Short range order structrures of lithium oxy-thiosilicophosphate glasses
In this work, the compositional series of sulfide and mixed oxysulfide (MOS) glasses 0.56Li2S + 0.44[(0.33-x)PS5/2 + xPO5/2 + 0.67SiS2] was prepared, where 0 ≤ x ≤ 0.33, and their short range order (SRO) structures and their thermal properties have been investigated. Powder x-ray diffraction (XRD) c...
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| Format: | Article |
| Language: | English |
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Elsevier
2023-09-01
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| Series: | Journal of Non-Crystalline Solids: X |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S259015912300050X |
| _version_ | 1827820634855440384 |
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| author | Guantai Hu Victor M. Torres, III Steve W. Martin |
| author_facet | Guantai Hu Victor M. Torres, III Steve W. Martin |
| author_sort | Guantai Hu |
| collection | DOAJ |
| description | In this work, the compositional series of sulfide and mixed oxysulfide (MOS) glasses 0.56Li2S + 0.44[(0.33-x)PS5/2 + xPO5/2 + 0.67SiS2] was prepared, where 0 ≤ x ≤ 0.33, and their short range order (SRO) structures and their thermal properties have been investigated. Powder x-ray diffraction (XRD) confirmed that the MOS glasses were free from crystallization, with only very minor diffraction peaks in the x = 0 glass being observed. Fourier transform infrared (FT-IR), Raman, and 29Si and 31P magic angle spinning (MAS) NMR spectroscopies were used to identify the SRO structures present in these glasses. These spectra revealed oxygen migration from P to Si during synthesis. Although oxygen was introduced in the form of phosphorus oxide, the majority of the oxygen in these glasses ends up being bonded to silicon, thereby creating sulfur-rich SROs centered by phosphorus and MOS SROs centered by silicon. It was further found that the P-S SRO species were predominantly charged non-bridging sulfurs (NBS). The Si SRO species were comprised of neutral bridging oxygens (BOs) and charged non-bridging oxygens (NBOs) and neutral bridging sulfurs (BS) and charged non-bridging sulfurs with the neutral BO and BS species being larger in fraction than the NBO and NBS. These results suggest that the preponderance of the mobile Li+ cations in these glasses are located near the more negatively charged P centers and not near the more neutrally charged Si centers. The average negative charge of the P SRO structures was found to be ∼ − 3.0 with ∼97% of the phosphorous species in the P0 SRO while the average negative charge of the Si SRO structures was found to be −2.3. Consistent with the creation of the large numbers of NBS on the P and more BOs and BSs on the Si, these values are more negative and more positive, respectively, than the compositionally expected average value of −2.55. Differential scanning calorimetry (DSC) measurements of their glass transition (Tg) and crystallization (Tc) temperatures showed that the Tgs of these glasses are higher than 300 °C and their working ranges, ΔT ≡ Tc – Tg, are ∼100 °C. |
| first_indexed | 2024-03-12T01:30:08Z |
| format | Article |
| id | doaj.art-4bb6687fc75c4ee6bd87ea3dd5e74586 |
| institution | Directory Open Access Journal |
| issn | 2590-1591 |
| language | English |
| last_indexed | 2024-03-12T01:30:08Z |
| publishDate | 2023-09-01 |
| publisher | Elsevier |
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| series | Journal of Non-Crystalline Solids: X |
| spelling | doaj.art-4bb6687fc75c4ee6bd87ea3dd5e745862023-09-12T04:16:23ZengElsevierJournal of Non-Crystalline Solids: X2590-15912023-09-0119100198Short range order structrures of lithium oxy-thiosilicophosphate glassesGuantai Hu0Victor M. Torres, III1Steve W. Martin2Department of Materials Science and Engineering, Iowa State University of Science & Technology, Ames, IA 50011, United StatesDepartment of Materials Science and Engineering, Iowa State University of Science & Technology, Ames, IA 50011, United StatesCorresponding author.; Department of Materials Science and Engineering, Iowa State University of Science & Technology, Ames, IA 50011, United StatesIn this work, the compositional series of sulfide and mixed oxysulfide (MOS) glasses 0.56Li2S + 0.44[(0.33-x)PS5/2 + xPO5/2 + 0.67SiS2] was prepared, where 0 ≤ x ≤ 0.33, and their short range order (SRO) structures and their thermal properties have been investigated. Powder x-ray diffraction (XRD) confirmed that the MOS glasses were free from crystallization, with only very minor diffraction peaks in the x = 0 glass being observed. Fourier transform infrared (FT-IR), Raman, and 29Si and 31P magic angle spinning (MAS) NMR spectroscopies were used to identify the SRO structures present in these glasses. These spectra revealed oxygen migration from P to Si during synthesis. Although oxygen was introduced in the form of phosphorus oxide, the majority of the oxygen in these glasses ends up being bonded to silicon, thereby creating sulfur-rich SROs centered by phosphorus and MOS SROs centered by silicon. It was further found that the P-S SRO species were predominantly charged non-bridging sulfurs (NBS). The Si SRO species were comprised of neutral bridging oxygens (BOs) and charged non-bridging oxygens (NBOs) and neutral bridging sulfurs (BS) and charged non-bridging sulfurs with the neutral BO and BS species being larger in fraction than the NBO and NBS. These results suggest that the preponderance of the mobile Li+ cations in these glasses are located near the more negatively charged P centers and not near the more neutrally charged Si centers. The average negative charge of the P SRO structures was found to be ∼ − 3.0 with ∼97% of the phosphorous species in the P0 SRO while the average negative charge of the Si SRO structures was found to be −2.3. Consistent with the creation of the large numbers of NBS on the P and more BOs and BSs on the Si, these values are more negative and more positive, respectively, than the compositionally expected average value of −2.55. Differential scanning calorimetry (DSC) measurements of their glass transition (Tg) and crystallization (Tc) temperatures showed that the Tgs of these glasses are higher than 300 °C and their working ranges, ΔT ≡ Tc – Tg, are ∼100 °C.http://www.sciencedirect.com/science/article/pii/S259015912300050XMOS glassSulfide glassSRO structureRamanFT-IRMAS NMR |
| spellingShingle | Guantai Hu Victor M. Torres, III Steve W. Martin Short range order structrures of lithium oxy-thiosilicophosphate glasses Journal of Non-Crystalline Solids: X MOS glass Sulfide glass SRO structure Raman FT-IR MAS NMR |
| title | Short range order structrures of lithium oxy-thiosilicophosphate glasses |
| title_full | Short range order structrures of lithium oxy-thiosilicophosphate glasses |
| title_fullStr | Short range order structrures of lithium oxy-thiosilicophosphate glasses |
| title_full_unstemmed | Short range order structrures of lithium oxy-thiosilicophosphate glasses |
| title_short | Short range order structrures of lithium oxy-thiosilicophosphate glasses |
| title_sort | short range order structrures of lithium oxy thiosilicophosphate glasses |
| topic | MOS glass Sulfide glass SRO structure Raman FT-IR MAS NMR |
| url | http://www.sciencedirect.com/science/article/pii/S259015912300050X |
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