The A2Mo3O12 family, where A3+ is a large trivalent cation, can show interesting thermal properties such as negative thermal expansion, also known as thermomiotic behavior, where the overall volume of the material contracts with increasing temperature. A selection of compounds in this family, namely HfMgMo3O12, In2Mo3O12, Y2Mo3O12, Al2Mo3O12, In(HfMg)0.5Mo3O12, and In1.5(HfMg)0.25Mo3O12, have been synthesized using solid-state and mechanical activation techniques as well as a simplified sol-gel approach (Al2Mo3O12). Coefficients of thermal expansion were found to range from large-negative to low-positive in the orthorhombic phase, including near-zero in In(HfMg)0.5Mo3O12 and In1.5(HfMg)0.25Mo3O12. This set of materials provided insight into the role of low-frequency phonon modes in open-framework materials. Low-temperature heat capacity and thermal conductivity measurements confirmed that low-frequency modes were active in thermomiotic materials, and also present to some extent in all members of the open-framework A2Mo3O12 family examined. A clear correlation exists between the magnitude and sign of the coefficient of thermal expansion in the orthorhombic phase and the contribution of low-energy modes to the low-temperature heat capacity, with negative thermal expansion materials having a larger contribution. The low-frequency phonon modes result in low thermal conductivity and reduced phonon mean free paths when compared to conventional ceramics and indicate that these low values are characteristic of open-framework materials in NTE families even if the materials in the families are not thermomiotic themselves.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:NSHD.ca#10222/15817 |
| Date | 06 December 2012 |
| Creators | Miller, Kimberly J |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
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