Structural Impact of Nitrogen Incorporation on Properties of Alkali Germanophosphate Glasses

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

3 Citationer (Scopus)

Resumé

The structure, atomic packing density, calorimetric glass transition, and hardness of mixed sodium–lithium germanophosphate oxynitride glasses with varying Ge/P and N/P ratios were investigated. The combined influences of nitridation and mixed network former effect (MNFE) on the glass structure were analyzed using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and 31P nuclear magnetic resonance (NMR) spectroscopy. Evidence for the existence of germanium in a higher coordination state, i.e., five- or sixfold coordination, was obtained by performing XPS analysis of the oxide glasses, with indication of conversion to tetrahedral coordination upon nitridation. Raman spectroscopy measurements implied that the germanate network was modified upon nitridation, including the removal of ring-like germanate structures and P–O–Ge mixed linkages. The partial anionic N-for-O substitution gave rise to the linear dependence of the glass transition temperature (T g) and hardness (H V) on nitrogen content (expressed as N/P ratio), especially for lower Ge/P ratio. However, nitridation also caused an unexpected increase in liquid fragility and decrease in density. This suggests that the governing structural parameter for property evolution in such LiNaGePON glasses is not only the increased degree of cross-linking of the phosphate chains, but rather the short- and intermediate-range structural modifications within the germanate component of the oxynitride glasses.

OriginalsprogEngelsk
TidsskriftJournal of the American Ceramic Society
Vol/bind101
Udgave nummer11
Sider (fra-til)5004-5019
ISSN0002-7820
DOI
StatusUdgivet - 2018

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Alkalies
Nitridation
Nitrogen
Glass
Raman spectroscopy
X ray photoelectron spectroscopy
Hardness
Germanium
Oxides
Nuclear magnetic resonance spectroscopy
Glass transition
Phosphates
Substitution reactions
Liquids

Citer dette

@article{977a01464b9b41838497586952e8dda6,
title = "Structural Impact of Nitrogen Incorporation on Properties of Alkali Germanophosphate Glasses",
abstract = "The structure, atomic packing density, calorimetric glass transition, and hardness of mixed sodium–lithium germanophosphate oxynitride glasses with varying Ge/P and N/P ratios were investigated. The combined influences of nitridation and mixed network former effect (MNFE) on the glass structure were analyzed using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and 31P nuclear magnetic resonance (NMR) spectroscopy. Evidence for the existence of germanium in a higher coordination state, i.e., five- or sixfold coordination, was obtained by performing XPS analysis of the oxide glasses, with indication of conversion to tetrahedral coordination upon nitridation. Raman spectroscopy measurements implied that the germanate network was modified upon nitridation, including the removal of ring-like germanate structures and P–O–Ge mixed linkages. The partial anionic N-for-O substitution gave rise to the linear dependence of the glass transition temperature (T g) and hardness (H V) on nitrogen content (expressed as N/P ratio), especially for lower Ge/P ratio. However, nitridation also caused an unexpected increase in liquid fragility and decrease in density. This suggests that the governing structural parameter for property evolution in such LiNaGePON glasses is not only the increased degree of cross-linking of the phosphate chains, but rather the short- and intermediate-range structural modifications within the germanate component of the oxynitride glasses.",
author = "Georgiana-Laura Paraschiv and Francisco Munoz and Jensen, {Lars Rosgaard} and Larsen, {Raino Mikael} and Yuanzheng Yue and Smedskj{\ae}r, {Morten Mattrup}",
year = "2018",
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Structural Impact of Nitrogen Incorporation on Properties of Alkali Germanophosphate Glasses. / Paraschiv, Georgiana-Laura; Munoz, Francisco; Jensen, Lars Rosgaard; Larsen, Raino Mikael; Yue, Yuanzheng; Smedskjær, Morten Mattrup.

I: Journal of the American Ceramic Society, Bind 101, Nr. 11, 2018, s. 5004-5019.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Structural Impact of Nitrogen Incorporation on Properties of Alkali Germanophosphate Glasses

AU - Paraschiv, Georgiana-Laura

AU - Munoz, Francisco

AU - Jensen, Lars Rosgaard

AU - Larsen, Raino Mikael

AU - Yue, Yuanzheng

AU - Smedskjær, Morten Mattrup

PY - 2018

Y1 - 2018

N2 - The structure, atomic packing density, calorimetric glass transition, and hardness of mixed sodium–lithium germanophosphate oxynitride glasses with varying Ge/P and N/P ratios were investigated. The combined influences of nitridation and mixed network former effect (MNFE) on the glass structure were analyzed using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and 31P nuclear magnetic resonance (NMR) spectroscopy. Evidence for the existence of germanium in a higher coordination state, i.e., five- or sixfold coordination, was obtained by performing XPS analysis of the oxide glasses, with indication of conversion to tetrahedral coordination upon nitridation. Raman spectroscopy measurements implied that the germanate network was modified upon nitridation, including the removal of ring-like germanate structures and P–O–Ge mixed linkages. The partial anionic N-for-O substitution gave rise to the linear dependence of the glass transition temperature (T g) and hardness (H V) on nitrogen content (expressed as N/P ratio), especially for lower Ge/P ratio. However, nitridation also caused an unexpected increase in liquid fragility and decrease in density. This suggests that the governing structural parameter for property evolution in such LiNaGePON glasses is not only the increased degree of cross-linking of the phosphate chains, but rather the short- and intermediate-range structural modifications within the germanate component of the oxynitride glasses.

AB - The structure, atomic packing density, calorimetric glass transition, and hardness of mixed sodium–lithium germanophosphate oxynitride glasses with varying Ge/P and N/P ratios were investigated. The combined influences of nitridation and mixed network former effect (MNFE) on the glass structure were analyzed using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and 31P nuclear magnetic resonance (NMR) spectroscopy. Evidence for the existence of germanium in a higher coordination state, i.e., five- or sixfold coordination, was obtained by performing XPS analysis of the oxide glasses, with indication of conversion to tetrahedral coordination upon nitridation. Raman spectroscopy measurements implied that the germanate network was modified upon nitridation, including the removal of ring-like germanate structures and P–O–Ge mixed linkages. The partial anionic N-for-O substitution gave rise to the linear dependence of the glass transition temperature (T g) and hardness (H V) on nitrogen content (expressed as N/P ratio), especially for lower Ge/P ratio. However, nitridation also caused an unexpected increase in liquid fragility and decrease in density. This suggests that the governing structural parameter for property evolution in such LiNaGePON glasses is not only the increased degree of cross-linking of the phosphate chains, but rather the short- and intermediate-range structural modifications within the germanate component of the oxynitride glasses.

U2 - 10.1111/jace.15747

DO - 10.1111/jace.15747

M3 - Journal article

VL - 101

SP - 5004

EP - 5019

JO - Journal of the American Ceramic Society

JF - Journal of the American Ceramic Society

SN - 0002-7820

IS - 11

ER -