Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

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 Laboratory (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.
Copy to clipboard
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
Copy to clipboard
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.
Copy to clipboard
@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 = {Wed Jul 03 00:00:00 EDT 2019},
month = {Wed Jul 03 00:00:00 EDT 2019}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1111/ijag.13479
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal

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.
All figures and tables (12 total)
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005

Infrared refractive index of diamond
journal, January 1981

  • Edwards, David F.; Ochoa, Ellen
  • Journal of the Optical Society of America, Vol. 71, Issue 5
  • DOI: 10.1364/JOSA.71.000607

Refractive index calculation using the structural properties of La4Ti9O24 glass
journal, May 2008

  • Arai, Yasutomo; Itoh, Keiji; Kohara, Shinji
  • Journal of Applied Physics, Vol. 103, Issue 9
  • DOI: 10.1063/1.2903544

Density of thin TiO2 films
journal, June 1996

  • Laube, M.; Rauch, F.; Ottermann, C.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 113, Issue 1-4
  • DOI: 10.1016/0168-583X(95)01331-8

Phase relationship in the TiO2–Nd2O3 pseudo-binary system
journal, January 2013

Liquid B 2 O 3 up to 1700 K: x-ray diffraction and boroxol ring dissolution
journal, October 2015

Continuous Structural Transition in Glass-Forming Molten Titanate BaTi 2 O 5
journal, November 2016

  • Alderman, O. L. G.; Benmore, C. J.; Tamalonis, A.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 47
  • DOI: 10.1021/acs.jpcc.6b08248

Structure of binary K2OTiO2 and Cs2OTiO2 glasses
journal, October 1989

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976

Study on upconversion luminescence and thermal properties of Ho3+/Yb3+ co-doped La2O3–TiO2–ZrO2 glasses
journal, July 2016

Aerodynamic levitator for in situ x-ray structure measurements on high temperature and molten nuclear fuel materials
journal, July 2016

  • Weber, J. K. R.; Tamalonis, A.; Benmore, C. J.
  • Review of Scientific Instruments, Vol. 87, Issue 7
  • DOI: 10.1063/1.4955210

Glass formation of rare earth aluminates by containerless processing
journal, December 2012

Natural widths of atomic K and L levels, K α X‐ray lines and several K L L Auger lines
journal, April 1979

  • Krause, M. O.; Oliver, J. H.
  • Journal of Physical and Chemical Reference Data, Vol. 8, Issue 2
  • DOI: 10.1063/1.555595

Borate melt structure: Temperature‐dependent B–O bond lengths and coordination numbers from high‐energy X‐ray diffraction
journal, March 2018

  • Alderman, Oliver L. G.; Benmore, Chris J.; Lin, Alex
  • Journal of the American Ceramic Society, Vol. 101, Issue 8
  • DOI: 10.1111/jace.15529

Comprehensive Structural Study of Glassy and Metastable Crystalline BaTi 2 O 5
journal, January 2009

  • Yu, Jianding; Kohara, Shinji; Itoh, Keiji
  • Chemistry of Materials, Vol. 21, Issue 2
  • DOI: 10.1021/cm802483w

Glass Formation in LaO3/2-TiO2 Binary System by Containerless Processing
journal, December 2011

Optical super-resolution by high-index liquid-immersed microspheres
journal, October 2012

  • Darafsheh, Arash; Walsh, Gary F.; Dal Negro, Luca
  • Applied Physics Letters, Vol. 101, Issue 14
  • DOI: 10.1063/1.4757600

Laser hearth melt processing of ceramic materials
journal, February 1996

  • Richard Weber, J. K.; Felten, J. J.; Nordine, Paul C.
  • Review of Scientific Instruments, Vol. 67, Issue 2
  • DOI: 10.1063/1.1146631

Rapid quenching on the binary systems of high temperature oxides
journal, June 1974

The Density of Titanium(IV) Oxide Liquid
journal, October 1991

Structure of molten titanium dioxide
journal, September 2014

Molten barium titanate: a high-pressure liquid silicate analogue
journal, March 2019

  • Alderman, O. L. G.; Benmore, C. J.; Neuefeind, J.
  • Journal of Physics: Condensed Matter, Vol. 31, Issue 20
  • DOI: 10.1088/1361-648X/ab0939

Vitreous forsterite (Mg 2 SiO 4 ): Synthesis, structure, and thermochemistry
journal, July 2001

  • Tangeman, Jean A.; Phillips, Brian L.; Navrotsky, Alexandra
  • Geophysical Research Letters, Vol. 28, Issue 13
  • DOI: 10.1029/2000GL012222

Low Cation Coordination in Oxide Melts
journal, April 2014

Influence of the Atmosphere on the Oxidation State of the Eu-Ion in a SiAIO(N) Glass and Glass-Ceramic
journal, January 2000

Local structural variation with oxygen fugacity in Fe2SiO4+ fayalitic iron silicate melts
journal, April 2017

Glass-forming region and high refractive index of TiO 2 -based glasses prepared by containerless processing : Glass-forming region and high refractive index of TiO
journal, October 2012

  • Masuno, Atsunobu; Watanabe, Yasuhiro; Inoue, Hiroyuki
  • physica status solidi (c), Vol. 9, Issue 12
  • DOI: 10.1002/pssc.201200313

Investigation of TiO2SiO2 glasses by X-ray absorption spectroscopy
journal, April 1983

  • Greegor, Robert B.; Lytle, Farrel W.; Sandstrom, Donald R.
  • Journal of Non-Crystalline Solids, Vol. 55, Issue 1
  • DOI: 10.1016/0022-3093(83)90005-4

Refractive index dispersion, optical transmittance, and Raman scattering of BaTi2O5 glass
journal, September 2010

  • Masuno, A.; Inoue, H.; Yu, J.
  • Journal of Applied Physics, Vol. 108, Issue 6
  • DOI: 10.1063/1.3482040

Measurements of liquid and glass structures using aerodynamic levitation and in-situ high energy x-ray and neutron scattering
journal, January 2014

Phase Relations in the System Y2O3-TiO2
journal, March 1976

Structure of Na2O�2TiO2 glass
journal, January 1991

  • Miyaji, F.; Yoko, T.; Kozuka, H.
  • Journal of Materials Science, Vol. 26, Issue 1
  • DOI: 10.1007/BF00576059

Phase stability and equilibria in the La2O3–TiO2 system
journal, July 2000

  • Škapin, Srečo D.; Kolar✠, Drago; Suvorov, Danilo
  • Journal of the European Ceramic Society, Vol. 20, Issue 8
  • DOI: 10.1016/S0955-2219(99)00270-8

Study on the structure of K2O·2TiO2 glass by X-ray radial distribution analysis
journal, January 1989

Synthesis of amorphous La 4 Ti 9 O 24 microspheres with high-refractive index via containerless flame-spraying method
journal, January 2018

Solidification and thermophysical property studies of barium titanate using electrostatic levitation furnace
journal, July 2006

Spectral Absorption Coefficient of Molten Aluminum Oxide from.0.385 to 0.780 mum
journal, March 1995

Phase equilibrium relationships in the system Gd2O3-TiO2
journal, May 1965

  • Waring, J. L.; Schneider, S. J.
  • Journal of Research of the National Bureau of Standards Section A: Physics and Chemistry, Vol. 69A, Issue 3
  • DOI: 10.6028/jres.069A.025

The Structural Role of Lanthanum and Yttrium in Aluminosilicate Glasses:  A 27 Al and 17 O MAS NMR Study
journal, December 1998

  • Schaller, Torsten; Stebbins, Jonathan F.
  • The Journal of Physical Chemistry B, Vol. 102, Issue 52
  • DOI: 10.1021/jp982387m

Iron K-edge X-ray absorption near-edge structure spectroscopy of aerodynamically levitated silicate melts and glasses
journal, March 2017

Density and refractive index of TiO2 films prepared by reactive evaporation
journal, August 2000

The partial molar volume and thermal expansivity of TiO 2 in alkali silicate melts: Systematic variation with Ti coordination
journal, July 2001

Preparation and properties of binary oxide glasses containing rare earth oxides. [希土類含有高融点酸化物ガラスの作製とその二，三の物性]
journal, January 1986

  • Kozuka, Hiromitsu; Ota, Rikuo; Soga, Naohiro
  • Journal of the Society of Materials Science, Japan, Vol. 35, Issue 388
  • DOI: 10.2472/jsms.35.73

Ti K -edge XANES studies of Ti coordination and disorder in oxide compounds: Comparison between theory and experiment
journal, July 1997

Surface Tensions and Densities of Melts in TiO<SUB>2</SUB>-BaO and TiO<SUB>2</SUB>-Na<SUB>2</SUB>O Systems [TiO2-BaO系融体およびTiO2-Na2O系融体の表面張力と密度]
journal, January 1993

Effect of atomic vibrations on the x-ray absorption spectra at the K edge of Al in α -Al 2 O 3 and of Ti in TiO 2 rutile
journal, March 2010

Borate melt structure: a short review
journal, February 2018

  • Alderman, Oliver
  • Physics and Chemistry of Glasses: European Journal of Glass Science and Technology Part B, Vol. 59, Issue 1
  • DOI: 10.13036/17533562.59.1.016

IFEFFIT  : interactive XAFS analysis and FEFF fitting
journal, March 2001

An interpretation of glass chemistry in terms of the optical basicity concept
journal, August 1976

Magnetosomes could be protective shields against metal stress in magnetotactic bacteria
journal, July 2020

    Sort by:
    [ × clear filter / sort ]

    Figures / Tables found in this record:

    Table 1 (p. 17)table
    Table 2 (p. 18)table
    Table 3 (p. 19)table
    Table 4 (p. 19)table
    Figure 1 (p. 20)figure
    Figure 2 (p. 21)figure
    Figure 3 (p. 22)figure
    Figure 4 (p. 24)figure
    Figure 5 (p. 25)figure
    Figure 6 (p. 26)figure
    Figure 7 (p. 27)figure
    Figure 8 (p. 28)figure
      [ × clear filter / sort ]
      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

      Similar Records in DOE PAGES and OSTI.GOV collections: