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Lamellar nanostructure in ‘Somasif’-based organoclays

Published online by Cambridge University Press:  01 January 2024

Mikhail Y. Gelfer ,
Christian Burger ,
Pranav Nawani ,
Benjamin S. Hsiao ,
Benjamin Chu ,
Mayu Si ,
Miriam Rafailovich ,
Grazyna Panek ,
Gunnar Jeschke  and
Alexander Y. Fadeev
...Show all authors
Mikhail Y. Gelfer
Affiliation:
Chemistry Department, Stony Brook University, Stony Brook, NY 11794, USA
Christian Burger
Affiliation:
Chemistry Department, Stony Brook University, Stony Brook, NY 11794, USA
Pranav Nawani
Affiliation:
Chemistry Department, Stony Brook University, Stony Brook, NY 11794, USA
Benjamin S. Hsiao*
Affiliation:
Chemistry Department, Stony Brook University, Stony Brook, NY 11794, USA
Benjamin Chu
Affiliation:
Chemistry Department, Stony Brook University, Stony Brook, NY 11794, USA
Mayu Si
Affiliation:
Materials Science and Engineering Department, Stony Brook University, Stony Brook, NY 11794, USA
Miriam Rafailovich
Affiliation:
Materials Science and Engineering Department, Stony Brook University, Stony Brook, NY 11794, USA
Grazyna Panek
Affiliation:
Max-Planck Institute for Polymer Research, Postfach 3148, 55021 Mainz, Germany
Gunnar Jeschke
Affiliation:
Max-Planck Institute for Polymer Research, Postfach 3148, 55021 Mainz, Germany
Alexander Y. Fadeev
Affiliation:
Chemistry Department, Seton Hall University, 800 South Orange Avenue, South Orange, NJ 07009, USA
Jeffrey W. Gilman
Affiliation:
Fire Research Division, National Institute of Standards and Technology, Gaithersburg, MD 20899-8665, USA
*
*E-mail address of corresponding author: bhsiao@notes.cc.sunysb.edu
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Abstract

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Thermally induced lamellar structure changes due to phase transition and degradation in organoclays based on a synthetic ‘Somasif’ mineral and two organic surfactants, di-methyl dihydro-ditallow ammonia chloride (DMDTA) and tri-butyl-hexadecyl phosphonium bromide (HTBP) were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, in situ simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) over the temperature range 30–280°C. Results indicated that the surfactant layer in ‘Somasif’-based organoclays underwent thermally induced melting-like order-disorder transition followed by desorption of surfactant molecules, resulting in drastic changes in the character of the layer periodicity. The transition temperature (Ttr), determined from the endothermic transition in DSC, was found to depend strongly on the type and the content of surfactant incorporated. Temperature-resolved SAXS indicated complex intercalated layered structures, containing multiple lamellar stack populations of two different organic layer thicknesses. A weak scattering peak (s0), located at exactly the half angular position of the strong first scattering maximum s1 (s0 = 0.5s1), was found in all tested ‘Somasif’ clays. The presence of this peak can be attributed to a slight breaking of the translational symmetry in the layered structure, causing the 1D repeat period in real space to be doubled. In other words, some portions of layers are grouped into pairs and a single pair forms the new repeat unit. This arrangement is reminiscent of the Peierls-like distortion.

Keywords

DegradationOrganoclays‘Somasif’SurfactantThermal TransitionSAXS
Type
Research Article
Information
Clays and Clay Minerals , Volume 55 , Issue 2 , April 2007 , pp. 140 - 150
Copyright
Copyright © 2007, The Clay Minerals Society

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