Anomalously strong viscosity behavior in mixed oxy-sulfide Na4P2S7-xOx invert glasses

Kmiec, Steven J.; Lovi, Jacob M.; Joyce, Adriana; Bayko, Dmitriy; Martin, Steve W.

doi:10.1016/j.jnoncrysol.2020.120493

Title: Anomalously strong viscosity behavior in mixed oxy-sulfide Na₄P₂S_7-xO_x invert glasses

Journal Article · Tue Nov 24 00:00:00 EST 2020 · Journal of Non-Crystalline Solids

DOI:https://doi.org/10.1016/j.jnoncrysol.2020.120493· OSTI ID:1848225

^[1]; Lovi, Jacob M. ^[1]; Joyce, Adriana ^[1]; Bayko, Dmitriy ^[1];

^[1]

Iowa State Univ., Ames, IA (United States). Dept. of Materials Science and Engineering

In this paper, the first observations have been made of anomalously strong viscosity behavior and correspondingly strong bulk glass formation and resistance to crystallization in a melt quenched (MQ) prepared series of invert, modifier content greater than the glass former content, mixed oxy-sulfide Na₄P₂S_7-xO_x, 0 ≤ x ≤ 5, (NaPSO) glasses. We find that these glasses even with 67 mole % modifier, Na₂S, and only 33 mole% glass former P₂S_5-xO_x, exhibit a calorimetric fragility index, m_cal, as small as 29 compared to typical values of ~ 60 to 80 for alkali silicate glasses with > 50 mole% SiO₂ and the theoretical minimum m_cal of ~ 15. The m_cal values were converted to kinetic viscosity fragility, m_vis, values and used with the measured glass transition temperatures, T_gs, to produce viscosity curves for the glasses using the Mauro-Yue-Ellison-Gupta-Allan (MYEGA) model. The viscosity of the glass with a minimum m_cal value of x = 2.5 was then shown to exhibit a viscosity that was as strong as, and for some compositions stronger than, the viscosity of alkali aluminosilicate glasses which have three dimensional network structures compared to the one dimensional chain structures observed in these MOS invert glasses. Consistent with these small values of fragility indices and therefore predicted higher viscosity above the glass transition temperature, T_g, in the supercooled liquid regime, these glasses are also particularly resistant to crystallization. For example, the x = 2.5 glass composition exhibits a crystallization temperature, T_C, more than 150K above its T_g. We find that the calorimetric fragility of these glasses varies systematically with the extent of network forming bridging oxygens (BOs) in the glasses. The structural change caused by incrementally replacing sulfur with oxygen has been found to have consistent, large effects on the thermal properties.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Iowa State Univ., Ames, IA (United States)

Sponsoring Organization:: USDOE Advanced Research Projects Agency - Energy (ARPA-E)

Grant/Contract Number:: AR0000654; AR0000778; EE0008852

OSTI ID:: 1848225

Alternate ID(s):: OSTI ID: 1775979

Journal Information:: Journal of Non-Crystalline Solids, Vol. 553, Issue C; ISSN 0022-3093

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

Preparation and Electrochemical Properties of the SiS[sub 2]-P[sub 2]S[sub 5]-Li[sub 2]S Glass Coformer System Kennedy, John H. Journal of The Electrochemical Society, Vol. 136, Issue 9 https://doi.org/10.1149/1.2097416	journal	January 1989
Glass Forming Ability Criterion Saad, Mohammed; Poulain, Marcel Materials Science Forum, Vol. 19-20 https://doi.org/10.4028/www.scientific.net/MSF.19-20.11	journal	January 1987
Glass Formation, Ionic Conductivity, and Conductivity/Viscosity Decoupling, in LiAlCl ₄ + LiClO ₄ and LiAlCl ₄ + LiAlCl ₃ ·Imide Solutions Videa, M.; Angell, C. A. The Journal of Physical Chemistry B, Vol. 103, Issue 20 https://doi.org/10.1021/jp984276t	journal	May 1999
Dependence of the glass transition temperature on heating and cooling rate Moynihan, Cornelius T.; Easteal, Allan J.; Wilder, James The Journal of Physical Chemistry, Vol. 78, Issue 26 https://doi.org/10.1021/j100619a008	journal	December 1974
Could dark energy be vector-like? Armendáriz-Picón, C. Journal of Cosmology and Astroparticle Physics, Vol. 2004, Issue 07 https://doi.org/10.1088/1475-7516/2004/07/007	journal	July 2004
Das thermische Verhalten der Mischungen Na2S?P4S10 und Na4Ge4S10?P4S10 des Systems Na2S?GeS2?P4S10 Blachnik, R.; Rabe, U. Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 462, Issue 1 https://doi.org/10.1002/zaac.19804620122	journal	March 1980
Formation and structure of Na2S+P2S5 amorphous materials prepared by melt-quenching and mechanical milling Berbano, Seth S.; Seo, Inseok; Bischoff, Christian M. Journal of Non-Crystalline Solids, Vol. 358, Issue 1 https://doi.org/10.1016/j.jnoncrysol.2011.08.030	journal	January 2012
Estimation of activation energies for structural relaxation and viscous flow from DTA and DSC experiments Moynihan, C. T.; Lee, S. -K.; Tatsumisago, M. Thermochimica Acta, Vol. 280-281 https://doi.org/10.1016/0040-6031(95)02781-5	journal	July 1996
Ionic Conductivity of Mixed Glass Former 0.35Na ₂ O + 0.65[ x B ₂ O ₃ + (1 – x )P ₂ O ₅ ] Glasses Christensen, Randilynn; Olson, Garrett; Martin, Steve W. The Journal of Physical Chemistry B, Vol. 117, Issue 51 https://doi.org/10.1021/jp409497z	journal	December 2013
Preparation and characterization of lithium ion conducting Li2S–P2S5–GeS2 glasses and glass-ceramics Minami, Keiichi; Hayashi, Akitoshi; Tatsumisago, Masahiro Journal of Non-Crystalline Solids, Vol. 356, Issue 44-49 https://doi.org/10.1016/j.jnoncrysol.2010.05.016	journal	October 2010
Glass formation and electrical conductivity studies of melt quenched and mechanically milled 50Li2O:(50−x) P2O5:xB2O3 Money, Benson K.; Hariharan, K. Solid State Ionics, Vol. 179, Issue 27-32 https://doi.org/10.1016/j.ssi.2007.12.068	journal	September 2008
Glass formation and structure of melt quenched mixed oxy-sulfide Na4P2S7-xOx glasses for 0 ≤ x ≤ 5 Kmiec, Steven; Joyce, Adriana; Bayko, Dmitriy Journal of Non-Crystalline Solids, Vol. 534 https://doi.org/10.1016/j.jnoncrysol.2019.119776	journal	April 2020
Viscosity of glass-forming systems Zheng, Qiuju; Mauro, John C. Journal of the American Ceramic Society, Vol. 100, Issue 1 https://doi.org/10.1111/jace.14678	journal	December 2016
Topological understanding of the mixed alkaline earth effect in glass Ding, Zhijie; Wilkinson, Collin J.; Zheng, Jinfeng Journal of Non-Crystalline Solids, Vol. 527 https://doi.org/10.1016/j.jnoncrysol.2019.119696	journal	January 2020
Molecular Glasses with High Fictive Temperatures for Energy Landscape Evaluations Velikov, V.; Borick, S.; Angell, C. A. The Journal of Physical Chemistry B, Vol. 106, Issue 5 https://doi.org/10.1021/jp012001z	journal	February 2002
Thermodynamic aspects of the glass transition in liquids and plastic crystals Angell, C. Austen Pure and Applied Chemistry, Vol. 63, Issue 10 https://doi.org/10.1351/pac199163101387	journal	January 1991
Structural and electronic features of binary Li2S-P2S5 glasses Ohara, Koji; Mitsui, Akio; Mori, Masahiro Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep21302	journal	February 2016
Electrical and electrochemical properties of glass–ceramic electrolytes in the systems Li2S–P2S5–P2S3 and Li2S–P2S5–P2O5 Minami, Keiichi; Hayashi, Akitoshi; Ujiie, Satoshi Solid State Ionics, Vol. 192, Issue 1 https://doi.org/10.1016/j.ssi.2010.06.018	journal	June 2011
Thermal and electrical properties of rapidly quenched glasses in the systems Li2S_SiS2_LixMOy (LixMOy = Li4SiO4, Li2SO4) Hirai, K. Solid State Ionics, Vol. 78, Issue 3-4 https://doi.org/10.1016/0167-2738(95)00094-M	journal	June 1995
Structural Motifs in Fluoride Glasses, and Their Influence on Liquid and Glassy State Properties Angell, C. A.; Phifer, Carol C. Materials Science Forum, Vol. 32-33 https://doi.org/10.4028/www.scientific.net/MSF.32-33.373	journal	January 1991
Preparation of Rapidly Quenched Glasses in Pseudobinary Systems Composed of Lithium Ortho-Oxosalts Tatsumisago, Masahiro; Narita, Hiroshi; Minami, Tsutomu Journal of the American Ceramic Society, Vol. 66, Issue 11 https://doi.org/10.1111/j.1151-2916.1983.tb10576.x	journal	November 1983
Preparation and Structure of Lithium-Ion-Conducting Mixed-Anion Glasses in the System LiBO2-LiBS2 Tatsumisago, Masahiro; Yoneda, Kazuya; Minami, Tsutomu Journal of the American Ceramic Society, Vol. 71, Issue 9 https://doi.org/10.1111/j.1151-2916.1988.tb06411.x	journal	September 1988
First principles study on electrochemical and chemical stability of solid electrolyte–electrode interfaces in all-solid-state Li-ion batteries Zhu, Yizhou; He, Xingfeng; Mo, Yifei Journal of Materials Chemistry A, Vol. 4, Issue 9 https://doi.org/10.1039/C5TA08574H	journal	January 2016
Universality of the high-temperature viscosity limit of silicate liquids Zheng, Qiuju; Mauro, John C.; Ellison, Adam J. Physical Review B, Vol. 83, Issue 21 https://doi.org/10.1103/PhysRevB.83.212202	journal	June 2011
Crystallization Process for Superionic Li7P3S11 Glass-Ceramic Electrolytes: Superionic Li7P3S11 Glass-Ceramic Electrolytes Minami, Keiichi; Hayashi, Akitoshi; Tatsumisago, Masahiro Journal of the American Ceramic Society, Vol. 94, Issue 6 https://doi.org/10.1111/j.1551-2916.2010.04335.x	journal	March 2011
Preparation of Li2S-P2S5 Amorphous Solid Electrolytes by Mechanical Milling Hayashi, Akitoshi; Hama, Shigenori; Morimoto, Hideyuki Journal of the American Ceramic Society, Vol. 84, Issue 2 https://doi.org/10.1111/j.1151-2916.2001.tb00685.x	journal	February 2001
Structural investigations of yNa2S+(1−y)PS5/2 glasses using Raman and infrared spectroscopies Bischoff, Christian; Schuller, Katherine; Haynes, Michael Journal of Non-Crystalline Solids, Vol. 358, Issue 23 https://doi.org/10.1016/j.jnoncrysol.2012.09.023	journal	December 2012
On the Temperature Dependence of Cooperative Relaxation Properties in Glass‐Forming Liquids Adam, Gerold; Gibbs, Julian H. The Journal of Chemical Physics, Vol. 43, Issue 1 https://doi.org/10.1063/1.1696442	journal	July 1965
Studies of Functional Defects for Fast Na-Ion Conduction in Na ₃₋ _y PS ₄₋ _x Cl _x with a Combined Experimental and Computational Approach Feng, Xuyong; Chien, Po-Hsiu; Zhu, Zhuoying Advanced Functional Materials, Vol. 29, Issue 9 https://doi.org/10.1002/adfm.201807951	journal	January 2019
Preparation and characterization of germanium oxy-sulfide GeS2–GeO2 glasses Kim, Youngsik; Saienga, Jason; Martin, Steve W. Journal of Non-Crystalline Solids, Vol. 351, Issue 24-26 https://doi.org/10.1016/j.jnoncrysol.2005.05.020	journal	August 2005
Synthesis, structure determination, and ionic conductivity of sodium tetrathiophosphate Jansen, M.; Henseler, U. Journal of Solid State Chemistry, Vol. 99, Issue 1 https://doi.org/10.1016/0022-4596(92)90295-7	journal	July 1992
Superionic glasses and glass–ceramics in the Li2S–P2S5 system for all-solid-state lithium secondary batteries Tatsumisago, Masahiro; Hayashi, Akitoshi Solid State Ionics, Vol. 225 https://doi.org/10.1016/j.ssi.2012.03.013	journal	October 2012
Synthesis of NiS–carbon fiber composites in high-boiling solvent to improve electrochemical performance in all-solid-state lithium secondary batteries Aso, Keigo; Hayashi, Akitoshi; Tatsumisago, Masahiro Electrochimica Acta, Vol. 83 https://doi.org/10.1016/j.electacta.2012.07.088	journal	November 2012
Effect of pressure on conductivity in liquid and glassy states of a superionic conducting glass Angell, C. Solid State Ionics, Vol. 34, Issue 4 https://doi.org/10.1016/0167-2738(89)90449-9	journal	June 1989
The liquid-glass transition: a mode-coupling perspective Cummins, H. Z. Journal of Physics: Condensed Matter, Vol. 11, Issue 10A https://doi.org/10.1088/0953-8984/11/10A/006	journal	January 1999
Lithium Thiophosphate Glasses and Glass-Ceramics as Solid Electrolytes: Processing, Microstructure, and Properties Berbano, Seth S.; Mirsaneh, Mehdi; Lanagan, Michael T. International Journal of Applied Glass Science, Vol. 4, Issue 4 https://doi.org/10.1111/ijag.12037	journal	August 2013
Influence of sulphate ion on the electrical conductivity of lithium -boro-phosphate glasses Reddy, C. Narayana; Chakradhar, R. P. S. IOP Conference Series: Materials Science and Engineering, Vol. 2 https://doi.org/10.1088/1757-899X/2/1/012053	journal	July 2009
Crystallization And Viscosity Of Heavy Metal Fluoride Glasses Moynihan, C. T.; Mossadegh, R.; Gupta, P. K. O-E/LASE'86 Symp (January 1986, Los Angeles), SPIE Proceedings https://doi.org/10.1117/12.961113	conference	May 1986
Lithium borate glasses: a quantitative study of strength and fragility Chryssikos, G. D.; Duffy, J. A.; Hutchinson, J. M. Journal of Non-Crystalline Solids, Vol. 172-174 https://doi.org/10.1016/0022-3093(94)90460-X	journal	September 1994
Glass formation and structural analysis of Na4P2S7-xOx, 0 ≤ x ≤ 7 sodium oxy-thiophosphate glasses Kmiec, Steven; Joyce, Adriana; Martin, Steve W. Journal of Non-Crystalline Solids, Vol. 498 https://doi.org/10.1016/j.jnoncrysol.2018.06.007	journal	October 2018
Role of PbO in lithium ion transport in Li2O–PbO–B2O3 glasses Ganguli, Munia; Bhat, M. Harish; Rao, K. J. Materials Research Bulletin, Vol. 34, Issue 10-11 https://doi.org/10.1016/S0025-5408(99)00154-3	journal	July 1999
Short time structural relaxation processes in liquids: Comparison of experimental and computer simulation glass transitions on picosecond time scales Angell, C. A.; Torell, L. M. The Journal of Chemical Physics, Vol. 78, Issue 2 https://doi.org/10.1063/1.444798	journal	January 1983
Viscosity properties of sodium borophosphate glasses Gaylord, S.; Tincher, B.; Petit, L. Materials Research Bulletin, Vol. 44, Issue 5 https://doi.org/10.1016/j.materresbull.2008.11.002	journal	May 2009
Improvement of chemical stability of Li3PS4 glass electrolytes by adding MxOy (M = Fe, Zn, and Bi) nanoparticles Hayashi, Akitoshi; Muramatsu, Hiromasa; Ohtomo, Takamasa Journal of Materials Chemistry A, Vol. 1, Issue 21 https://doi.org/10.1039/c3ta10247e	journal	January 2013
Oxide Glasses in Light of the “Ideal Glass” Concept: I, Ideal and Nonideal Transitions, and Departures from Ideality Angell, C. A. Journal of the American Ceramic Society, Vol. 51, Issue 3 https://doi.org/10.1111/j.1151-2916.1968.tb11854.x	journal	March 1968
Study on crystallization of glass by differential thermal analysis. Effect of added oxide on crystallization of Li2O-SiO2 Matusita, K.; Sakka, S.; Maki, T. Journal of Materials Science, Vol. 10, Issue 1 https://doi.org/10.1007/BF00541035	journal	January 1975
Electrochemical properties of ionically conductive glasses Souquet, J. L. Solid State Ionics, Vol. 5 https://doi.org/10.1016/0167-2738(81)90198-3	journal	October 1981
Structure and properties of the Na2S–P2S5 glasses and glass–ceramics prepared by mechanical milling Noi, Kousuke; Hayashi, Akitoshi; Tatsumisago, Masahiro Journal of Power Sources, Vol. 269 https://doi.org/10.1016/j.jpowsour.2014.06.158	journal	December 2014
Mechanochemical synthesis of Li2S–P2S5 glass electrolytes with lithium salts Minami, Keiichi; Hayashi, Akitoshi; Tatsumisago, Masahiro Solid State Ionics, Vol. 181, Issue 33-34 https://doi.org/10.1016/j.ssi.2010.08.021	journal	October 2010
Homogeneous nucleation and glass formation in aqueous alkali halide solutions at high pressures Kanno, H.; Angell, C. A. The Journal of Physical Chemistry, Vol. 81, Issue 26 https://doi.org/10.1021/j100541a013	journal	December 1977
Interface Stability in Solid-State Batteries Richards, William D.; Miara, Lincoln J.; Wang, Yan Chemistry of Materials, Vol. 28, Issue 1 https://doi.org/10.1021/acs.chemmater.5b04082	journal	December 2015
Ionic conductivities of various GeS2-based oxy-sulfide amorphous materials prepared by melt-quenching and mechanical milling methods Kim, Y.; Martin, S. Solid State Ionics, Vol. 177, Issue 33-34 https://doi.org/10.1016/j.ssi.2006.09.001	journal	November 2006
Glass-forming liquids, anomalous liquids, and polyamorphism in liquids and biopolymers Angell, C. A.; Poole, P. H.; Shao, J. Il Nuovo Cimento D, Vol. 16, Issue 8 https://doi.org/10.1007/BF02458784	journal	August 1994
Phase stability, electrochemical stability and ionic conductivity of the Li _10±1 MP ₂ X ₁₂ (M = Ge, Si, Sn, Al or P, and X = O, S or Se) family of superionic conductors Ong, Shyue Ping; Mo, Yifei; Richards, William Davidson Energy Environ. Sci., Vol. 6, Issue 1 https://doi.org/10.1039/C2EE23355J	journal	January 2013
Effect of Li2SO4 on the structure of Li2OB2O3 glasses Chryssikos, G. D.; Kamitsos, E. I.; Patsis, A. P. Journal of Non-Crystalline Solids, Vol. 202, Issue 3 https://doi.org/10.1016/0022-3093(96)00200-1	journal	July 1996
Electrochemical Properties of B 2 S 3 ‐ Li2 S ‐ LiI Vitreous Electrolytes Menetrier, M.; Levasseur, A.; Hagenmuller, P. Journal of The Electrochemical Society, Vol. 131, Issue 9 https://doi.org/10.1149/1.2116002	journal	September 1984
Low-Temperature Synthesis of the Li2S-P2S5 Electrolytes by a Milling Process Combined with Heat Treatment [粉砕と加熱処理の繰り返しによるＬｉ２Ｓ‐Ｐ２Ｓ５系電解質の低温合成] Nakashima, Sho; Kondo, Shigeo; Ooura, Yuji Electrochemistry, Vol. 79, Issue 9 https://doi.org/10.5796/electrochemistry.79.701	journal	January 2011
Viscosity of glass-forming liquids Mauro, J. C.; Yue, Y.; Ellison, A. J. Proceedings of the National Academy of Sciences, Vol. 106, Issue 47 https://doi.org/10.1073/pnas.0911705106	journal	November 2009
Composition Dependence of the Na ⁺ Ion Conductivity in 0.5Na ₂ S + 0.5[ x GeS ₂ + (1 – x )PS _5/2 ] Mixed Glass Former Glasses: A Structural Interpretation of a Negative Mixed Glass Former Effect Martin, Steve W.; Bischoff, Christian; Schuller, Katherine The Journal of Physical Chemistry B, Vol. 119, Issue 51 https://doi.org/10.1021/acs.jpcb.5b07383	journal	December 2015
Glassforming Liquids with Microscopic to Macroscopic Two-State Complexity Angell, C. A. Progress of Theoretical Physics Supplement, Vol. 126 https://doi.org/10.1143/PTPS.126.1	journal	January 1997
Preparation and ionic conductivity of (100−x)(0.8Li2S·0.2P2S5)·xLiI glass–ceramic electrolytes Ujiie, Satoshi; Hayashi, Akitoshi; Tatsumisago, Masahiro Journal of Solid State Electrochemistry, Vol. 17, Issue 3 https://doi.org/10.1007/s10008-012-1900-7	journal	October 2012
Reconciling calorimetric and kinetic fragilities of glass-forming liquids Zheng, Qiuju; Mauro, John C.; Yue, Yuanzheng Journal of Non-Crystalline Solids, Vol. 456 https://doi.org/10.1016/j.jnoncrysol.2016.11.014	journal	January 2017

Similar Records

Comment on “A model for phosphate glass topology considering the modifying ion sub-network” [J. Chem. Phys. 140, 154501 (2014)]

Journal Article · Sat Mar 14 00:00:00 EDT 2015 · Journal of Chemical Physics · OSTI ID:1848225

Viscosities and working region predictions for bismuth aluminoborosilicate glasses

Journal Article · Tue Oct 09 00:00:00 EDT 2018 · International Journal of Applied Glass Science · OSTI ID:1848225

Gardner, Levi D.; Riley, Brian J.; Elliott, Casey; +2 more

Viscosities and working region predictions for bismuth aluminoborosilicate glasses

Journal Article · Mon Apr 01 00:00:00 EDT 2019 · International Journal of Applied Glass Science · OSTI ID:1848225

Gardner, Levi; Riley, Brian J.; Elliott, Casey; +2 more

Related Subjects

36 MATERIALS SCIENCE
Materials Science
Glass
Glass transition
Crystallization
Fragility
Oxy-sulfide
Mixed anion
Viscosity

Title: Anomalously strong viscosity behavior in mixed oxy-sulfide Na4P2S7-xOx invert glasses

Citation Formats

References (62)

Similar Records

Related Subjects

Title: Anomalously strong viscosity behavior in mixed oxy-sulfide Na₄P₂S_7-xO_x invert glasses