if evaporated gases are taken away immediately and no back reaction occurs (an open system). Because enstatite grains in the solar nebula would be comparable to the estimated steady thickness of forsterite, evaporation of such enstatite grains under kinetic conditions could play an important role in producing variations in Mg/Si ratios between solid and gas in the solar nebula.     

贵州水银洞卡林型金矿床首次发现大量次显微-显微可见自然金颗粒

在贵州水银洞卡林型金矿床原生富矿石的一条含砷黄铁矿细脉中发现有100余粒次显微-显微自然金颗粒(0.1~6μm),并具有清晰的显微岩相学结构。提出了该类型金矿次显微-显微可见自然金颗粒的形成过程可能与含Au热液-岩石相互作用过程中含Fe碳酸盐矿物溶解释放Fe的大量硫化物化而导致热液中Au的过饱和有关,含Fe碳酸盐赋矿围岩是形成高品位大型卡林型金矿床最重要的控制因素之一。     

Fixation of CO2 by chrysotile in low-pressure dry and moist carbonation: Ex-situ and in-situ characterizations

A detailed study of low-pressure gas-solid carbonation of chrysotile in dry and humid environments has been carried out. The evolving structure of chrysotile and its reactivity as a function of temperature (300-1200 °C), humidity (0-10 mol %) and CO₂ partial pressure (20-67 mol %), thermal preconditioning, and alkali metal doping (Li, Na, K, Cs) have been monitored through in-situ X-ray photoelectron spectroscopy, isothermal thermogravimetry/mass spectrometry, ex-situ X-ray powder diffraction, and water and nitrogen adsorption/desorption. Based on chrysotile crystalline structure and its nanofibrilar orderliness, a multistep carbonation mechanism was elaborated to explain the role of water during chrysotile partial amorphisation, formation of periclase, brucite, and hydromagnesite crystalline phases, and surface passivation thereof, during humid carbonation. The weak carbonation reactivity was rationalized in terms of incongruent CO₂ van der Waals molecular diameters with the octahedral-tetrahedral lattice constants of chrysotile. This lack of reactivity appeared to be relatively indifferent to the facilitated water crisscrossing during chrysotile core dehydroxylation/pseudo-amorphisation and surface hydroxylation induced product stabilization during humid carbonation. Thermodynamic stability domains of the species observed at low pressure have been thoroughly discussed on the basis of X-ray powder diffraction patterns and X-ray photoelectron spectroscopy evidence. The highest carbon dioxide uptake occurred at 375 °C in moist atmospheres. On the basis of chrysotile fresh N₂ BET area, nearly 15 atoms out of 100 of the surface chrysotile brucitic Mg moiety have been carbonated at this temperature which was tantamount to the carbonation of about 2.5 at. % of the total brucitic Mg moiety in chrysotile. The carbonation of brucite (Mg(OH)₂) impurities coexisting in chrysotile was minor and estimated to contribute by less than 17.6 at. % of the total converted magnesium. The presence of cesium traces (3 Cs atoms per 100 Mg atoms) was found to boost chrysotile carbonation capacity by a factor 2.7.     

即时合成Zn-Mg-Al层状双氢氧化物处理含Zn2+废水实验研究

在模拟含Zn2 废水中加入Mg2 和Al3 ,以NaOH为沉淀剂,研究金属盐水解即时合成层状双氢氧化物(LDH)去除Zn2 的可行性。详细探讨了体系终点pH值、配料中Mg2 /Zn2 摩尔比值及反应温度和时间对Zn2 去除率的影响,结合X射线衍射分析(XRD)探讨了Zn2 去除机理,并与化学沉淀法进行了比较。结果表明,实验条件下只有pH值显著影响Zn2 去除率(p<0.05),在9.0~11.0范围内去除效果最佳,达99%以上。通过XRD分析结合即时合成法特点,废水中Zn2 主要是在晶体生成阶段以Zn-Mg-Al三元LDH化合物形式被去除的。与化学沉淀法相比,即时合成法效果更好,适用pH值范围更广,用来处理含Zn2 废水更具优势。     

Crystal chemistry of ferric iron in (Mg,Fe)(Si,Al)O<Subscript>3</Subscript> majorite with implications for the transition zone

Fifteen samples of (Mg,Fe)SiO₃ majorite with varying Fe/Mg composition and one sample of (Mg,Fe)(Si,Al)O₃ majorite were synthesized at high pressure and temperature under different conditions of oxygen fugacity using a multianvil press, and examined ex situ using X-ray diffraction and Mössbauer and optical absorption spectroscopy. The relative concentration of Fe³⁺ increases both with total iron content and increasing oxygen fugacity, but not with Al concentration. Optical absorption spectra indicate the presence of Fe²⁺–Fe³⁺ charge transfer, where band intensity increases with increasing Fe³⁺ concentration. Mössbauer data were used in conjunction with electron microprobe analyses to determine the site distribution of all cations. Both Al and Fe³⁺ substitute on the octahedral site, and charge balance occurs through the removal of Si. The degree of Mg/Si ordering on the octahedral sites in (Mg,Fe)SiO₃ majorite, which affects both the c/a ratio and the unit cell volume, is influenced by the thermal history of the sample. The Fe³⁺ concentration of (Mg,Fe)(Si,Al)O₃ majorite in the mantle will reflect prevailing redox conditions, which are believed to be relatively reducing in the transition zone. Exchange of material across the transition boundary to (Mg,Fe) (Si,Al)O₃ perovskite would then require a mechanism to oxidize sufficient iron to satisfy crystal-chemical requirements of the lower-mantle perovskite phase.     

Compositional effects on element partitioning between Mg-silicate perovskite and silicate melts

High-pressure melting experiments were performed at ~26 GPa and ~2,200–2,400°C on synthetic peridotite compositions with varying FeO and Al₂O₃ contents and on a synthetic CI chondrite analogue composition. Peridotite liquids show a crystallisation sequence of ferropericlase (Fp) followed down temperature by Mg-silicate perovskite (MgPv) + Fp, which contrasts a sequence of MgPv followed by MgPv + Fp observed in the chondritic composition. The difference in crystallisation sequence is a consequence of the different bulk Mg/Si ratios. MgPv/melt partition coefficients for major, minor and trace elements were determined by electron microprobe and secondary ion mass spectrometry. Partition coefficients of tri- and tetravalent elements increase with increasing Al concentration in MgPv. A lattice strain model indicates that Al³⁺ substitutes predominantly onto the Si-site in MgPv, whereas most elements substitute onto the Mg-site, which is consistent with a charge-compensating coupled substitution mechanism. MgPv/melt partition coefficients for Mg (D_Mg) and Si (D_Si) are related to the melt Mg/Si ratio such that D_Si becomes lower than D_Mg at low Mg/Si melt ratios. We use a crystal fractionation model, based on upper mantle refractory lithophile element ratios, to constrain the amount of MgPv and Ca-silicate perovskite (CaPv) that could have fractionated during a Hadean magma ocean event and could still be present as a chemically distinct heterogeneity in the lower mantle today. We show that a fractionated crystal pile composed of 96% MgPv and 4% CaPv could comprise up to 13 wt% of the entire mantle.     

大洋橄榄岩的蛇纹石化过程:从海底水化到俯冲脱水SCIEI北大核心CSCD

蛇纹石化是海底最重要的水岩相互作用之一,指基性岩和超基性岩中的橄榄石和辉石等镁铁质矿物在相对低温条件下发生水热蚀变产生蛇纹石等矿物的热液变质作用。蛇纹石族矿物主要有三种,分别是利蛇纹石、纤蛇纹石和叶蛇纹石。低温状态蛇纹石族矿物主要以利蛇纹石和纤蛇纹石的形式存在,高温状态下主要以叶蛇纹石的形式存在。影响大洋蛇纹石化过程的因素不容忽视,温度、氧化还原程度、pH值、水岩比(W/R)等都在其中扮演着重要的角色。总的来说,地幔物质易出露在地壳减薄区域和断裂构造处,这有利于与流体充分接触反应,从而决定了大洋蛇纹石化作用发生的可能位置。对蛇纹石化程度的描述,当前人们大多通过岩石微观结构、地球化学指标来定性指示,磁学指标有望实现对蛇纹石化程度的定量解释。蛇纹石化作用对海底磁异常、地球生命演化进程、成矿作用等都有一定的贡献。此外,俯冲带脱水及弧岩浆的形成都与之有联系。总之,基性与超基性岩石蛇纹石化与俯冲带蛇纹岩脱水过程是地球水循环过程的重要机制,但未来揭示蛇纹岩的磁学性质和俯冲变质过程,仍需进一步探索。     

Dissolution kinetics of synthetic Na-smectite. An integrated experimental approach

The effect of pH and Gibbs energy on the dissolution rate of a synthetic Na-montmorillonite was investigated by means of flow-through experiments at 25 and 80 °C at pH of 7 and 9. The dissolution reaction took place stoichiometrically at 80 °C, whereas at 25 °C preferential release of Mg over Si and Al was observed. The TEM-EDX analyses (transmission electronic microscopy with quantitative chemical analysis) of the dissolved synthetic phase at 25 °C showed the presence of newly formed Si-rich phases, which accounts for the Si deficit. At low temperature, depletion of Si concentration was attributed to incongruent clay dissolution with the formation of detached Si tetrahedral sheets (i.e., alteration product) whereas the Al behaviour remains uncertain (e.g., possible incorporation into Al-rich phases). Hence, steady-state rates were based on the release of Mg. Ex situ AFM measurements were used to investigate the variations in reactive surface area. Accordingly, steady-state rates were normalized to the initial edge surface area (11.2 m² g⁻¹) and used to propose the dissolution rate law for the dissolution reactions as a function of ΔG_r at 25 °C and pH∼9: