溶胶—凝胶工艺制备二氧化钛超微细粉过程中的物相和显微结构的变化

用溶胶—凝胶工艺制备了不同晶型的TiO_2超微细粉,锐钛矿型TiO_2超微细粉呈分散的球形颗粒,平均粒径约为0.03μm;金红石型TiO_2超微细粉呈分散的圆柱状颗粒,平均粒径约为0.07μm。用FT-IR.XRD.DTA/TGA和TEM等手段研究了TiO_2凝胶在煅烧过程中物相和显微结构的变化。发现TiO_2凝胶在200℃以下呈非晶态,在300℃时结晶成锐钛矿,在700℃时,锐钛矿开始转变为金红石,在1000℃时,锐钛矿消失,全部转变为金红石。     

Geology and Geochemistry of the Yangtizishan‐Moshishan Metamorphosed Sedimentary Anatase Deposit in Zhenglan Qi,Inner Mongolia: Discovery of a New Genetic Type of Titanium Deposit

Anatase and its allomorphic mineral rutile have the most prominent economic significance among titanium mineral resources and constitute one of the badly needed mineral resources currently in China. The Yantizishan-Moshishan anatase deposit was formerly referred to as an iron deposit. Based on recent investigation and exploration the authors believe that it is actually a large metamorphosed sedimentary anatase-dominated deposit belonging to a new genetic type. Ore bodies occur in stratoid and lenticular forms in Mesoproterozoic (1751 Ma) schist, metasandstone (metasiltstone), and amphibolite. Rich ores have perthitic structure comprising chiefly interbedded quartz perthite (with disseminated anatase and rutile) and anatase perthite. Ore minerals are mainly anatase and subordinately rutile and ilmenite (±hematite), while nonmetallic minerals are chiefly quartz with a certain amount of anthophyllite and biotite (±garnet). The grain sizes of anatase, rutile and ilmenite are 0.01–0.1 mm. Rich ores contain 3.14% to 15.46% TiO2, averaging 6.91%, while the low-grade ores have TiO2 content about 1.2%to 2.97%, averaging 1.76%. The ores have relatively high TFe and V contents. Trace elements in anatase and rutile such as Nb and Cr were analyzed by the electron microprobe. According to their relatively low Nb and Cr contents, source anatase and rutile must have come from meta-mafic rocks. Trace elements of the associated ilmenite show relatively high MnO and low MgO contents, just in contrast to those of ilmenite in V-Ti-magnetite ores of magmatic origin. The protoliths of amphibolite wall rocks should be basalt and picrite-basalt. Pertochemical data suggest that the tectonic setting of these rocks belongs to an island arc or a transitional belt between the island arc and oceanic ridge. Silicon isotope study shows that δ30Si values of different anatase ores, quartzite, and schist in this deposit are 0.1‰ to –0.9‰, similar to those of marine hydrothermal exhalative sedimentary deposits. All of these geological and geochemical characteristics of the ore deposit suggest that the anatase ores and amphibolite are products of submarine basic volcanism. The ores had chemical precipitation features, but were later subjected to regional intermediate (or somewhat lower) grade metamorphism (1158 Ma). Rutile was formed mainly in the process of this metamorphism. The ore belt locally underwent hydrothermal modification during the emplacement of Late Yanshanian granite (118?Ma).     

Pre-orogenic upper crustal softening by lower greenschist facies metamorphic reactions in granites of the central Pyrenees

Pre-kinematic greenschist facies metamorphism is often observed in granites and basement units of mountain belts, but rarely dated and accounted for in orogenic cycle reconstructions. Studying pre-kinematic alteration is challenging because of its usual obliteration by subsequent syn-kinematic metamorphism often occurring at conditions typical of the brittle–ductile transition. It is, however, to be expected that pre-kinematic alteration has major implications for the rheology of the upper crust. In the 305 Ma-old Variscan basement of the Bielsa massif (located in the Axial Zone of the Pyrenees), successive fluid–rock interaction events are recorded in granites below 350°C. Combined microstructural and petrographic analysis, low-T thermobarometry and in situ U–Th/Pb dating of anatase, titanite and monazite show extensive pre-orogenic (pre-Alpine) and pre-kinematic alteration related to feldspar sericitization and chloritization of biotite and amphibole at temperatures of 270–350°C at 230–300 Ma. This event is followed by a second fluid–rock interaction stage marked by new crystallization of phyllosilicates at 200–280°C and is associated with the formation of mylonitic shear zones and fractures parallel to the shear planes. U–Pb anatase and monazite ages as well as the microtextural relationships of accessory minerals suggest an age for this event at 40–70 Ma, consistent with independent regional geology constraints. The Variscan basement was therefore softened at late to post-Variscan time, at least 150–200 Ma before the main Alpine shortening while Alpine-age compression (c. 35–50 Ma) leads to the formation of a dense net of mylonites. The associated deformation, both distributed at the scale of the Bielsa massif and localized at decametric scale in mylonitic corridors, precedes the strain localization along the major thrusts of the Axial Zone. The Bielsa massif is a good example where inherited, pre-orogenic upper crustal softening controls the deformation patterns in granitic basement units through low-grade metamorphic reactions.     

LA-ICP-MS独居石U-Th-Pb测年方法研究

金红石、锐钛矿和板钛矿为TiO₂的三种同质异象矿物。在进行金红石微区原位U-Pb定年时,通常主要依据电子探针数据、辅以阴极发光图像确定研究矿物为金红石,而电子探针数据和阴极发光图像有时并不能有效地区分金红石、锐钛矿和板钛矿,若用于进行定年的矿物中同时存在三种或其中两种TiO₂矿物,获得的年龄可能是混合年龄,无显著地质意义。因此,对TiO₂同质异象矿物的快速准确鉴别具有重要意义。本文以桂中铝土矿中TiO₂矿物为研究对象,将激光拉曼光谱应用于TiO₂同质异象矿物的鉴别,准确识别出桂中铝土矿TiO₂矿物中存在四组不同特征的激光拉曼光谱谱线。前三组分别具有锐钛矿、金红石和板钛矿的激光拉曼光谱特征峰;第四组具有两种激光拉曼光谱特征谱线,第一种同时具有锐钛矿的特征峰144、198、397、513、636cm^-1和金红石的特征峰442、607cm^-1,第二种同时具有锐钛矿的特征峰144cm^-1和板钛矿特征峰153、247、325、636cm^-1。结果表明：桂中铝土矿TiO₂矿物中除金红石、锐钛矿和板钛矿外,还存在同时具有两种矿物结构特征的中间矿物。分析认为研究区可能经历了后期的区域变质作用,导致TiO₂同质异象矿物发生相变,这类中间矿物则记录了相变的过程。本文应用激光拉曼光谱快速准确地鉴别出桂中铝土矿TiO₂同质异象矿物,为金红石微区原位U-Pb定年研究中矿物的鉴别提供了新思路。

     

内蒙古羊蹄子山-磨石山锐钛矿矿床斜长角闪岩类的岩石学和地球化学特征

内蒙古羊蹄子山-磨石山是本项目组近几年来发现和勘查研究的一个以锐钛矿为主的沉积变质型钛矿床,是钛矿床的一个新的成因类型。矿体产于中元古代二道凹群变质岩〔(1751±8)Ma〕中,其围岩为石英绢云片岩、绢云石英片岩、变质(粉)砂岩和斜长角闪岩等。矿石实际上是富含锐钛矿等钛矿物和直闪石、黑云母的变质石英(粉)砂岩和片岩。斜长角闪岩是矿体的重要围岩之一,多呈似层状、透镜状产出,与矿体在时、空、成因上有密切关系。按矿物组合特征,斜长角闪岩可分为角闪岩、斜长角闪岩和斜长岩等3类。恢复其原岩,大致相当于苦橄玄武岩、玄武岩、玄武安山岩和粗面质安山岩。岩石化学和微量元素地球化学特征表明,它们主要属于活动大陆边缘岛弧和洋脊过渡带的拉班玄武岩类,而且岩石分异演化较彻底。矿体和斜长角闪岩都是海底基性火山活动的产物,后又遭受了区域变质作用。     

制备方法对纳米TiO2介孔柱撑蒙脱石结构和性能的影响

分别通过离子交换方法和离子交换-水热法制备纳米TiO2介孔柱撑蒙脱石,利用XRD、DSC-TG、N2吸附-脱附等方法对材料进行结构特征与性能的表征。实验结果表明,传统的离子交换方法可使制备的钛柱撑蒙脱石比表面积、孔体积增大;离子交换-水热法可使TiO2介孔柱撑蒙脱石中锐钛矿晶型更好,晶粒变大,柱撑蒙脱石结构更稳定,而且水热的温度越高,所需反应时间越短,锐钛矿的晶型更好,发育更完善。     

内蒙古羊蹄子山-磨石山锐钛矿矿床富矿层和花岗岩锆石SHRIMP U-Pb定年及其地质意义

在详细地质勘查和岩石学研究的基础上,选取了矿区北部磨石山矿带元古宙沉积变质型富锐钛矿矿层和南部羊蹄子山矿带西段与热液改造型富矿体接触的花岗岩体中的锆石,分别进行了较系统的SHRIMP锆石U-Pb定年研究。结果显示,富矿层的火山-沉积变质岩系中锆石存在2540～1158Ma(207Pb/206Pb年龄)的年龄谱范围,具有1751Ma、1859Ma和2525Ma3个主要年龄峰,其中以1751Ma左右的岩浆事件最为强烈,可能代表了海底火山热液喷气或喷流作用形成的锆石年龄或与之有关的成矿年龄;1158Ma的数据点为锆石增生事件年龄,可能记录了含矿岩系遭受低角闪岩相或绿片岩相的变质事件或与之有关的变质成矿作用年龄,由此确定火山-沉积岩的沉积作用应发生于1751Ma,时代为中元古代,是华北地台北缘结晶基底最早的沉积盖层,而非前人认为的古元古界上部二道凹群;其他几组较老年龄的碎屑锆石是沉积物源区的或由强烈的海底火山喷发作用从深部结晶基底带来的,它们主要表现为岩浆事件。花岗岩体的侵位(或结晶)年龄为118Ma,属燕山晚期产物,代表了羊蹄子山矿带西段局部遭受后期热液改造的成矿期年龄。     

锐钛矿光电子强化黑曲霉吸附铅离子实验研究

铅元素在自然界分布广泛,其可溶性盐对动植物及人体有巨大毒性,借助真菌等生物修复技术手段清除环境中铅污染逐渐成为研究热点之一。本文使用溶胶凝胶法合成了锐钛矿电极,通过X射线衍射(XRD)、拉曼测试、环境扫描电镜和电化学测试等对其进行了系统表征,进而联合实验室分离筛选出的一株黑曲霉Aspergillus niger Bpb1成功构建了光-半导体矿物-微生物系统。研究了光电子对黑曲霉吸附铅离子的影响,实验结果表明锐钛矿光电子与黑曲霉协同作用下,实验组较对照组铅离子吸附速率平均增加33.6%,最高增加42%。进一步使用环境扫描电镜观察黑曲霉外部形态,发现光电子不影响铅矿物的形态。结合能谱测试和前人文献得知铅离子与有机酸结合形成以有机铅盐为主的矿物,缠绕在菌丝中。本研究实现了利用光能加速真菌代谢的过程,表明锐钛矿光电子与黑曲霉协同作用只对真菌吸附铅离子速率产生一定的加强,并未影响其成矿形态。     

Supported TiO2 on Kaolin,Cordierite, and Calcite for Photocatalytic Removal of Dyes from Wastewater

Kaolin, cordierite, and calcite are investigated as supports for TiO₂. The prepared TiO₂/support samples are examined for the removal of organic dyes from wastewater. The samples are preliminarily investigated to identify the optimal loaded system using synthetic wastewater containing methylene blue (MB). Data indicate that the investigated support significantly affects the photocatalytic activity of the supported TiO₂. Low photocatalytic activity toward MB degradation is observed upon using TiO₂/calcite when compared to the unsupported TiO₂. Interaction between calcite and titania species probably occurrs to produce the less photoactive CaTiO₃ amorphous species. Anatase TiO₂ is obtained upon using kaolin and cordierite as supports. The low photocatalytic performance of the TiO₂/kaolin sample is also observed. A high concentration of MB on TiO₂/kaolin surfaces blocks the photoactive sites. TiO₂/cordierite shows the highest photocatalytic activity compared to the unsupported TiO₂ as well as the other TiO₂/support samples. Rigid cordierite particles suppress the agglomeration of TiO₂ particles during the preparation, leading to a high exposed surface of TiO₂ towards light illumination. TiO₂/cordierite is investigated for the removal of organic dye from real wastewater collected from a textile dyeing factory. Color removal of up to 46% is achieved upon UV irradiation.     

内蒙古正蓝旗羊蹄子山-磨石山锐钛矿矿床地质与地球化学

锐钛矿及其同质异象金红石是钛矿资源中最具经济意义的,也是中国当前的紧缺矿种之一。前人把羊蹄子山矿床确定为铁矿床(点),通过近几年的研究和勘查,笔者认为这是一个以锐钛矿为主的沉积变质型矿床,是钛矿床的一个新的类型。矿体产于中元古代〔(1751±8)Ma〕片岩、变质石英(粉)砂岩和斜长角闪岩中,呈似层状、透镜状产出。富矿石具有细纹状构造,表现为以石英为主(含浸染状锐钛矿)和锐钛矿条纹互层。矿石矿物主要为锐钛矿,次有金红石和钛铁矿(±赤铁矿),脉石矿物以石英为主,含一定量的直闪石和黑云母(±石榴子石)。锐钛矿、金红石和钛铁矿的粒度很细,粒径为0.01～0.1mm。富矿TiO2含量为3.14%～15.46%,平均6.91%,而贫矿的TiO2含量为1.2%～2.97%,平均1.76%。矿石含较高的TFe和V。电子探针分析表明锐钛矿和金红石的Nb和Cr含量较低,说明矿物的源区来自变质基性岩。钛铁矿微量元素的特点是富锰贫镁,和岩浆型钒钛磁铁矿中钛铁矿的微量元素正好相反。围岩斜长角闪岩恢复其原岩大致相当于玄武岩、苦橄玄武岩等。岩石化学揭示其生成构造环境为岛弧或岛弧和洋脊的过渡带。硅同位素组成结果显示,不同锐钛矿矿石、石英岩和片岩等的δ30Si值为0.1‰～-0.9‰,与海底热液喷气沉积矿床的数据相似。所有上述矿床的地质和地球化学特征表明,锐钛矿矿石和斜长角闪岩都是海底基性火山活动的产物,矿石具有化学沉积特征,而后来遭到中级(偏低)区域变质作用(1158Ma)的影响,金红石主要形成于区域变质作用。该矿床在燕山晚期〔(118±3)Ma〕由于花岗岩的侵位又局部受到热液改造。