Solid-state NMR investigations of sodium-cesium mixed-alkali phosphate glasses

S. Prabakar, Karl Todd Mueller

Research output: Contribution to journalConference article

14 Citations (Scopus)

Abstract

Simultaneous structural correlations between 31P and 23Na nuclei and between 31P and 133Cs nuclei in a series of mixed-alkali sodium-cesium phosphate glasses are investigated by transfer of populations via double resonance (TRAPDOR) NMR spectroscopy. The variations in spatial proximity between 31P nuclei at the center of phosphate tetrahedra and sodium (or cesium) modifier ions in the system xCs 2O: (56 - x) Na2O: 44 P2O5 (where x = 0 - 40) are followed systematically as a function of alkali oxide composition. The TRAPDOR method probes specific interactions between 31P and 23Na (or 133Cs) nuclei through the direct nuclear spin dipolar interaction. 31P MAS NMR spectra of these polyphosphate glasses reveal two phosphate environments corresponding to phosphorus atoms with two (Q2) and one (Q1) non-bridging oxygens in a 2.7:1 ratio, as expected from a simple depolymerization model. The Q 2/Q1 ratios measured using the TRAPDOR technique show a mixed-alkali effect as a function of alkali oxide concentration, revealing a maximum in the effect for 31P-23Na pairings and a minimum interaction for 31P-133Cs at concentrations of approximately 35mol% for each of the respective alkali cations.

Original languageEnglish (US)
Pages (from-to)80-87
Number of pages8
JournalJournal of Non-Crystalline Solids
Volume349
Issue number1-3
DOIs
StatePublished - Dec 1 2004
EventGlass Science for High Technology. 16th University Conference - Troy, NY, United States
Duration: Aug 13 2004Aug 15 2004

Fingerprint

Cesium
Alkalies
cesium
alkalies
phosphates
Phosphates
Sodium
Nuclear magnetic resonance
sodium
solid state
Glass
nuclear magnetic resonance
glass
phosphorus pentoxide
nuclei
Depolymerization
Oxides
Nuclear magnetic resonance spectroscopy
Phosphorus
cesium ions

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Ceramics and Composites
  • Condensed Matter Physics
  • Materials Chemistry

Cite this

Prabakar, S. ; Mueller, Karl Todd. / Solid-state NMR investigations of sodium-cesium mixed-alkali phosphate glasses. In: Journal of Non-Crystalline Solids. 2004 ; Vol. 349, No. 1-3. pp. 80-87.
@article{8f2c367d4cb8424db284ceebaba84696,
title = "Solid-state NMR investigations of sodium-cesium mixed-alkali phosphate glasses",
abstract = "Simultaneous structural correlations between 31P and 23Na nuclei and between 31P and 133Cs nuclei in a series of mixed-alkali sodium-cesium phosphate glasses are investigated by transfer of populations via double resonance (TRAPDOR) NMR spectroscopy. The variations in spatial proximity between 31P nuclei at the center of phosphate tetrahedra and sodium (or cesium) modifier ions in the system xCs 2O: (56 - x) Na2O: 44 P2O5 (where x = 0 - 40) are followed systematically as a function of alkali oxide composition. The TRAPDOR method probes specific interactions between 31P and 23Na (or 133Cs) nuclei through the direct nuclear spin dipolar interaction. 31P MAS NMR spectra of these polyphosphate glasses reveal two phosphate environments corresponding to phosphorus atoms with two (Q2) and one (Q1) non-bridging oxygens in a 2.7:1 ratio, as expected from a simple depolymerization model. The Q 2/Q1 ratios measured using the TRAPDOR technique show a mixed-alkali effect as a function of alkali oxide concentration, revealing a maximum in the effect for 31P-23Na pairings and a minimum interaction for 31P-133Cs at concentrations of approximately 35mol{\%} for each of the respective alkali cations.",
author = "S. Prabakar and Mueller, {Karl Todd}",
year = "2004",
month = "12",
day = "1",
doi = "10.1016/j.jnoncrysol.2004.08.253",
language = "English (US)",
volume = "349",
pages = "80--87",
journal = "Journal of Non-Crystalline Solids",
issn = "0022-3093",
publisher = "Elsevier",
number = "1-3",

}

Solid-state NMR investigations of sodium-cesium mixed-alkali phosphate glasses. / Prabakar, S.; Mueller, Karl Todd.

In: Journal of Non-Crystalline Solids, Vol. 349, No. 1-3, 01.12.2004, p. 80-87.

Research output: Contribution to journalConference article

TY - JOUR

T1 - Solid-state NMR investigations of sodium-cesium mixed-alkali phosphate glasses

AU - Prabakar, S.

AU - Mueller, Karl Todd

PY - 2004/12/1

Y1 - 2004/12/1

N2 - Simultaneous structural correlations between 31P and 23Na nuclei and between 31P and 133Cs nuclei in a series of mixed-alkali sodium-cesium phosphate glasses are investigated by transfer of populations via double resonance (TRAPDOR) NMR spectroscopy. The variations in spatial proximity between 31P nuclei at the center of phosphate tetrahedra and sodium (or cesium) modifier ions in the system xCs 2O: (56 - x) Na2O: 44 P2O5 (where x = 0 - 40) are followed systematically as a function of alkali oxide composition. The TRAPDOR method probes specific interactions between 31P and 23Na (or 133Cs) nuclei through the direct nuclear spin dipolar interaction. 31P MAS NMR spectra of these polyphosphate glasses reveal two phosphate environments corresponding to phosphorus atoms with two (Q2) and one (Q1) non-bridging oxygens in a 2.7:1 ratio, as expected from a simple depolymerization model. The Q 2/Q1 ratios measured using the TRAPDOR technique show a mixed-alkali effect as a function of alkali oxide concentration, revealing a maximum in the effect for 31P-23Na pairings and a minimum interaction for 31P-133Cs at concentrations of approximately 35mol% for each of the respective alkali cations.

AB - Simultaneous structural correlations between 31P and 23Na nuclei and between 31P and 133Cs nuclei in a series of mixed-alkali sodium-cesium phosphate glasses are investigated by transfer of populations via double resonance (TRAPDOR) NMR spectroscopy. The variations in spatial proximity between 31P nuclei at the center of phosphate tetrahedra and sodium (or cesium) modifier ions in the system xCs 2O: (56 - x) Na2O: 44 P2O5 (where x = 0 - 40) are followed systematically as a function of alkali oxide composition. The TRAPDOR method probes specific interactions between 31P and 23Na (or 133Cs) nuclei through the direct nuclear spin dipolar interaction. 31P MAS NMR spectra of these polyphosphate glasses reveal two phosphate environments corresponding to phosphorus atoms with two (Q2) and one (Q1) non-bridging oxygens in a 2.7:1 ratio, as expected from a simple depolymerization model. The Q 2/Q1 ratios measured using the TRAPDOR technique show a mixed-alkali effect as a function of alkali oxide concentration, revealing a maximum in the effect for 31P-23Na pairings and a minimum interaction for 31P-133Cs at concentrations of approximately 35mol% for each of the respective alkali cations.

UR - http://www.scopus.com/inward/record.url?scp=9744280478&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=9744280478&partnerID=8YFLogxK

U2 - 10.1016/j.jnoncrysol.2004.08.253

DO - 10.1016/j.jnoncrysol.2004.08.253

M3 - Conference article

VL - 349

SP - 80

EP - 87

JO - Journal of Non-Crystalline Solids

JF - Journal of Non-Crystalline Solids

SN - 0022-3093

IS - 1-3

ER -