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Title: Local Structure of amorphous (PbO){sub x}[(B{sub 2}O{sub 3}){sub 1-z}(Al{sub 2}O{sub 3}){sub z}]{sub y} (SiO{sub 2}){sub y} Dielectric Materials by Multinuclear Solid State NMR

Abstract

Structural speciation of glasses in the systems PbO-B{sub 2}O{sub 3}-SiO{sub 2}, PbO-B{sub 2}O{sub 3}-Al{sub 2}O{sub 3}-SiO{sub 2}, and PbO-Al{sub 2}O{sub 3}-SiO{sub 2} were studied using solid-state {sup 29}Si, {sup 27}Al, {sup 11}B, and {sup 207}Pb nuclear magnetic resonance (NMR) and Raman spectroscopy. Application of these methods provided insight into the role of Al{sub 2}O{sub 3} incorporation in the lead-borosilicate glass networks. The general composition range studied was (PbO){sub x} [(B{sub 2}O{sub 3}){sub 1-z} (Al{sub 2}O{sub 3})z]{sub y}(SiO{sub 2}){sub y} where x = 0.35, 0.5, and 0.65, y = (1-x)/2 and z = 0.0, 0.5 and 1.0. Additional insight was obtained via {sup 27}Al 2D-3QMAS experiments. The {sup 207}Pb spin echo mapping spectra showed a transition from ionic (Pb{sup 2+}) to covalently bound lead species with increased PbO contents in the borosilicate glasses. The addition of aluminum to the glass network further enhanced the lead species transition resulting in a higher relative amount of covalent lead bonding in the high PbO content alumino-borosilicate glass. The number of BO{sub 4} units present in the {sup 11}B MAS NMR decreased with increasing PbO contents for both the borosilicate and the alumino-borosilicate glass systems, with the addition of aluminum further promoting the BO{sub 3}more » species. A deshielding of the {sup 11}B chemical shifts and the {sup 27}Al chemical shifts with increased lead contents (independent of changes in the quadrupolar coupling) was also observed for both glass systems and was attributed to increasingly homogeneous glass structure. The {sup 29}Si spectra of the borosilicate and alumino-borosilicate glasses showed a downfield shift with increased PbO concentrations representing incorporation of Pb into the silicate and aluminosilicate networks. The Raman spectra were characterized by increased intensities of Si-O-Pb peaks and decreased intensities of Q{sup 3} peaks with increased PbO contents and showed no evidence of BO{sub 3} or BO{sub 4} ring species. Both the NMR and the Raman data point toward systems where lead is increasingly incorporated into the B{sub 2}O{sub 3}-SiO{sub 2} and the B{sub 2}O{sub 3}-SiO{sub 2}-Al{sub 2}O{sub 3} networks at high PbO concentrations, with the addition of Al{sub 2}O{sub 3} enhancing the trend.« less

Authors:
; ; ;
Publication Date:
Research Org.:
Lawrence Livermore National Lab., Livermore, CA (US)
Sponsoring Org.:
US Department of Energy (US)
OSTI Identifier:
15016013
Report Number(s):
UCRL-JRNL-200058
Journal ID: ISSN 0897-4756; CMATEX; TRN: US200509%%748
DOE Contract Number:  
W-7405-ENG-48
Resource Type:
Journal Article
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 17; Journal Issue: 6; Other Information: Publication date is April 1, 2005; PDF-FILE: 31 ; SIZE: 0.6 MBYTES; PBD: 5 Sep 2003; Journal ID: ISSN 0897-4756
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 58 GEOSCIENCES; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ALUMINIUM; BONDING; BOROSILICATE GLASS; CHEMICAL SHIFT; DIELECTRIC MATERIALS; GLASS; NUCLEAR MAGNETIC RESONANCE; RAMAN SPECTRA; RAMAN SPECTROSCOPY; SILICATES; SPECTRA; SPIN ECHO

Citation Formats

Sawvel, A, Chinn, S, Bourcier, W, and Maxwell, R. Local Structure of amorphous (PbO){sub x}[(B{sub 2}O{sub 3}){sub 1-z}(Al{sub 2}O{sub 3}){sub z}]{sub y} (SiO{sub 2}){sub y} Dielectric Materials by Multinuclear Solid State NMR. United States: N. p., 2003. Web.
Sawvel, A, Chinn, S, Bourcier, W, & Maxwell, R. Local Structure of amorphous (PbO){sub x}[(B{sub 2}O{sub 3}){sub 1-z}(Al{sub 2}O{sub 3}){sub z}]{sub y} (SiO{sub 2}){sub y} Dielectric Materials by Multinuclear Solid State NMR. United States.
Sawvel, A, Chinn, S, Bourcier, W, and Maxwell, R. Fri . "Local Structure of amorphous (PbO){sub x}[(B{sub 2}O{sub 3}){sub 1-z}(Al{sub 2}O{sub 3}){sub z}]{sub y} (SiO{sub 2}){sub y} Dielectric Materials by Multinuclear Solid State NMR". United States. https://www.osti.gov/servlets/purl/15016013.
@article{osti_15016013,
title = {Local Structure of amorphous (PbO){sub x}[(B{sub 2}O{sub 3}){sub 1-z}(Al{sub 2}O{sub 3}){sub z}]{sub y} (SiO{sub 2}){sub y} Dielectric Materials by Multinuclear Solid State NMR},
author = {Sawvel, A and Chinn, S and Bourcier, W and Maxwell, R},
abstractNote = {Structural speciation of glasses in the systems PbO-B{sub 2}O{sub 3}-SiO{sub 2}, PbO-B{sub 2}O{sub 3}-Al{sub 2}O{sub 3}-SiO{sub 2}, and PbO-Al{sub 2}O{sub 3}-SiO{sub 2} were studied using solid-state {sup 29}Si, {sup 27}Al, {sup 11}B, and {sup 207}Pb nuclear magnetic resonance (NMR) and Raman spectroscopy. Application of these methods provided insight into the role of Al{sub 2}O{sub 3} incorporation in the lead-borosilicate glass networks. The general composition range studied was (PbO){sub x} [(B{sub 2}O{sub 3}){sub 1-z} (Al{sub 2}O{sub 3})z]{sub y}(SiO{sub 2}){sub y} where x = 0.35, 0.5, and 0.65, y = (1-x)/2 and z = 0.0, 0.5 and 1.0. Additional insight was obtained via {sup 27}Al 2D-3QMAS experiments. The {sup 207}Pb spin echo mapping spectra showed a transition from ionic (Pb{sup 2+}) to covalently bound lead species with increased PbO contents in the borosilicate glasses. The addition of aluminum to the glass network further enhanced the lead species transition resulting in a higher relative amount of covalent lead bonding in the high PbO content alumino-borosilicate glass. The number of BO{sub 4} units present in the {sup 11}B MAS NMR decreased with increasing PbO contents for both the borosilicate and the alumino-borosilicate glass systems, with the addition of aluminum further promoting the BO{sub 3} species. A deshielding of the {sup 11}B chemical shifts and the {sup 27}Al chemical shifts with increased lead contents (independent of changes in the quadrupolar coupling) was also observed for both glass systems and was attributed to increasingly homogeneous glass structure. The {sup 29}Si spectra of the borosilicate and alumino-borosilicate glasses showed a downfield shift with increased PbO concentrations representing incorporation of Pb into the silicate and aluminosilicate networks. The Raman spectra were characterized by increased intensities of Si-O-Pb peaks and decreased intensities of Q{sup 3} peaks with increased PbO contents and showed no evidence of BO{sub 3} or BO{sub 4} ring species. Both the NMR and the Raman data point toward systems where lead is increasingly incorporated into the B{sub 2}O{sub 3}-SiO{sub 2} and the B{sub 2}O{sub 3}-SiO{sub 2}-Al{sub 2}O{sub 3} networks at high PbO concentrations, with the addition of Al{sub 2}O{sub 3} enhancing the trend.},
doi = {},
url = {https://www.osti.gov/biblio/15016013}, journal = {Chemistry of Materials},
issn = {0897-4756},
number = 6,
volume = 17,
place = {United States},
year = {2003},
month = {9}
}