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Unexpected Magnetic Properties of Preovskite-Based Transition Metal Oxides

<p>Various transition metal oxides with interesting magnetic properties (often based on the perovskite structure) were prepared using conventional solid-state methodologies and fully characterized using a variety of techniques such as powder X-ray diffraction, variable temperature neutron diffraction, SEM-EDS, TEM-EDS, SQUID magnetometry
and heat capacity measurements.</p>
<p>One family of compounds that was investigated intensively were the 'pillared perovskites'. In this structure type, perovskite-like layers of comer shared octahedra are separated. by about 10 A by diamagnetic edge-shared octahedral dimer 'pillars'. Despite this long distance between layers, long-range order is present in both the La5Re3Co016
and La5Re3Ni016 members. In fact, a new magnetic structure was discovered for the Ni compound consisting of ferromagnetically ordered layers, coupled antiferromagnetically.</p>
<p>In addition, for the first time, substitution of the 5+ ion within the layer was successful, yielding compounds with general formula, La5Re3-xTaxB016 (B =Mn, Fe, Co, Ni; x ~ 0.5). Surprisingly, despite replacing about half of the magnetic ions within the perovskite layers with non-magnetic tantalum, the materials had the same ordering temperatures and magnetic structures as their unsubstituted analogues. This observation is evidence that the longer interlayer coupling pathway is the key to long-range ordering in this structure type.</p>
<p>The lanthanum rhenium oxide, La3Re20 10, involves the edge-shared octahedral dimer 'pillar' unit from the pillared perovskite structure, but with one unpaired electron per dimer unit. Prepared for the first time by solid-state synthesis, and studied magnetically in depth, long-range order was evident at 18 K. Theoretical investigations hinted that the magnetic structure consists of antiferromagnetically coupled chains of dimers, coupled antiferromagnetically.</p>
<p>The magnetic properties of the double perovskite, SrLaRuNi06, were also explored for the first time. This study demonstrates the power of neutron diffraction at elucidating magnetic information, such as the ordering temperature and magnetic structure, despite the presence of a ferromagnetic impurity that dominated much of the
measurements.</p>
<p>The candidate's examination of the magnetism of the rock-salt oxides, Na2Cu2Te06 and Na3Cu2Sb06 has raised some controversy in the literature, as the exact nature of the one-dimensional order (either antiferromagnetic-antiferromagnetic or
antiferromagnetic-ferromagnetic alternating linear chains) is uncertain. Again, theoretical calculations and comparison with other magnetic data can aide in the ultimate understanding of the overriding magnetism.</p>
<p>This thesis has focused on the synthesis and study of transition metal oxides with interesting or unusual magnetic properties. In many cases, the compounds exhibited long-range magnetic order despite convoluted or non-existent magnetic superexchange pathways.</p> / Thesis / Doctor of Philosophy (PhD)

Identiferoai:union.ndltd.org:mcmaster.ca/oai:macsphere.mcmaster.ca:11375/16867
Date11 1900
CreatorsCuthbert, Heather Lynn
ContributorsGreedan, John E., Chemistry
Source SetsMcMaster University
LanguageEnglish
Detected LanguageEnglish
TypeThesis

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