黏土矿物-十六烷基三甲基氯化铵作用机理及其结构
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摘要
黏土矿物有机插层复合物作为重要的功能材料现已被广泛应用于吸附、化工和环保等众多领域。采用插层法将十六烷基三甲基氯化铵(CTAC)插入到黏土矿物高岭石、钠基蒙脱石和蛭石层间,利用X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、热重-差示扫描量热(TG-DSC)及扫描电镜(SEM)等表征方法对插层复合物的作用机理及结构进行研究。结果表明:高岭石在经过多次"替代"插层后,层间氢键被破坏,层间作用力减弱,CTAC分子进入其层间,这引起高岭石片层由于层间的束缚力释放形成卷曲形貌。蒙脱石与蛭石以离子交换的形式与CTAC分子发生反应,该过程尚未对它们的形貌产生明显影响。此外,进一步建立了黏土矿物-CTAC插层复合物的结构模型,提出CTAC分子在高岭石和蒙脱石层间分别以35°和32°的夹角双层斜立,在蛭石层间以44°的夹角单层斜立。
Clay mineral organic intercalation compounds are used as important functional materials in adsorption,chemical engineering and environmental protection. Cetyl trimethyl ammonium chloride( CTAC) was intercalated into clay minerals,kaolinite,montmorillonite and vermiculite interlayer by intercalating method,the mechanism and structure of the intercalation compounds were analysed by XRD,FTIR and TG-DSC and SEM. It could be revealed that the interlayer hydrogen bonds are destroyed and the CTAC molecules enter the interlayer after multiple " replacement" of kaolinite. This leads to the formation of a curled morphology of the kaolinite sheet due to release of the binding force between the layers. The montmorillonite and vermiculite react with the CTAC molecules in the form of ion exchange,which does not affect their morphology. structural models of the clay mineral-CTAC intercalation compounds was constructed. The CTAC molecules erectdouble layers between the kaolinite and montmorillonite layers at an angle of 35° and 32° respectively,and slanted single layer at an angle of 44°between the vermiculite layers.
Clay mineral organic intercalation compounds are used as important functional materials in adsorption,chemical engineering and environmental protection. Cetyl trimethyl ammonium chloride( CTAC) was intercalated into clay minerals,kaolinite,montmorillonite and vermiculite interlayer by intercalating method,the mechanism and structure of the intercalation compounds were analysed by XRD,FTIR and TG-DSC and SEM. It could be revealed that the interlayer hydrogen bonds are destroyed and the CTAC molecules enter the interlayer after multiple " replacement" of kaolinite. This leads to the formation of a curled morphology of the kaolinite sheet due to release of the binding force between the layers. The montmorillonite and vermiculite react with the CTAC molecules in the form of ion exchange,which does not affect their morphology. structural models of the clay mineral-CTAC intercalation compounds was constructed. The CTAC molecules erectdouble layers between the kaolinite and montmorillonite layers at an angle of 35° and 32° respectively,and slanted single layer at an angle of 44°between the vermiculite layers.
引文
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[2] Matusik J,Kapyta Z. Characterization of Kaolinite Intercalation Compounds with Benzylalkylammonium Chlorides Using XRD,TGA/DTA and CHNS Elemental Analysis[J]. Applied Clay Science,2013,83-84:433-440.
[3] Frost R L,Kristof J,Horvath E,et al. Effect of Water on the Formamide-Intercalation of Kaolinite[J]. Spectrochimica Acta Part A Molecular&Biomolecular Spectroscopy,2000,56(9):1711-1729.
[4] Olejnik S,Aylmore L A G,Posner A M,et al. Infrared Spectra of Kaolin Mineral-Dimethyl Sulfoxide Complexes[J]. Journal of Physical Chemistry,1968,72(1):241-249.
[5] Frost R L,Kristof J,Paroz G H,et al. Modification of the Kaolinite Hydroxyl Surfaces through Intercalation with Potassium Acetate under Pressure[J]. Journal of Colloid&Interface Science,1998,208(2):478.
[6] Frost R L,Kristof J,Schmidt J M,et al. Raman Spectroscopy of Potassium Acetate-intercalated Kaolinites at Liquid Nitrogen Temperature[J].Spectrochimica Acta Part A Molecular&Biomolecular Spectroscopy,2015,57(3):603-609.
[7] Komori Y,Sugahara Y,Kuroda K. A Kaolinite-NMF-methanol Intercalation Compound as a Versatile Intermediate for Further Intercalation Reaction of Kaolinite[J]. Journal of Materials Research,1998,13(4):930-934.
[8]刘钦甫,李晓光,郭鹏,等.高岭石-烷基胺插层复合物的制备与纳米卷的形成[J].硅酸盐学报,2014,42(8):1064-1069.
[9]刘钦甫,王定,郭鹏,等.季铵盐-高岭石系列插层复合物的制备及结构表征[J].硅酸盐学报,2015,43(2):222-230.
[10] Zheng J P,Luan L,Wang K Y,et al. Study on Ibuprofen/montmorillonite Intercalation Composites as Drug Release System[J]. Applied Clay Science,2007,36(4):297-301.
[11] Gao D G,Ma J Z,Lv B,et al. Study on Montmorillonite Intercalation with Polymer Diallyldimethylammonium Chloride-acrylamide[J]. Journal of Functional Materials,2010,41:67-71.
[12]孙红娟,彭同江,刘颖.吡咯单体-有机蒙脱石插层复合物制备的实验研究[J].西南科技大学学报,2007,22(2):1-4.
[13]赵彦钊,郭文姬,王兰.头孢拉定/蒙脱石插层化合物的制备[J].无机材料学报,2012,27(6):655-659.
[14] Gahleitner M,Kretzschmar B,Pospiech D,et al. Morphology and Mechanical Properties of Polypropylene/polyamide 6 Nanocomposites Prepared by a Two-step Melt-compounding Process[J]. Journal of Applied Polymer Science,2006,100(1):283-291.
[15] Tjong S C,Meng Y Z,Xu Y. Structure and Properties of Polyamide-6/vermiculite Nanocomposites Prepared by Direct Melt Compounding[J].Journal of Polymer Science Part B Polymer Physics,2002,40(24):2860-2870.
[16]陈志坤,何素琴,辛建泉,等.蛭石的钠化和有机插层蛭石的制备与表征[J].非金属矿,2009,32(1):18-21.
[17]程宏飞,刘庆贺,贾晓辉,等.高岭石/甲醇复合物结构及其脱嵌动力学研究[J].人工晶体学报,2018,47(2):389-396.
[18] Lagaly G. Characterization of Clays by Organic Compounds[J]. Clay Minerals,1981,16(1):1-21.
[19]蔡冬雪,廖立兵,张泽朋.不同链长季铵盐干法球磨插层蒙脱石的研究[J].矿物学报,2012,(s1):84-84.
[20]王丽娟.蛭石结构改性、有机插层及微波膨胀研究[D].北京:中国地质大学(北京),2014.
[21] Slade P G,Gates W P. The Ordering of Hdtma in the Interlayers of Vermiculite and the Influence of Solvents[J]. Clays&Clay Minerals,2004,52(2):204-210.
[22]吴平霄.有机插层蛭石功能材料的制备与表征研究[J].功能材料,2003,34(6):728-731.
[23]李雪梅,廖立兵,谷勤,等.蛭石精矿的有机改性试验[J].岩矿测试,2008,27(1):63-66.
[24]程宏飞,李凯华,徐占杰,等.煤层夹矸型黏土矿物对甲烷的吸附研究[J].煤炭学报,2017,42(8):2052-2063.
[25] Liu D,Yuan P,Liu H,et al. High-pressure Adsorption of Methane on Montmorillonite,Kaolinite and Illite[J]. Applied Clay Science,2013,85(1):25-30.