高岭石/乙酰胺插层复合物的制备及结构表征

乙酰胺在熔融状态下直接插层高岭石，产物经无水乙醇洗涤，得到纯净的高岭石／乙酰胺插层复合物。XRD结果显示高岭石层间距从0．721nm膨胀到1．102nm。插层作用使得高岭石内表面羟基伸缩振动峰由3651cm^-1。移动至3647cm^-1。处，变形振动峰由911cm^-1移动至907cm^-1处；乙酰胺3211cm^-1和3390cm^-1处NH2基伸缩振动峰消失，并在3478cm^-1处产生一新的振动峰，这些表明原高岭石层问氢键的损失及与乙酰胺分子之间氢键的形成。高岭石内羟基的吸收峰由3616cm^-1移动至3611cm^-1处，以及其硅氧面的骨架振动峰变化表明乙酰胺的甲基中CH嵌入到高岭石的复三方空穴中。进而构建高岭石／乙酰胺插层复合物的结构模型，结果表明该模型的理论计算值与实际测量结果具有很好的一致性。     

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。     

快速制备肼—高岭石插层复合物的方法及意义

将一定浓度的肼溶液与高岭土混合，施以机械研磨，不仅加快了肼分子插入高岭石的速率(10分钟内可使插层率达96％)，而且超细效果明显。在加温120℃后，插入高岭石层间的肼分子挥发，产生的气体能进一步将高岭土剥离，最后得到—2μm＞90％的超细高岭土粉体，且片状晶形完好。这种技术为制备“双90”超细高岭土提供了新的思路和方法。     

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。     

微波辐射制备高岭石/聚丙烯酰胺插层复合物

本文将微波技术引入到制备高岭石/有机物插层复合物的研究中,以DMSO为前驱体,研究了微波辐射对高岭石的有机插层、取代、原位聚合作用.发现微波能加快插层和置换反应,极大地缩短反应时间.微波辐射下插层时间为30 min时,插层率即可达到75%以上,置换反应50 min,置换率达到77%以上.同时发现微波在反应中对高岭石具有剥片效果.采用X射线衍射、FT-IR光谱、TG、TEM等技术对插层复合物及微波作用机理进行了探讨.     

醇解条件下高岭石-硅烷插层复合物的制备与表征

以张家口高岭石为原料,通过二甲基亚砜和甲醇处理获得高岭石-甲醇插层复合物,以此为前驱体,常温条件下在γ-氨丙基三乙氧基硅烷(APTES)及APTES与甲醇组成的反应液中制备出了一系列高岭石-硅烷插层复合物,并利用XRD、FTIR、TEM对其结构和形貌进行了表征。结果表明:反应液中甲醇的加入会使插层复合物的层间距减小,且反应液中甲醇所占的比重越大,所得插层复合物的层间距越小。透射电子显微镜发现:当反应液中不加入甲醇时,所得插层复合物(K-APTES)仍呈现出六方片状的晶形,但加入甲醇后,所得插层复合物出现明显的卷曲剥离现象。上述现象均是由于甲醇与APTES发生醇解反应生成γ-氨丙基三甲氧基硅烷(APTMS)并随APTES分子一起插入高岭石层间造成的。     

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℃。     

高岭石/醋酸钾插层复合物的制备及其影响因素

利用浸泡法制备了高岭石/醋酸钾插层复合物,进行X射线衍射分析,探讨了影响插层的因素。结果表明,醋酸钾对高岭石的插层作用与高岭石的结晶度、插层剂浓度、pH值密切相关。高岭石结晶度越高,越有利于插层作用的进行;高浓度的插层剂(≥30%)可以在较短的时间(12 h)内完成插层作用,而低浓度的插层溶液则需要非常长的时间(≥144 h)才能完成,且获得的插层率较低;pH=10的弱碱性条件最有利于插层的进行;温度对高岭石的插层作用影响不大,在室温就可获得较好的插层效果。     

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.     

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。     

Exfoliation of kaolinite by urea-intercalation precursor and microwave irradiation assistance process

A type of exfoliated kaolinite was produced by urea-intercalation and original microwave irradiation assisted method. The product was investigated by Fourier transformation infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), scanning electronic microscopy (SEM), Brunauer-Emmett-Teller (BET) and laser particle analysis techniques. FT-IR spectra show that NHCO molecule exists in the intercalated kaolinite. XRD analyses indicate that the kaolinite sheet-like structure was disordered after microwave irradiation. The urea decomposition process and explosion effect between the sheet-like structures of kaolinite under microwave irradiation were discussed. The SEM and BET analyses reveal that the end product is exfoliated kaolinite with thin particles and increased surface area. Size and zeta potential analyses show that the particle size distribution is between 250 nm and 550 nm with normal distribution and the particle is negatively charged. In comparison with the conventional grind method, the process adopted appears to be economic and the exfoliated kaolinite end product may display a significantly enhanced performance in industrial applications.     

机械研磨对平鲁煤系高岭石热行为的影响

对煤系高岭石进行0-2h的研磨之后，再在900℃、1000℃、1400℃的温度条件下分别对其加热1h，然后利用X射线衍射（XRD）、差热分析（DTA）、红外光谱（IR）等手段，研究机械研磨对于煤系高岭石晶体结构的破坏作用以及对其热行为的影响。结果显示，煤系高岭石被研磨1h之后，高岭石的晶体结构几乎全部跨塌。把研磨1h的煤系高岭石加热到1000℃（加热1h），便能形成结晶良好的莫来石。     

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。     

Sorption of phenanthrene on the complexes of kaolinite and different organic component

Sorption of hydrophobic organic chemicals by various components influences their behavior and fate in environment. In the natural environment, mineral components, organic matter and microorganism didn＇t exist alone. They combined or reacted one another and formed the mineral-humic, mineral-microorganic and mineral- humic- microorganic complexes. A clear understanding of the sorption of organic chemicals by the complexes of mineral and humic acid and/or microorganism will help to determine their sorptive mechanisms in environment. In this paper, the sorption patterns of phenanthrene on the complexes of kaolinite and different organic component （humic acid and microorganism） have been carried on. The results show that the combination of HA and kaolinite not only changed the structure of HA, but also modified the surface chemistry of clay mineral. Interaction between HA and kaolinite is presumably ascribable to coulombic interactions and ligand exchange between the -COOH groups of HA and OH groups at the kaolinite surface. During the sorption on mineral surface, aliphatic fractions of HA were preferentially sored by kaolinite while aromatic fractions were left in the solution. More linear isotherms and higher Koc values were observed for kaolinite-HA complex in comparison of the pure HA. The sorption capacity of kaolinite-HA complex increased with increasing ionic strength and pH, and showed more nonlinear character. Kaolinite, microorganism and kaolinite-microorganism complex can all sorb phenanthrene, but the sorption capacity significantly differed. Bacterial cell sorbed more phenanthrene than kaolinite. The biofllm coating of kaolinite affected its sorption to phenanthrene. Kaolinite with biolfilm coating sorbed more phenanthrene than that without biofilm coating. The sorption capacity of kaolinite-microorganism complex decreased with increasing ionic strength and decreasing pH, but showed more nonlinear character. Both HA and microorganism can alter the nature of kaolinite sorbing phenanthrene respectively.     

土样制备对自由膨胀率的影响及其改进方法

着重论述了土样制备对自由膨胀率试验成果的影响。试验研究发现,3种口径（4.5,5,5.5 mm）和3种下落高度(5,10,15 mm)对取土质量和试验结果影响不大,但颗粒粉碎程度的影响非常明显。规程中土颗粒过0.5 mm筛的规定不够完善,在此粒径范围内3种粒组（0.25～0.5,0.1～0.25,<0.1 mm）的土样,其自由膨胀率结果存在差异。其中,前两者差别不大,<0.1 mm粒组土样的试验结果一般较前两者低30 %～45 %,与膨胀土其他属性指标不匹配。研究结果表明：不同粒径土样在10 mL量土杯中质量相差多达2 g,取土质量是影响自由膨胀率结果的主要因素之一,颗粒结构变化也有可能是影响因素之一,建议土样粒径范围为0.1～0.5 mm。     

Comparative study of microstructural characteristics and stored energy of mechanically activated hematite in different grinding environments

Hematite concentrate was mechanically treated using different milling machines and experimental conditions in air atmosphere. The changes in phase constitution, particles size, specific surface area, lattice parameters and X-ray amorphous phase fraction of activated hematite were determined. It was found that the agglomeration of the particles take place during extended milling with accessible pores for Nitrogen gas. The higher media surface brought about the largest specific surface area whatever milling devices used. After 9 h of grinding with higher media surface, the maximum and minimum specific surface area resulted from the grinding in the tumbling and vibratory mills, accounting for 6.83 m²/g and 18.42 m²/g, respectively. For the same grinding condition, tumbling mill produced the lowest X-ray amorphous phase. The maximum X-ray amorphous material estimated around 85% from the grinding in the planetary mill with higher media surface for 9 h of milling.     

膨胀土CBR强度特性机制分析

以在建的周集-六安高速公路为依托工程,采集典型弱、中膨胀土开展系统的试验研究,探讨了膨胀土CBR强度随含水率、击实功和膨胀潜势的变化规律。试验研究表明：CBR峰值含水率要大于最优含水率,且膨胀潜势越高,击实功越大,CBR峰值含水率与最优含水率的差值越大。结合非饱和土气水状态理论,分析了膨胀土CBR强度特性的内在机制。研究发现,CBR强度特性的上述规律性,主要是由不同饱和度条件下膨胀土所处的气水状态所决定的。当饱和度小于界限饱和度时,土体处于非饱和状态,CBR强度随饱和度的增加呈指数增长,说明膨胀土的固有特性对CBR强度的影响很大;当饱和度大于等于界限饱和度时,膨胀土强度特性与饱和土类似,CBR强度主要受干密度控制。     

A-type granites induced by a breaking-off and delamination of the subducted Junggar oceanic plate,West Junggar,Northwest China

The A-type granites with highly positive ε_Nd(t) values in the West Junggar, Central Asian Orogenic Belt (CAOB), have long been perceived as a group formed under the same tectonic and geodynamic setting, magmatic sourceq and petrogenetic model. Geological evidence shows that these granites occurred at two different tectonic units related to the southeastern subduction of Junggar oceanic plate: the Hongshan and Karamay granites emplaced in the southeast of West Junggar in the Baogutu continental arc; whereas the Akebasitao and Miaoergou granites formed in the accretionary prism. Here the authors present new bulk-rock geochemistry and Sr-Nd isotopes, zircon U-Pb ages and Hf-O isotopes data on these granites. The granites in the Baogutu continental arc and accretionary prism contain similar zircon ε_Hf(t) values (+10.9 to +16.2) and bulk-rock geochemical characteristics (high SiO₂ and K₂O contents, enriched LILEs (except Sr), depleted Sr, Ta and Ti, and negative anomalies in Ce and Eu). The Hongshan and Karamay granites in the Baogutu continental arc have older zircon U-Pb ages (315–305 Ma) and moderate ¹⁸O enrichments (δ¹⁸O_zircon=+6.41‰–+7.96‰); whereas the Akebasitao and Miaoergou granites in the accretionary prism have younger zircon U-Pb ages (305–301 Ma) with higher ¹⁸O enrichments (δ¹⁸O_zircon=+8.72‰–+9.89‰). The authors deduce that the elevated ¹⁸O enrichments of the Akebasitao and Miaoergou granites were probably inherited from low-temperature altered oceanic crusts. The Akebasitao and Miaoergou granites were originated from partial melting of low-temperature altered oceanic crusts with juvenile oceanic sediments below the accretionary prism. The Hongshan and Karamay granites were mainly derived from partial melting of basaltic juvenile lower crust with mixtures of potentially chemical weathered ancient crustal residues and mantle basaltic melt (induced by hot intruding mantle basaltic magma at the bottom of the Baogutu continental arc). On the other hand, the Miaoergou charnockite might be sourced from a deeper partial melting reservoir under the accretionary prism, consisting of the low-temperature altered oceanic crust, juvenile oceanic sediments, and mantle basaltic melt. These granites could be related to the asthenosphere’s counterflow and upwelling, caused by the break-off and delamination of the subducted oceanic plate beneath the accretionary prism Baogutu continental arc in a post-collisional tectonic setting.©2022 China Geology Editorial Office.