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Changes in Structure, Morphology, Porosity, and Surface Activity of Mesoporous Halloysite Nanotubes Under Heating

Published online by Cambridge University Press:  01 January 2024

Peng Yuan ,
Daoyong Tan ,
Faïza Annabi-Bergaya ,
Wenchang Yan ,
Mingde Fan ,
Dong Liu  and
Hongping He
Peng Yuan*
Affiliation:
CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China
Daoyong Tan
Affiliation:
CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China Graduate School of the Chinese Academy of Science, Beijing 100049, China
Faïza Annabi-Bergaya
Affiliation:
Centre de Recherche sur la Matière Divisée, CNRS-Université d’Orléans, 1b, Rue de La Férollerie, Orléans Cedex 2, France
Wenchang Yan
Affiliation:
CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China Graduate School of the Chinese Academy of Science, Beijing 100049, China
Mingde Fan
Affiliation:
College of Environment and Resources, Inner Mongolia University, Hohhot 010021, China
Dong Liu
Affiliation:
CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China
Hongping He
Affiliation:
CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China
*
*E-mail address of corresponding author: [email protected]
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Abstract

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The objective of the present study was to investigate changes in the structural, textural, and surface properties of tubular halloysite under heating, which are significant in the applications of halloysite as functional materials but have received scant attention in comparison with kaolinite. Samples of a purified halloysite were heated at various temperatures up to 1400°C, and then characterized by X-ray diffraction, electron microscopy, Fourier-transform infrared spectroscopy, thermal analysis, and nitrogen adsorption. The thermal decomposition of halloysite involved three major steps. During dehydroxylation at 500–900°C, the silica and alumina originally in the tetrahedral and octahedral sheets, respectively, were increasingly separated, resulting in a loss of long-range order. Nanosized (5–40 nm) γ-Al2O3 was formed in the second step at 1000–1100°C. The third step was the formation of a mullite-like phase from 1200 to 1400°C and cristobalite at 1400°C. The rough tubular morphology and the mesoporosity of halloysite remained largely intact as long as the heating temperature was <900°C. Calcination at 1000°C led to distortion of the tubular nanoparticles. Calcination at higher temperatures caused further distortion and then destruction of the tubular structure. The formation of hydroxyl groups on the outer surfaces of the tubes during the disconnection and disordering of the original tetrahedral and octahedral sheets was revealed for the first time. These hydroxyl groups were active for grafting modification by an organosilane (γ-aminopropyltriethoxysilane), pointing to some very promising potential uses of halloysite for ceramic materials or as fillers for novel clay-polymer nanocomposites.

Keywords

GroupMetahalloysiteOrganosilane ModificationThermal TransformationTubular HalloysiteStructural and Textural Properties
Type
Article
Information
Clays and Clay Minerals , Volume 60 , Issue 6 , December 2012 , pp. 561 - 573
Copyright
Copyright © Clay Minerals Society 2012

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