Degree Type

Dissertation

Date of Award

2003

Degree Name

Doctor of Philosophy

Department

Materials Science and Engineering

First Advisor

Steve W. Martin

Abstract

Homogeneous xB2O3 + (1-x)B 2S3 glasses were prepared between 0 ≤ x ≤ 0.80. Raman, IR, and 11B NMR spectroscopies show that the boron oxide structures of B2O3, especially the six-membered rings, quickly diminish with increasing sulfide content, whereas the corresponding sulfide structures in B2S3 remain relatively intense as oxide content is increased. Differential scanning calorimetry (DSC) and density measurements show that physical properties of these boron oxysulfide glasses heavily favor the B2S3 properties regardless of the amount of B2O3 added to the system. It is hypothesized that the stability of the thioboroxol ring group relative to that of the BS 3/2 trigonal group is a possible source of this behavior. The formation of mixed boron oxysulfide structures of composition BSzO3-z where 0 < z < 3 is proposed.;Structural studies of the ternary xLi2S + (1-x)[0.5 B2S3 + 0.5 GeS2] glasses using IR, Raman, and 11B NMR show that these glasses do not have equal sharing of the lithium atoms between GeS2 and B2S3. The IR spectra indicates that the B2S3 glass network are under-doped in comparison to corresponding compositions in the xLi 2S + (1-x)B2S3 binary system. Additionally, the Raman spectra show that the GeS2 glass network is over-modified. 11Boron static NMR gives evidence that ~80% of the boron atoms are in tetrahedral coordinated. A super macro tetrahedron is proposed as one of the structures in these glasses in which some of them may contain boron sites substituted by germanium atoms at lower Li2S content.;Nuclear Spin Lattice Relaxation and ionic conductivity measurements of Li doped Li2S + GeS2 + B2S3 glasses were performed to investigate the ion hopping dynamics and the non-Arrhenius conductivity behavior that has been observed in some fast ion conducting glasses. A distribution of activation energies model was used to fit the NSLR results and conductivity results. Comparisons are made to previously studied binary lithium thio-germanate and binary lithium thio-borate glasses to help yield information about the conduction mechanisms in these new glasses. An ion trapping model is used in conjunction with the distribution of activation energies model to describe the non-Arrhenius behavior observed in the dc conductivity.

DOI

https://doi.org/10.31274/rtd-180813-11087

Publisher

Digital Repository @ Iowa State University, http://lib.dr.iastate.edu

Copyright Owner

Benjamin Michael Meyer

Language

en

Proquest ID

AAI3085932

File Format

application/pdf

File Size

194 pages

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