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Title: Rare-earth titanate melt structure and glass formation

Abstract

The structure of rare–earth titanate melts and glasses of composition 17RE2O3.83TiO2 have been investigated in situ by aerodynamic levitation with laser heating. Ti K–edge X–ray absorption near–edge structure (XANES) spectroscopy reveals an effect of RE cation size on mean Ti–O coordination numbers (nTiO), which increase from ~4.8(2) in glass–forming La titanate to ~5.1(2) in non–glass–forming Sc titanate liquids. We suggest that the associated increase in OTi3 triclusters in melts bearing smaller RE cations tends to inhibit glass formation. Both XANES and high–energy X–ray diffraction indicate increases in nTiO as the liquids supercool and vitrify. Results are discussed in the context of alkali and alkaline–earth titanate glasses, extending the observed dependence of nTiO on structural basicity (modifier content divided by potential) to trivalent modifiers and the molten state. We suggest that the most stable titanate glasses form close to compositions where, on average, two oxygen anions bond to each titanium, allowing a continuous, disordered Ti–O network of bridging oxygen (OTi2), or with equal numbers of OTi3 triclusters and OTi1 non–bridging oxygen in charge–balance. Here, we report on new glasses formed from praseodymium, europium, and gadolinium titanate melts, the latter being the smallest rare–earth for which binary titanate glasses have been obtained.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [3]
+ Show Author Affiliations
  1. Materials Development, Inc., Arlington Heights, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States). X-Ray Science Div.
  3. Materials Development, Inc., Arlington Heights, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States). X-Ray Science Div.
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Small Business Innovation Research (SBIR) and Small Business Technology Transfer (STTR); USDOE
OSTI Identifier:
1574297
Alternate Identifier(s):
OSTI ID: 1560342
Grant/Contract Number:  
AC02-06CH11357; SC0015241; SC0018601
Resource Type:
Accepted Manuscript
Journal Name:
International Journal of Applied Glass Science
Additional Journal Information:
Journal Volume: 10; Journal Issue: 4; Journal ID: ISSN 2041-1286
Publisher:
American Ceramic Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; characterization; glass forming melts; glass forming systems; structure; X‐ray absorption; X‐ray diffraction

Citation Formats

Alderman, Oliver L. G., Benmore, Chris J., Tamalonis, Anthony J., and Weber, Rick. Rare-earth titanate melt structure and glass formation. United States: N. p., 2019. Web. doi:10.1111/ijag.13479.
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Alderman, Oliver L. G., Benmore, Chris J., Tamalonis, Anthony J., & Weber, Rick. Rare-earth titanate melt structure and glass formation. United States. https://doi.org/10.1111/ijag.13479
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Alderman, Oliver L. G., Benmore, Chris J., Tamalonis, Anthony J., and Weber, Rick. Wed . "Rare-earth titanate melt structure and glass formation". United States. https://doi.org/10.1111/ijag.13479. https://www.osti.gov/servlets/purl/1574297.
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@article{osti_1574297,
title = {Rare-earth titanate melt structure and glass formation},
author = {Alderman, Oliver L. G. and Benmore, Chris J. and Tamalonis, Anthony J. and Weber, Rick},
abstractNote = {The structure of rare–earth titanate melts and glasses of composition 17RE2O3.83TiO2 have been investigated in situ by aerodynamic levitation with laser heating. Ti K–edge X–ray absorption near–edge structure (XANES) spectroscopy reveals an effect of RE cation size on mean Ti–O coordination numbers (nTiO), which increase from ~4.8(2) in glass–forming La titanate to ~5.1(2) in non–glass–forming Sc titanate liquids. We suggest that the associated increase in OTi3 triclusters in melts bearing smaller RE cations tends to inhibit glass formation. Both XANES and high–energy X–ray diffraction indicate increases in nTiO as the liquids supercool and vitrify. Results are discussed in the context of alkali and alkaline–earth titanate glasses, extending the observed dependence of nTiO on structural basicity (modifier content divided by potential) to trivalent modifiers and the molten state. We suggest that the most stable titanate glasses form close to compositions where, on average, two oxygen anions bond to each titanium, allowing a continuous, disordered Ti–O network of bridging oxygen (OTi2), or with equal numbers of OTi3 triclusters and OTi1 non–bridging oxygen in charge–balance. Here, we report on new glasses formed from praseodymium, europium, and gadolinium titanate melts, the latter being the smallest rare–earth for which binary titanate glasses have been obtained.},
doi = {10.1111/ijag.13479},
journal = {International Journal of Applied Glass Science},
number = 4,
volume = 10,
place = {United States},
year = {2019},
month = {7}
}
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https://doi.org/10.1111/ijag.13479
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Figures / Tables:

Table 1 Table 1: Properties of the rare earth ions and rare-earth sesquioxide-titanium dioxide systems. The ionic radii54 are for trivalent cations in 6-fold coordination to oxygen, for sake of comparison. Hyphens (–) indicate lack of any glass formation for the 17RE2O3.83TiO2 compositions tested herein.
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    Table 3 (p. 19)table
    Table 4 (p. 19)table
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    Figure 2 (p. 21)figure
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