An extensive study of a-FexTM 1-xZr2 with TM = {V, Cr, Mn, Co, Ni, Cu} was undertaken in order to gain insight into the glassy structure, the metastable "big-cube" structure of the intermediate crystallisation product, and the evolution process involved therein. The stability of the glassy state was examined by differential scanning calorimetry (DSC). Generally higher temperatures and more negative enthalpies of crystallisation were observed for the glass system where Fe was substituted with {Co, Ni, Cu} than for the system where Fe was substituted with {V, Cr, Mn}. A proposed hypothetical crystallisation mechanism involved in the evolution of the metastable cF96 state (instead of the equilibrium tI12 state) was tested. Oxygen impurities present in the amorphous state were shown to be responsible for nucleating the cF96 big cube. Upon removal of the oxygen nucleation sites through hydrogenation of the glasses, the crystallisation proceeded directly to the equilibrium tetragonal structure bypassing the metastable phase. The validity of an assumed invariant structure in late transition-early transition metal (LT-ET) binary glasses was examined by means of Mossbauer spectroscopy. Variations in isomer shift (delta) and quadrupole splitting (Delta) upon TM substitution were consistent with variations in the density of states (DOS) at the Fermi level (EF). An assumed constant structure for (4d ET)-(3d LT) glasses is indeed justified. Variations in atomic packing were followed by measuring Delta. Delta increased as the atomic number of the TM increased. For the a-Fe xCu1-xZr 2 series, a break in the concentration dependence of Delta at x ≈ 0.3 is observed which mirrors the change in crystallisation from cF96 to tI6. Furthermore, comparisons of the glassy, metastable cubic and equilibrium tetragonal Mossbauer spectral data show obvious similarities between the glass and big cube which strongly suggest the existence of a common local (short-range) order between the two
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.38181 |
| Date | January 2001 |
| Creators | Dikeakos, Maria. |
| Contributors | Altounian, Zaven (advisor) |
| Publisher | McGill University |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Format | application/pdf |
| Coverage | Doctor of Philosophy (Department of Physics.) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 001875431, proquestno: NQ78678, Theses scanned by UMI/ProQuest. |
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