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This paper reports the first example of the direct intercalation of an organic polymer into the interlamellar spaces of kaolinite. Poly(ethylene glycols) (PEG 3400 and PEG 1000) were intercalated into kaolinite by displacing dimethyl sulfoxide (DMSO) from the DMSO−kaolinite intercalate (Kao−DMSO). This was done directly from the polymer melt at temperatures between 150 and 200 °C. XRD showed that the intercalated oxyethylene units were arranged in flattened monolayer arrangements, such that the interlayer expansion was 4.0 Å. Infrared analysis of Kao−PEG 3400 supported the assignment of a trans conformation to at least a portion of the (O−CH2CH2−O) groups of the PEG polymer while 13C CP and DD/MAS NMR indicated that the polymer was intercalated intact and was more constrained in the interlamellar spaces of kaolinite than it was in its bulk form. TGA/DSC analysis revealed that the complete decomposition of the organic component of the oxyethylene-based organokaolinites did not occur until greater than 1000 °C. The formulas were estimated to be Al2Si2O5(OH)4(−OCH2CH2−)0.77(DMSO)0.27 and Al2Si2O5(OH)4(−OCH2CH2−)0.99(DMSO)0.17, respectively for the cases of PEG 1000 and PEG 3400. The calculated formulas for both samples are consistent with one unit of oxyethylene or DMSO per Al2Si2O5(OH)4 unit. Given the known density of hydroxyl groups on the aluminol surface, a polymer conformation where ethyleneoxy groups repeat every 2.8 Å with the oxygens all facing toward the hydroxyl surface should be favored. It is suggested that the polymer adopts a conformation TG2T‘G2‘, in which the repeat unit per ethyleneoxy group is 2.94 Å, and all the oxygens are lined up on one side of the chain. The tension resulting from the imperfect fit could be relaxed by a certain degree of trans conformations.

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Abstract--A new, well-ordered, thermally robust ethylene glycol intercalate of kaolinite was formed by refluxing the dimethyl sulfoxide intercalate of kaolinite (Kao-DMSO) with dry ethylene glycol (EG). This new phase (Kao-EG 9.4 A) which is characterized by a dool of 9.4 A is distinct from a previously reported ethylene glycol intercalated phase of kaolinite (Kao-EG 10.8/k) which has a dool of 10.8 ,~. The characterization of these two phases was studied by XRD, NMR, FTIR, and TGA/DSC. It was found that the concentration of water in the ethylene glycol reaction media played a crucial role in governing which of the phases predominated. Water favored Kao-EG 10.8 A formation, while anhydrous conditions favored the formation of Kao-EG 9.4 A. It is hypothesized that Kao-EG 9.4 A is a grafted phase resulting from the product of the condensation reaction between an aluminol group on the interlamenar surface of kaolinite and the alcohol group of ethylene glycol. Ethylene glycol units would be attached to the interlamellar surface of kaolinite via A1-O-C bonds. The Kao-EG 9.4 A phase was found to be resistant to both thermal decomposition up to 330~ and also, once formed, in the absence of interlamellar water molecules, to decomposition by hydrolysis in refluxing water.

The members of the p-type semiconducting SrTi 1−x Fe x O 3−δ family of perovskites have been studied as novel materials for hydrocarbon sensor applications. Screen-printed thick film devices are contrasted to thin films prepared by pulsed laser deposition (PLD). In order to enhance sensor specificity towards hydrocarbons, the influence of iron content, x, film thickness and operating temperature in the range from 300 to 500• C has been investigated. In addition, the use of a catalytically active cover layer made of a platinum-doped zeolite has been successfully studied to reduce the influence of species with cross-interference. An initial model explaining the underlying sensing mechanism is proposed.

The interlamellar surface of kaolinite has been modified with molecules possessing amino functionalities. Either the dimethyl sulfoxide intercalate of kaolinite (Kao/DMSO) or the N-methylformamide intercalate of kaolinite (Kao/NMF) were used as starting materials. One of the products, an ethanolamine functionalized kaolinite (Kao–EOA) was resistant to thermal decomposition in both air and N2 atmospheres up to temperatures greater than 150 °C. Based on results from thermal analysis, IR analysis, 13CCP/MAS NMR spectroscopy, and elemental analysis, a structural model is proposed in which every third interlayer surface hydroxyl group on the aluminol (Al-OH) surface of kaolinite is either replaced with an interlayer Al-OCH2CH2NH2 group or is strongly H-bonded to an aminoalcohol molecule. A mixture of both types of linkages could coexist. The amino groups that point away from this surface are each keyed into the -(SiO−)6 macro-rings of the adjacent silicate surface, resulting in an amino-functionalized ordered two-dimensional organo-mineral assembly. Keywords: kaolinite, halloysite, organo-mineral nanocomposites, clay functionalization, supramolecular assemblies.

Abstract--A stable 8.4/~ hydrate of kaolinite was prepared by exchanging ethylene glycol for water in the 10.8 A intercalate of ethylene glycol in kaolinite. The hydrate of kaolinite was characterized by XRD, FTIR and TGA/DSC. From the TGA data, one can estimate that there is 0.60 water molecule per A12Si20~(OH)4 units. The IR data suggest a similarity of the local environment of the intercalated water in this 8.4 A hydrate of kaolinite and the 8.4 A hydrate of nacrite previously described by Wada (1965).

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