Short Range Structural Models of the Glass Transition Temperatures and Densities of 0.5Na2S + 0.5[xGeS2 + (1 – x)PS5/2] Mixed Glass Former Glasses

dc.contributor.author Bischoff, Christian
dc.contributor.author Martin, Steve
dc.contributor.author Schuller, Katherine
dc.contributor.author Martin, Steve
dc.contributor.department Materials Science and Engineering
dc.date 2018-02-14T17:30:51.000
dc.date.accessioned 2020-06-30T06:06:59Z
dc.date.available 2020-06-30T06:06:59Z
dc.date.copyright Wed Jan 01 00:00:00 UTC 2014
dc.date.embargo 2013-11-05
dc.date.issued 2014-03-07
dc.description.abstract <p>The 0.5Na<sub>2</sub>S + 0.5[<em>x</em>GeS<sub>2</sub> + (1 – <em>x</em>)PS<sub>5/2</sub>] mixed glass former (MGF) glass system exhibits a nonlinear and nonadditive negative change in the Na<sup>+</sup> ion conductivity as one glass former, PS<sub>5/2</sub>, is exchanged for the other, GeS<sub>2</sub>. This behavior, known as the mixed glass former effect (MGFE), is also manifest in a negative deviation from the linear interpolation of the glass transition temperatures (<em>T</em><sub>g</sub>) of the binary end-member glasses, <em>x</em> = 0 and <em>x</em> = 1. Interestingly, the composition dependence of the densities of these ternary MGF glasses reveals a slightly positive MGFE deviation from a linear interpolation of the densities of the binary end-member glasses, <em>x</em> = 0 and <em>x</em> = 1. From our previous studies of the structures of these glasses using IR, Raman, and NMR spectroscopies, we find that a disproportionation reaction occurs between PS<sub>7/2</sub><sup>4-</sup> and GeS<sub>3</sub><sup>2-</sup> units into PS<sub>4</sub><sup>3-</sup> and GeS<sub>5/2</sub><sup>1-</sup> units. This disproportionation combined with the formation of Ge<sub>4</sub>S<sub>10</sub><sup>4-</sup> anions from GeS<sub>5/2</sub><sup>1-</sup> groups leads to the negative MGFE in <em>T</em><sub>g</sub>. A best-fit model of the <em>T</em><sub>g</sub>s of these glasses was developed to quantify the amount of GeS<sub>5/2</sub><sup>1-</sup> units that form Ge<sub>4</sub>S<sub>10</sub><sup>4-</sup> molecular anions in the ternary glasses (∼5–10%). This refined structural model was used to develop a short-range structural model of the molar volumes, which shows that the slight densification of the ternary glasses is due to the improved packing efficiency of the germanium sulfide species.</p>
dc.description.comments <p>Reprinted with permission from <em>Journal of Physical Chemistry B</em> 118 (2014): 3710, <a href="http://dx.doi.org/10.1021/jp411942t" target="_blank">doi: 10.1021/jp411942t</a>. Copyright 2014 American Chemical Society.<strong></strong></p>
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dc.identifier archive/lib.dr.iastate.edu/mse_pubs/160/
dc.identifier.articleid 1155
dc.identifier.contextkey 6155145
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath mse_pubs/160
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/55489
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/mse_pubs/160/0-2014_Martin_Short_Range_License.pdf|||Fri Jan 14 20:53:30 UTC 2022
dc.source.bitstream archive/lib.dr.iastate.edu/mse_pubs/160/2014_Martin_ShortRange.pdf|||Fri Jan 14 20:53:32 UTC 2022
dc.source.uri 10.1021/jp411942t
dc.subject.disciplines Materials Science and Engineering
dc.title Short Range Structural Models of the Glass Transition Temperatures and Densities of 0.5Na2S + 0.5[xGeS2 + (1 – x)PS5/2] Mixed Glass Former Glasses
dc.type article
dc.type.genre article
dspace.entity.type Publication
relation.isAuthorOfPublication e0385671-f8e7-4ceb-ba14-162c8acd29dd
relation.isOrgUnitOfPublication bf9f7e3e-25bd-44d3-b49c-ed98372dee5e
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