TY - GEN
T1 - Structure and energetics of vitreous and crystalline tectosilicates
AU - Navrotsky, Alexandra
N1 - Copyright:
Copyright 2004 Elsevier B.V., All rights reserved.
PY - 1991
Y1 - 1991
N2 - The energetics of complex framework silicates is related to their structure and composition in a systematic fashion. This is illustrated by thermochemical data for crystalline silicas including zeolites and the silica polymorphs, and for amorphous silicas, including glasses, CVD and sol-gel materials. Relative to quartz as the stable crystalline polymorph and bulk glass as the most stable amorphous form, enthalpy increases with both increasing density (coesite, stishovite and pressure or radiation densified glasses) and with decreasing density (tridymite, cristobalite, zeolitic silicas, sol-gel and CVD amorphous structures). Preliminary data suggest the most open structures (e.g. faujasite approaching SiO2 in composition) are not as destabilized as their large molar volume would imply, suggesting that large pores, with normal framework density between them, are more stable than a relatively uniform expansion of structure. Coupled substitution: Si4+ = (l/n) Mn+ + T3+ stabilizes tectosilicates. Stabilization increases in the order M = Mg, Ca, Sr, Ba, Li, Na, K, Rb, Cs and in the order T = B, Fe3+, Ga, Al, that is, with increasing basicity of the nonframework cation and with increasing similarity to Si of the cation substituting in the framework. These trends are discussed in terms of structure and bonding.
AB - The energetics of complex framework silicates is related to their structure and composition in a systematic fashion. This is illustrated by thermochemical data for crystalline silicas including zeolites and the silica polymorphs, and for amorphous silicas, including glasses, CVD and sol-gel materials. Relative to quartz as the stable crystalline polymorph and bulk glass as the most stable amorphous form, enthalpy increases with both increasing density (coesite, stishovite and pressure or radiation densified glasses) and with decreasing density (tridymite, cristobalite, zeolitic silicas, sol-gel and CVD amorphous structures). Preliminary data suggest the most open structures (e.g. faujasite approaching SiO2 in composition) are not as destabilized as their large molar volume would imply, suggesting that large pores, with normal framework density between them, are more stable than a relatively uniform expansion of structure. Coupled substitution: Si4+ = (l/n) Mn+ + T3+ stabilizes tectosilicates. Stabilization increases in the order M = Mg, Ca, Sr, Ba, Li, Na, K, Rb, Cs and in the order T = B, Fe3+, Ga, Al, that is, with increasing basicity of the nonframework cation and with increasing similarity to Si of the cation substituting in the framework. These trends are discussed in terms of structure and bonding.
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M3 - Conference contribution
AN - SCOPUS:0026360923
SN - 0937140368
T3 - Transactions of the American Crystallographic Association
SP - 1
EP - 12
BT - Transactions of the American Crystallographic Association
A2 - Wright, Adrian C.
PB - Publ by American Crystallographic Assoc
T2 - Proceedings of the Symposium on The Structural Chemistry of Silicates
Y2 - 22 July 1991 through 24 July 1991
ER -