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Title: Polycarboxylic acids as network modifiers for water durability improvement of inorganic-organic hybrid tin-silico-phosphate low-melting glasses

Abstract

We investigated the water durability of the inorganic-organic hybrid tin-silico-phosphate glasses Me{sub 2}SiO-SnO-P{sub 2}O{sub 5} (Me designs the organic methyl group) doped with organic acids (salicylic acid (SA), tartaric acid (TA), citric acid (Canada) and butane tetracarboxylic acid (BTCA)) containing one or more of carboxylic groups per molecule. The structure, thermal properties and durability of the final glasses obtained via a non-aqueous acid-base reaction were discussed owing to the nature and the concentration of the acid added. {sup 29}Si magic angle spinning (MAS) NMR and {sup 31}P MAS NMR spectra, respectively, showed clearly a modification of the network in the host glass matrix of the Me{sub 2}SiO-SnO-P{sub 2}O{sub 5} system. The polycondensation enhancement to form -P-O-Si-O-P- linkages (PSP) and the increase of the Q {sup 2} unit (two bridging oxygens per phosphorus atom) over the Q {sup 3} unit (three bridging oxygens per phosphorus atom) as a function of the acid in the order SA<TA<CA<BTCA, suggest the formation of a chain-like structure which contrasts with the high cross-linkage in the Me{sub 2}SiO-SnO-P{sub 2}O{sub 5} matrix. In addition, this structural change is accompanied by a decrease of the coefficient of thermal expansion and an increase of the water durability of themore » glasses with the acids containing a large number of carboxylic groups per molecule. The presence of carboxylic groups of the acid acting as network modifier may retard the movement of water molecules through the glasses due to the steric hindrance strengthening the PSP connections in a chain-like structure.« less

Authors:
 [1];  [2];  [3];  [2];  [2]
  1. Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011 (Japan) and PRESTO, Japan Science and Technology Agency, Kawaguchi, Saitama (Japan). E-mail: bouzidmenaa@noncry.kuicr.kyoto-u.ac.jp
  2. Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011 (Japan)
  3. Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011 (Japan) and PRESTO, Japan Science and Technology Agency, Kawaguchi, Saitama (Japan). E-mail: masahide@noncry.kuicr.kyoto-u.ac.jp
Publication Date:
OSTI Identifier:
20784888
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 179; Journal Issue: 2; Other Information: DOI: 10.1016/j.jssc.2005.11.001; PII: S0022-4596(05)00512-8; Copyright (c) 2005 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CITRIC ACID; DOPED MATERIALS; NMR SPECTRA; PHOSPHATE GLASS; PHOSPHORUS OXIDES; SALICYLIC ACID; SILICON COMPOUNDS; TARTARIC ACID; THERMODYNAMIC PROPERTIES; TIN COMPOUNDS; WATER

Citation Formats

Menaa, Bouzid, Mizuno, Megumi, Takahashi, Masahide, Tokuda, Yomei, and Yoko, Toshinobu. Polycarboxylic acids as network modifiers for water durability improvement of inorganic-organic hybrid tin-silico-phosphate low-melting glasses. United States: N. p., 2006. Web. doi:10.1016/j.jssc.2005.11.001.
Menaa, Bouzid, Mizuno, Megumi, Takahashi, Masahide, Tokuda, Yomei, & Yoko, Toshinobu. Polycarboxylic acids as network modifiers for water durability improvement of inorganic-organic hybrid tin-silico-phosphate low-melting glasses. United States. doi:10.1016/j.jssc.2005.11.001.
Menaa, Bouzid, Mizuno, Megumi, Takahashi, Masahide, Tokuda, Yomei, and Yoko, Toshinobu. Wed . "Polycarboxylic acids as network modifiers for water durability improvement of inorganic-organic hybrid tin-silico-phosphate low-melting glasses". United States. doi:10.1016/j.jssc.2005.11.001.
@article{osti_20784888,
title = {Polycarboxylic acids as network modifiers for water durability improvement of inorganic-organic hybrid tin-silico-phosphate low-melting glasses},
author = {Menaa, Bouzid and Mizuno, Megumi and Takahashi, Masahide and Tokuda, Yomei and Yoko, Toshinobu},
abstractNote = {We investigated the water durability of the inorganic-organic hybrid tin-silico-phosphate glasses Me{sub 2}SiO-SnO-P{sub 2}O{sub 5} (Me designs the organic methyl group) doped with organic acids (salicylic acid (SA), tartaric acid (TA), citric acid (Canada) and butane tetracarboxylic acid (BTCA)) containing one or more of carboxylic groups per molecule. The structure, thermal properties and durability of the final glasses obtained via a non-aqueous acid-base reaction were discussed owing to the nature and the concentration of the acid added. {sup 29}Si magic angle spinning (MAS) NMR and {sup 31}P MAS NMR spectra, respectively, showed clearly a modification of the network in the host glass matrix of the Me{sub 2}SiO-SnO-P{sub 2}O{sub 5} system. The polycondensation enhancement to form -P-O-Si-O-P- linkages (PSP) and the increase of the Q {sup 2} unit (two bridging oxygens per phosphorus atom) over the Q {sup 3} unit (three bridging oxygens per phosphorus atom) as a function of the acid in the order SA<TA<CA<BTCA, suggest the formation of a chain-like structure which contrasts with the high cross-linkage in the Me{sub 2}SiO-SnO-P{sub 2}O{sub 5} matrix. In addition, this structural change is accompanied by a decrease of the coefficient of thermal expansion and an increase of the water durability of the glasses with the acids containing a large number of carboxylic groups per molecule. The presence of carboxylic groups of the acid acting as network modifier may retard the movement of water molecules through the glasses due to the steric hindrance strengthening the PSP connections in a chain-like structure.},
doi = {10.1016/j.jssc.2005.11.001},
journal = {Journal of Solid State Chemistry},
number = 2,
volume = 179,
place = {United States},
year = {Wed Feb 15 00:00:00 EST 2006},
month = {Wed Feb 15 00:00:00 EST 2006}
}
  • This study is focused on structural characterization of hybrid glasses obtained by consolidation of melting gels. The melting gels were prepared in molar ratios of methyltriethoxysilane (MTES) and dimethyldiethoxysilane (DMDES) of 75%MTES-25%DMDES and 65%MTES-35%DMDES. Following consolidation, the hybrid glasses were characterized using Raman, 29Si and 13C Nuclear Magnetic Resonance (NMR) spectroscopies, synchrotron Small Angle X-Ray Scattering (SAXS) and scanning electron microscopy (SEM). Raman spectroscopy revealed the presence of Si–C bonds in the hybrid glasses and 8-membered ring structures in the Si–O–Si network. Qualitative NMR spectroscopy identified the main molecular species, while quantitative NMR data showed that the ratio of trimersmore » (T) to dimers (D) varied between 4.6 and 3.8. Two-dimensional 29Si NMR data were used to identify two distinct types of T3 environments. SAXS data showed that the glasses are homogeneous across the nm to micrometer length scales. The scattering cross section was one thousand times lower than what is expected when phase separation occurs. The SEM images show a uniform surface without defects, in agreement with the SAXS results, which further supports that the hybrid glasses are nonporous.« less
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