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Dehydration dynamics of analcime by in situ synchrotron powder diffraction

Giuseppe Cruciani and Alessandro Gualtieri
Dehydration dynamics of analcime by in situ synchrotron powder diffraction
American Mineralogist (February 1999) 84 (1-2): 112-119

Abstract

The continuous structural transformation of tetragonal analcime (Na (sub 15.87) Al (sub 15.20) Si (sub 32.64) O (sub 96) .16.3H (sub 2) O) upon dehydration was studied, using Rietveld structure analysis of temperature-resolved powder diffraction data collected using synchrotron radiation. The variation of the a-c axis length difference and normalized intensity of the (200) reflection as a function of temperature suggest that tetragonal analcime evolves toward a cubic structure at high temperature. The removal of water was accompanied by a spreading of the initial Na sites into many positions bonded to the framework O atoms. The migration of H (sub 2) O molecules through the [111] channels during dehydration caused the six-member ring apertures to open as widely as possible: this was accompanied by a twisting of the tetragonal prism, constituting the analcime framework, which led to an opposite tilting of tetrahedra connecting the prisms. These modifications induced by water diffusion are not energetically favored because they would increase the elastic energy of the system, and require a substantial thermal activation energy. The analcime framework reached a maximum distortion at about 650 K, the temperature of complete water loss, then underwent a relaxation process during which the T-O-T angles were restored to the starting value. The relative variation of cell volume associated with the opening of wide six-member ring channels during water migration, and then due to the framework relaxation process after complete dehydration, provides an explanation of the "negative thermal expansion" (i.e., volume contraction) effect in dehydrated analcime, which is complementary to that based on the Rigid Unit Modes theory.


ISSN: 0003-004X
EISSN: 1945-3027
Coden: AMMIAY
Serial Title: American Mineralogist
Serial Volume: 84
Serial Issue: 1-2
Title: Dehydration dynamics of analcime by in situ synchrotron powder diffraction
Affiliation: Universita di Ferrara, Istituto di Mineralogia, Ferrara, Italy
Pages: 112-119
Published: 199902
Text Language: English
Publisher: Mineralogical Society of America, Washington, DC, United States
References: 24
Accession Number: 1999-022426
Categories: Geophysics of minerals and rocks
Document Type: Serial
Bibliographic Level: Analytic
Illustration Description: illus. incl. 3 tables
Secondary Affiliation: Universita di Modena, ITA, Italy
Country of Publication: United States
Secondary Affiliation: GeoRef, Copyright 2018, American Geosciences Institute.
Update Code: 199908
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