煤系高岭石/醋酸钾插层复合物热相变研究

高岭石插层复合物作为新型矿物材料现已被广泛应用。然而,插层复合物热稳定性较难控制使其在聚合物中的应用一直受到限制。本文应用热分析、X射线衍射、质谱及发射红外光谱等表征技术对煤系高岭石/醋酸钾插层复合物受热分解产物及微结构变化进行了研究。结果表明,煤系高岭石/醋酸钾插层复合物热相变主要经历以下几个阶段:插层水脱嵌(约350℃),插层剂醋酸钾脱嵌(约400℃),脱羟基(约450℃),偏高岭石形成(450~550℃),KHCO3出现(约600℃),KHCO3热分解形成K2CO3和KAl Si O4出现(约700℃),热解产品K2Al2Si O4出现(约800℃),K4Al2Si2O3出现(900~1000℃),大量K3Al O3形成阶段(1100℃及以上)。此外,还发现通过控制插层率和加热温度,可实现高岭石插层复合物的可控分解、新物相合成与转变,从而有利于新材料的合成。     

醋酸钾/偏高岭石插层复合材料的制备及机理研究

采用机械研磨法,成功制备了醋酸钾/偏高岭石插层复合材料.通过XRD、FTIR和TEM研究了插层前后偏高岭石结构的变化,提出了该复合材料的插层机理和结构模型:首先醋酸钾与水分子以配位键结合,然后通过机械研磨作用进入偏高岭石层间,并将偏高岭石片层撑开.当进行热处理时,水的挥发也会对偏高岭石片层起到撑开作用.最终导致偏高岭石被撑开、剥离.在插层复合材料中,醋酸根与偏高岭石的铝氧层通过水分子桥接方式连接,钾离子水合物为保持电中性,位于带负电的硅氧层附近.     

1,4-丁二醇插层高岭石的实验研究

以二甲亚砜为前驱物,1,4-丁二醇为插层剂,采用二步插层法制备1,4-丁二醇与高岭石的复合材料。实验研究了温度、时问对插层效果的影响及该复合物在水中的稳定性。采用XRD和IR法对试样进行分析表征。结果表明,在140℃,180℃条件下插层一定时间,均可获得1,4-丁二醇插层高岭石,在180（、条件下反应16h以上,同时高岭石的层间距增大到1．157nm,制备的1,4-丁二醇插层高岭石结构稳定,180℃反应32h可导致高岭石层间1,4-丁二醇转变为其他物质,形成稳定的有机插层高岭石。     

插层-磨剥法制备不同径厚比的高岭石

通过对醋酸钾/高岭石插层复合物的机械磨剥制备了不同径厚比的高岭石样品,并利用X射线粉晶衍射(XRD)、激光粒度仪、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和傅里叶变换红外光谱(FTIR)表征了4个样品的粒径、结构以及形貌。实验结果表明:随着插层磨剥次数的增加,高岭石的结晶度指数(HI)由原矿的1.29降至0.69,结晶度降低,晶体结构在一定程度上遭到破坏。同时,4个样品的粒径及厚度逐渐减少,径厚比依次增大至11.7。此外,经过3次插层磨剥洗涤后,部分剥离的片层发生卷曲,但很少完全卷曲成纳米卷。     

煤系高岭石的原始晶粒尺寸及结晶度对插层作用的影响

采用SEM、XRF、XRD和IR研究了大同、平朔和淮北煤系高岭石的结构、粒度及其特性,探讨了粒度大小对高岭石插层作用的影响及其机理。研究发现:粒度中等且结晶有序的平朔煤系高岭石插层率最高,其次为晶体粗大但结晶有序的大同高岭石,粒度最小且结晶无序的淮北高岭石插层率最低。研究认为高岭石原始晶粒粒度对高岭石插层作用有重要影响,中等粒度最有利于高岭石插层作用的进行,粒度过大或过小均不利于高岭石插层作用的进行,其原因是由于不同粒度的高岭石插层作用过程中导致的差异弹性变形引起的。结晶有序度对高岭石插层作用也有重要影响,结构无序不利于插层作用的进行。     

插层高岭石层间醋酸钾的作用和取向

利用X粉晶衍射和激光拉曼光谱实验分析高岭石及其醋酸钾插层物的结构。通过实验表明醋酸钾对结晶指数(HI)为0．9的高岭石进行插层．插层率为73％，使高岭石的d(001)由0．72075nm增加到1．42093nm。进入高岭石层间的醋酸根利用其羧基上的两个氧同时和高岭石的面内羟基形成氢键，在高岭石层间直立取向，而对其内羟基基本无影响。当温度升高时，与面内羟基伸缩振动有关的峰(3698cm^-1,3684cm^-1，3672cm^-1等)发生红移，且强度增加；而与内羟基伸缩振动有关的峰(3621cm^-1)则发生蓝移。温度升高到100C以上，开始发生去插层过程；直到250C，插层分子还不能完全从高岭石层间脱去。     

高岭石有机插层机理及其复合物的应用

综述了近几十年来国内外高岭石有机插层纳米复合材料领域中有机插层理论的研究进展，主要对插层剂在纳米层问的形态及结构、插层过程中水的作用、吸附与插层、脱嵌过程等方面以及纳米复合材料的应用进行了详细的阐述，并在此基础上提出了该领域研究的重点及热点。     

反复插层对高岭石结构和性能的影响

利用二甲基亚砜(DMSO)和去离子水对高岭石进行重复的插层与水洗,并采用X射线衍射(XRD)、傅立叶变换红外光谱(FT-IR)、旋转魔角核磁共振(MAS NMR)、扫描电镜(SEM)对产物进行表征。研究发现,经10次重复插层与水洗,高岭石结晶度降低,结构遭到一定程度破坏但未发生崩塌。MAS NMR数据显示,Si谱未发生较大变化,Al谱化学位移变化了3.5×10-6,但Si原子和Al原子聚合度保持不变,高岭石主体结构仍呈层状结构。此外,随着水洗次数的增加,高岭石叠置片层减少,晶形遭到一定破坏。     

高岭土/肼插层材料的制备与表征

以高岭土为原料,选取50%水合肼作为插层剂,采用直接液相插层法,并辅以磁力搅拌,成功地将肼分子插入到高岭石结构层间,制得肼插层高岭土材料。利用红外光谱和粒度分析仪对产品进行了表征。IR谱表明, 插层中肼分子中的NH基与高岭石内表面羟基之间产生了N-H-OH作用,形成了新的氢键;插层反应后的样品,其粒径小于5 μm的颗粒占总颗粒数的比例降低了10.55%,平均粒径增大了46.84%。     

大同粗晶高岭石-二甲基亚砜插层复合物的制备及表征

首先研究了大同高岭石的矿物学特征,结果表明大同高岭石晶粒粗大,主要由高岭石组成,样品的有序度高,Hinckley指数为1.12。在此基础上,用二甲基亚砜对大同高岭石进行插层,采用XRD、IR和TG-DSC研究插层复合物的结构。XRD结果表明DMSO已插入高岭石层间,d001由原来的0.717nm增至1.13nm,插层率达96.01%;红外光谱证明DMSO中的S=O基团与高岭石的外羟基发生了化学键合作用;热分析结果显示插层复合物于120℃~240℃发生DMSO的脱嵌作用,高岭石的脱羟基温度在400℃~750℃。     

The terrestrial fauna of the Late Triassic Pant-y-ffynnon Quarry fissures,South Wales,UK and a new species of Clevosaurus (Lepidosauria: Rhynchocephalia)

Pant-y-ffynnon Quarry in South Wales yielded a rich cache of fossils in the early 1950s, including articulated specimens of new species (the small sauropodomorph dinosaur Pantydraco caducus and the crocodylomorph Terrestrisuchus gracilis), but no substantial study of the wider fauna of the Pant-y-ffynnon fissure systems has been published. Here, our overview of existing specimens, a few described but mostly undescribed, as well as freshly processed material, provides a comprehensive picture of the Pant-y-ffynnon palaeo-island of the Late Triassic. This was an island with a relatively impoverished fauna dominated by small clevosaurs (rhynchocephalians), including a new species, Clevosaurus cambrica, described here from a partially articulated specimen and isolated bones. The new species has a dental morphology that is intermediate between the Late Triassic Clevosaurus hudsoni, from Cromhall Quarry to the east, and the younger C. convallis from Pant Quarry to the west, suggesting adaptive radiation of clevosaurs in the palaeo-archipelago. The larger reptiles on the palaeo-island do not exceed 1.5?m in length, including a small carnivorous crocodylomorph, Terrestrisuchus, and a possible example of insular dwarfism in the basal dinosaur Pantydraco.     

The effect of water on accessory phase solubility in subaluminous and peralkaline granitic melts

The solubilities of columbite, tantalite, wolframite, rutile, zircon and hafnon were determined as a function of the water contents in peralkaline and subaluminous granite melts. All experiments were conducted at 1035 °C and 2 kbar and the water contents of the melts ranged from nominally dry to approximately 6 wt.% H₂O. Accessory phase solubilities are not affected by the water content of the peralkaline melt. By contrast, solubilities are affected by the water content of the subaluminous melt, where the solubilities of all the accessory phases examined increase with the water content of the melt, up to 2 wt.% H₂O. At higher water contents, solubilities are nearly constant. It can be concluded that water is not an important control of accessory phase solubility, although the water content will affect diffusivities of components in the melt, thus whether or not accessory phases will be present as restite material. The solubility behaviour in the subaluminous and peralkaline melts supports previous spectroscopic studies, which have observed differences in the coordination of high field strength elements in dry vs. wet subaluminous granitic glasses, but not for peralkaline granitic glasses. Lastly, the fact that wolframite solubility increases with increasing water content in the subaluminous melt suggests that tungsten dissolved as a hexavalent species.     

Quaternary stresses revealed by calcite twinning inversion: insights from observations in the Savonnières underground quarry (eastern France)

Calcite samples were extracted both from the rock matrix and the superficial coating of a karstified fault plane of an underground quarry, located in the eastern border of the Paris basin. The karstification is dated as Quaternary. Analysis of mechanical calcite twinning reveals that only the calcite matrix has also undergone a compression trending WNW that can be attributed to the Mio-Pliocene alpine collision. Both coating and matrix have undergone a strike-slip regime with σ₁ roughly trending north–south, that could correspond to the regional present-day state of stress, a strike-slip compression rather trending NNW, modified by local phenomena. To cite this article: M. Rocher et al., C. R. Geoscience 335 (2003).     

HYDROGEOLOGY

正20141756 Chen Ruige(Mathematical College,China University of Geosciences,Beijing100083,China);Zhou Xun Numerical Simulation of Groundwater Level Fluctuation in a Coastal Confined Aquifer with Sloping Initial Groundwater Level Induced by the Tide(Geological Bulletin of China,ISSN1671-2552,CN11-4648/P,32(7),2013,p.1099-1104,6 illus.,16 refs.) Key words:confined water,groundwater level     

METAMORPHIC PETROLOGY

正20141408 Cai Jia(Institute of Geology,Chinese Academy of Geological Sciences,Beijing100037,China);Liu Fulai Petrogenesis and Metamorphic P-T Conditions of Garnet-Spinel-Biotitebearing Paragneiss in Danangou Area,Daqingshan-Wulashan Metamorphic Complex Belt(Acta Petrologica Sinica,ISSN1000-0569,CN11-1922/P,29(7),     

SERIALS

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GEOPHYSICAL EXPLORATION

正20142386An Guoying(China Aero Geophysical Survey and Remote Sensing Center for Land and Resources,Beijing 100083,China)Application of Satellite Remote Sensing in Regional Hydrogeological Investigation:Taking Cenozoic Strata in Wenquan Sheet(1∶250 000)of Karakoram Range as an Example(Geosci-     

QUATERNARY GEOLOGY & GEOMORPHOLOGY

正20141016An Chengbang(Key Laboratory of Western China’s Environmental Systems,Ministry of Education,Lanzhou University,Lanzhou 730000,China);Zhao Yongtao Lake Records during the Last Glacial Maximum from Xinjiang,NW China and Their Climatic Impli-     

PETROLEUM GEOLOGY

正20141538 Cao Qing(School of Earth Sciences and Engineering,Xi’an Petroleum University,Xi’an 710065,China);Zhao Jingzhou Characteristics and Significance of Fluid Inclusions from Majiagou Formation,Yichuan Huangling Area,Ordos Basin(Advances in Earth Science,ISSN1001-8166,CN62-1091/P,28(7),2013,p.819-828,7 illus.,3 tables,43 refs.)     

GEOCHEMISTRY

正20142002 Wei Hualing(Institute of Geophysical and Geochemical Exploration,Chinese Academy of Geological Sciences,Langfang065000,China);Zhou Guohua Element Content and Mineral Compositions in Different Sizes of Soil in Tongling Area,Anhui Province(Geological Bulletin of China,ISSN1671-2552,CN11-4648/P,32(11),2013,p.1861