TY - JOUR
T1 - Predicting Q-Speciation in Binary Phosphate Glasses Using Statistical Mechanics
AU - Bødker, Mikkel S.
AU - Mauro, John C.
AU - Goyal, Sushmit
AU - Youngman, Randall E.
AU - Smedskjaer, Morten M.
N1 - Funding Information:
This work was supported by the Independent Research Fund Denmark (grant no. 7017-00019).
Publisher Copyright:
© 2018 American Chemical Society.
Copyright:
Copyright 2018 Elsevier B.V., All rights reserved.
PY - 2018/8/2
Y1 - 2018/8/2
N2 - Predicting the compositional evolution of the atomic-scale structure of oxide glasses is important for developing quantitative composition-property models. In binary phosphate glasses, the addition of network modifiers generally leads to depolymerization of the networks as described by the Q-speciation, where Qn denotes PO4 tetrahedra with n number (between 0 and 3) of bridging P-O-P linkages per tetrahedron. Upon the initial creation of nonbridging oxygens and thus partly depolymerized Q species, a variety of network former-modifier interactions exist. Here, on the basis of 31P magic angle spinning nuclear magnetic resonance spectroscopy data from the literature, we present a statistical description of the compositional evolution of Q-speciation in these glasses by accounting for the relative enthalpic and entropic contributions to the bonding preferences. We show that the entire glass structure evolution can be predicted based on experimental structural information for only a few glass compositions in each series. The model also captures the differences in bonding preferences in glasses with different field strengths (charge-to-size ratio) of the modifier cations.
AB - Predicting the compositional evolution of the atomic-scale structure of oxide glasses is important for developing quantitative composition-property models. In binary phosphate glasses, the addition of network modifiers generally leads to depolymerization of the networks as described by the Q-speciation, where Qn denotes PO4 tetrahedra with n number (between 0 and 3) of bridging P-O-P linkages per tetrahedron. Upon the initial creation of nonbridging oxygens and thus partly depolymerized Q species, a variety of network former-modifier interactions exist. Here, on the basis of 31P magic angle spinning nuclear magnetic resonance spectroscopy data from the literature, we present a statistical description of the compositional evolution of Q-speciation in these glasses by accounting for the relative enthalpic and entropic contributions to the bonding preferences. We show that the entire glass structure evolution can be predicted based on experimental structural information for only a few glass compositions in each series. The model also captures the differences in bonding preferences in glasses with different field strengths (charge-to-size ratio) of the modifier cations.
UR - http://www.scopus.com/inward/record.url?scp=85049902936&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85049902936&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcb.8b04604
DO - 10.1021/acs.jpcb.8b04604
M3 - Article
C2 - 29995414
AN - SCOPUS:85049902936
SN - 1520-6106
VL - 122
SP - 7609
EP - 7615
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 30
ER -