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Giant Multistep Crystalline vs. Osmotic Swelling of Synthetic Hectorite in Aqueous Acetonitrile

Published online by Cambridge University Press:  01 January 2024

Raphael Kunz ,
Sonja Amschler ,
Andreas Edenharter ,
Lina Mayr ,
Sebastian Herlitz ,
Sabine Rosenfeldt  and
Josef Breu
Raphael Kunz
Affiliation:
Department of Chemistry and Bavarian Polymer Institute, University of Bayreuth, 95447 Bayreuth, Germany
Sonja Amschler
Affiliation:
Department of Chemistry and Bavarian Polymer Institute, University of Bayreuth, 95447 Bayreuth, Germany
Andreas Edenharter
Affiliation:
Department of Chemistry and Bavarian Polymer Institute, University of Bayreuth, 95447 Bayreuth, Germany
Lina Mayr
Affiliation:
Department of Chemistry and Bavarian Polymer Institute, University of Bayreuth, 95447 Bayreuth, Germany
Sebastian Herlitz
Affiliation:
Department of Chemistry and Bavarian Polymer Institute, University of Bayreuth, 95447 Bayreuth, Germany
Sabine Rosenfeldt
Affiliation:
Department of Chemistry and Bavarian Polymer Institute, University of Bayreuth, 95447 Bayreuth, Germany
Josef Breu*
Affiliation:
Department of Chemistry and Bavarian Polymer Institute, University of Bayreuth, 95447 Bayreuth, Germany
*
*E-mail address of corresponding author: josef.breu@uni-bayreuth.de
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Abstract

Intercalation of large organocations into 2:1 clay minerals may be hampered by two problems: on one hand, the solubility of organocations in water is limited and the resulting high selectivity for adsorption in the polar solvent may lead to non-equilibrium structures. On the other hand, the large expansion of the interlayer space will slow down kinetics of ion exchange considerably. The best workaround for these obstacles is to suspend the clay minerals in mixtures of water with more hydrophobic organic solvents that nevertheless trigger a considerable expansion of the interlayer space by swelling. This in turn fosters ion exchange. The current study, therefore, revisited pioneering work by Bradley (1945) and investigated the swelling behavior of synthetic sodium hectorite (Na-hec) as a function of the composition of the swelling solvent, a mixture of acetonitrile and water. Up to a maximum acetonitrile content of 65 vol.%, delamination by osmotic swelling occurred. At even higher acetonitrile concentrations, swelling was limited to the crystalline swelling regime where a step-like adjustment of the d value was observed. Several mixtures were identified yielding a well defined and uniform interlayer height as evidenced by rational 00l-series with the d spacing decreasing with increasing acetonitrile content. Surprisingly, for a specific acetonitrile:water ratio even an ordered interstratification of two strictly alternating interlayer heights with distinctly different solvent compositions was observed.

Keywords

Crystalline swellingHectoriteOrdered interstratificationOsmotic swellingSolvent mixtures
Type
Article
Information
Clays and Clay Minerals , Volume 67 , Issue 6 , December 2019 , pp. 481 - 487
Copyright
Copyright © Clay Minerals Society 2019

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