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      Kaolinite Nanocomposite Platelets Synthesized by Intercalation and Imidization of Poly(styrene- co-maleic anhydride)

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          Abstract

          A synthesis route is presented for the subsequent intercalation, exfoliation and surface modification of kaolinite (Kln) by an imidization reaction of high-molecular weight poly(styrene- co-maleic anhydride) or SMA in the presence of ammonium hydroxide. In a first step, the intercalation of ammonolyzed SMA by guest displacement of intercalated dimethylsulfoxide has been proven. In a second step, the imidization of ammonolyzed SMA at 160 °C results in exfoliation of the kaolinite layers and deposition of poly(styrene-co-maleimide) or SMI nanoparticles onto the kaolinite surfaces. Compared with a physical mixture of Kln/SMI, the chemically reacted Kln/SMI provides more efficient exfoliation and hydrogen bonding between the nanoparticles and the kaolinite. The kaolinite nanocomposite particles are synthesized in aqueous dispersion with solid content of 65 wt %. The intercalation and exfoliation are optimized for a concentration ratio of Kln/SMI = 70:30, resulting in maximum intercalation and interlayer distance in combination with highest imide content. After thermal curing at 135 °C, the imidization proceeds towards a maximum conversion of the intermediate amic acid moieties. The changes in O–H stretching and kaolinite lattice vibrations have been illustrated by infrared and FT-Raman spectroscopy, which allow for a good quantification of concentration and imidization effects.

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          Raman spectroscopic investigation of the structure of silicate glasses. III. Raman intensities and structural units in sodium silicate glasses

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            On the physical origin of blue-shifted hydrogen bonds.

            For blue-shifted hydrogen-bonded systems, the hydrogen stretching frequency increases rather than decreases on complexation. In computations at various levels of theory, the blue-shift in the archetypical system, F(3)C-H.FH, is reproduced at the Hartree-Fock level, indicating that electron correlation is not the primary cause. Calculations also demonstrate that a blue-shift does not require either a carbon center or the absence of a lone pair on the proton donor, because F(3)Si-H.OH(2), F(2)NH.FH, F(2)PH.NH(3), and F(2)PH.OH(2) have substantial blue-shifts. Orbital interactions are shown to lengthen the X-H bond and lower its vibrational frequency, and thus cannot be the source of the blue-shift. In the F(3)CH.FH system, the charge redistribution in F(3)CH can be reproduced very well by replacing the FH with a simple dipole, which suggests that the interactions are predominantly electrostatic. When modeled with a point charge for the proton acceptor, attractive electrostatic interactions elongate the F(3)C-H, while repulsive interactions shorten it. At the equilibrium geometry of a hydrogen-bonded complex, the electrostatic attraction between the dipole moments of the proton donor and proton acceptor must be balanced by the Pauli repulsion between the two fragments. In the absence of orbital interactions that cause bond elongation, this repulsive interaction leads to compression of the X-H bond and a blue-shift in its vibrational frequency.
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              FT-IR and XPS studies of polyurethane-urea-imide coatings

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                Author and article information

                Contributors
                Role: Academic Editor
                Journal
                Materials (Basel)
                Materials (Basel)
                materials
                Materials
                MDPI
                1996-1944
                16 July 2015
                July 2015
                : 8
                : 7
                : 4363-4388
                Affiliations
                [1 ]Chair for Bio-based Materials Engineering, Faculty for Environment and Natural Resources, Freiburg Institute for Advanced Studies (FRIAS), University of Freiburg, Werthmannstrasse 6, D-79085 Freiburg, Germany
                [2 ]Department of Textiles, Ghent University, Technologiepark 907, B-9052 Zwijnaarde, Belgium; E-Mail: Gustaaf.Schoukens@ 123456UGent.be
                [3 ]Topchim N.V., Nijverheidstraat 98, B-2160 Wommelgem, Belgium; E-Mail: info@ 123456topchim.be
                Author notes
                [†]

                These authors contributed equally to this work.

                [* ]Author to whom correspondence should be addressed; E-Mail: Pieter.Samyn@ 123456fobawi.uni-freiburg.de ; Tel.: +49-761-203-97202; Fax: +49-761-203-3674.
                Article
                materials-08-04363
                10.3390/ma8074363
                5455644
                e06180b3-fce9-4358-9571-f5aa7f935b34
                © 2015 by the authors.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution license ( http://creativecommons.org/licenses/by/4.0/).

                History
                : 07 June 2015
                : 09 July 2015
                Categories
                Article

                kaolinite,guest displacement,poly(styrene-co-maleimide),nanoparticles

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