{"id":{"repo_id":"birmingham","oai_identifier":"oai:etheses.bham.ac.uk:1185"},"canonical_url":"https://search.dev.ndltd.org/etd/birmingham/oai:etheses.bham.ac.uk:1185","repository":{"repo_id":"birmingham","name":"University of Birmingham","base_url":"https://etheses.bham.ac.uk/cgi/oai2"},"display":{"title":"Synthesis and characterisation of d-Bi2O3 related materials stabilised by substitutions of Ca, Ga, Nb and Re.","abstract":"The work reported in this thesis is based around substitutions into bismuth oxide, which has proven to be highly adaptable chemically as it can accommodate a wide variety of substituents. The synthesis and characterisation of stabilised \\(\\delta\\)-Bi\\(_2\\)O\\(_3\\) related materials containing small amounts of Ca, Ga, Nb and Re are described. A body of work is presented exploring the structural and physical properties of such materials, characterised by neutron powder diffraction, X-ray powder diffraction, electron diffraction, extended X-ray absorption of fine structure measurements, differential thermal analysis and impedance spectroscopy. The structure of two new fluorite-related materials, Bi\\(_6\\)Ca\\(_3\\)ReO\\(_{15.5}\\) and Bi\\(_{10}\\)Ca\\(_5\\)ReO\\(_{23.5}\\), were studied. Bi\\(_6\\)Ca\\(_3\\)ReO\\(_{15.5}\\) formed a face-centred cubic fluorite-related structure and Bi\\(_{10}\\)Ca\\(_5\\)ReO\\(_{23.5}\\) a body-centred cubic material that is a 4 x 4 x 4 superstructure of the Bi\\(_6\\)Ca\\(_3\\)ReO\\(_{15.5}\\) phase. The structure of novel isostructural materials Bi\\(_{20}\\)Ca\\(_7\\)NbO\\(_{39.5}\\) and Bi\\(_{10.75}\\)Ca\\(_{4.375}\\)GaO\\(_{22}\\) were also investigated. Both materials formed distorted \\(\\delta\\)-Bi\\(_2\\)O\\(_3\\) related superstructures, derived as a monoclinic supercell based on a fluorite-related hexagonal subcell. Detailed structural analysis and local environments of cations in the ordered monoclinic fluorite-related superstructure of Bi\\(_9\\)ReO\\(_{17}\\) are also explored. All materials synthesised in this thesis have structures related to that of \\(\\delta\\)-Bi\\(_2\\)O\\(_3\\), which is known to have high oxide ion conducting properties at elevated temperatures. Oxide ion conducting properties are therefore also described.","abstract_html":"The work reported in this thesis is based around substitutions into bismuth oxide, which has proven to be highly adaptable chemically as it can accommodate a wide variety of substituents. The synthesis and characterisation of stabilised <span class=\"etd-inline-math\">&delta;</span>-Bi<span class=\"etd-inline-math\"><sub>2</sub></span>O<span class=\"etd-inline-math\"><sub>3</sub></span> related materials containing small amounts of Ca, Ga, Nb and Re are described. A body of work is presented exploring the structural and physical properties of such materials, characterised by neutron powder diffraction, X-ray powder diffraction, electron diffraction, extended X-ray absorption of fine structure measurements, differential thermal analysis and impedance spectroscopy. The structure of two new fluorite-related materials, Bi<span class=\"etd-inline-math\"><sub>6</sub></span>Ca<span class=\"etd-inline-math\"><sub>3</sub></span>ReO<span class=\"etd-inline-math\"><sub>15.5</sub></span> and Bi<span class=\"etd-inline-math\"><sub>10</sub></span>Ca<span class=\"etd-inline-math\"><sub>5</sub></span>ReO<span class=\"etd-inline-math\"><sub>23.5</sub></span>, were studied. Bi<span class=\"etd-inline-math\"><sub>6</sub></span>Ca<span class=\"etd-inline-math\"><sub>3</sub></span>ReO<span class=\"etd-inline-math\"><sub>15.5</sub></span> formed a face-centred cubic fluorite-related structure and Bi<span class=\"etd-inline-math\"><sub>10</sub></span>Ca<span class=\"etd-inline-math\"><sub>5</sub></span>ReO<span class=\"etd-inline-math\"><sub>23.5</sub></span> a body-centred cubic material that is a 4 x 4 x 4 superstructure of the Bi<span class=\"etd-inline-math\"><sub>6</sub></span>Ca<span class=\"etd-inline-math\"><sub>3</sub></span>ReO<span class=\"etd-inline-math\"><sub>15.5</sub></span> phase. The structure of novel isostructural materials Bi<span class=\"etd-inline-math\"><sub>20</sub></span>Ca<span class=\"etd-inline-math\"><sub>7</sub></span>NbO<span class=\"etd-inline-math\"><sub>39.5</sub></span> and Bi<span class=\"etd-inline-math\"><sub>10.75</sub></span>Ca<span class=\"etd-inline-math\"><sub>4.375</sub></span>GaO<span class=\"etd-inline-math\"><sub>22</sub></span> were also investigated. Both materials formed distorted <span class=\"etd-inline-math\">&delta;</span>-Bi<span class=\"etd-inline-math\"><sub>2</sub></span>O<span class=\"etd-inline-math\"><sub>3</sub></span> related superstructures, derived as a monoclinic supercell based on a fluorite-related hexagonal subcell. Detailed structural analysis and local environments of cations in the ordered monoclinic fluorite-related superstructure of Bi<span class=\"etd-inline-math\"><sub>9</sub></span>ReO<span class=\"etd-inline-math\"><sub>17</sub></span> are also explored. All materials synthesised in this thesis have structures related to that of <span class=\"etd-inline-math\">&delta;</span>-Bi<span class=\"etd-inline-math\"><sub>2</sub></span>O<span class=\"etd-inline-math\"><sub>3</sub></span>, which is known to have high oxide ion conducting properties at elevated temperatures. Oxide ion conducting properties are therefore also described.","abstract_has_math":true,"creators":["Thompson, Maria"],"institution":"University of Birmingham","degree_name":"d_ph","degree_level":"d_ph","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2010,"date_issued":"2010-12","date_published":"2010-12","updated_at":"2026-07-24T01:11:23Z","subjects":["QD Chemistry"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":null,"outbound_label":null,"outbound_source":null},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.sponsor","label":"Sponsor","values":["epsrc","other"]},{"key":"dc:creator","label":"Author","values":["Thompson, Maria"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2010-12"]},{"key":"dc:date.issued","label":"Date","values":["2010-12"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["College of Engineering & Physical Sciences","School of Chemistry"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["University of Birmingham"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["http://etheses.bham.ac.uk//id/eprint/1185/"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["d_ph"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["d_ph"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["QD Chemistry"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://etheses.bham.ac.uk//id/eprint/1185/1/Thompson10PhD.pdf","http://etheses.bham.ac.uk//id/eprint/1185/2/Decl_IS_Thompson10PhD.pdf"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The work reported in this thesis is based around substitutions into bismuth oxide, which has proven to be highly adaptable chemically as it can accommodate a wide variety of substituents. The synthesis and characterisation of stabilised \\(\\delta\\)-Bi\\(_2\\)O\\(_3\\) related materials containing small amounts of Ca, Ga, Nb and Re are described. A body of work is presented exploring the structural and physical properties of such materials, characterised by neutron powder diffraction, X-ray powder diffraction, electron diffraction, extended X-ray absorption of fine structure measurements, differential thermal analysis and impedance spectroscopy. The structure of two new fluorite-related materials, Bi\\(_6\\)Ca\\(_3\\)ReO\\(_{15.5}\\) and Bi\\(_{10}\\)Ca\\(_5\\)ReO\\(_{23.5}\\), were studied. Bi\\(_6\\)Ca\\(_3\\)ReO\\(_{15.5}\\) formed a face-centred cubic fluorite-related structure and Bi\\(_{10}\\)Ca\\(_5\\)ReO\\(_{23.5}\\) a body-centred cubic material that is a 4 x 4 x 4 superstructure of the Bi\\(_6\\)Ca\\(_3\\)ReO\\(_{15.5}\\) phase. The structure of novel isostructural materials Bi\\(_{20}\\)Ca\\(_7\\)NbO\\(_{39.5}\\) and Bi\\(_{10.75}\\)Ca\\(_{4.375}\\)GaO\\(_{22}\\) were also investigated. Both materials formed distorted \\(\\delta\\)-Bi\\(_2\\)O\\(_3\\) related superstructures, derived as a monoclinic supercell based on a fluorite-related hexagonal subcell. Detailed structural analysis and local environments of cations in the ordered monoclinic fluorite-related superstructure of Bi\\(_9\\)ReO\\(_{17}\\) are also explored. All materials synthesised in this thesis have structures related to that of \\(\\delta\\)-Bi\\(_2\\)O\\(_3\\), which is known to have high oxide ion conducting properties at elevated temperatures. Oxide ion conducting properties are therefore also described."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Synthesis and characterisation of d-Bi2O3 related materials stabilised by substitutions of Ca, Ga, Nb and Re."]}]}],"canonical_facts":{"dc:contributor.sponsor":["epsrc","other"],"dc:creator":["Thompson, Maria"],"dc:date":["2010-12"],"dc:date.issued":["2010-12"],"dc:description.abstract":["The work reported in this thesis is based around substitutions into bismuth oxide, which has proven to be highly adaptable chemically as it can accommodate a wide variety of substituents. The synthesis and characterisation of stabilised \\(\\delta\\)-Bi\\(_2\\)O\\(_3\\) related materials containing small amounts of Ca, Ga, Nb and Re are described. A body of work is presented exploring the structural and physical properties of such materials, characterised by neutron powder diffraction, X-ray powder diffraction, electron diffraction, extended X-ray absorption of fine structure measurements, differential thermal analysis and impedance spectroscopy. The structure of two new fluorite-related materials, Bi\\(_6\\)Ca\\(_3\\)ReO\\(_{15.5}\\) and Bi\\(_{10}\\)Ca\\(_5\\)ReO\\(_{23.5}\\), were studied. Bi\\(_6\\)Ca\\(_3\\)ReO\\(_{15.5}\\) formed a face-centred cubic fluorite-related structure and Bi\\(_{10}\\)Ca\\(_5\\)ReO\\(_{23.5}\\) a body-centred cubic material that is a 4 x 4 x 4 superstructure of the Bi\\(_6\\)Ca\\(_3\\)ReO\\(_{15.5}\\) phase. The structure of novel isostructural materials Bi\\(_{20}\\)Ca\\(_7\\)NbO\\(_{39.5}\\) and Bi\\(_{10.75}\\)Ca\\(_{4.375}\\)GaO\\(_{22}\\) were also investigated. Both materials formed distorted \\(\\delta\\)-Bi\\(_2\\)O\\(_3\\) related superstructures, derived as a monoclinic supercell based on a fluorite-related hexagonal subcell. Detailed structural analysis and local environments of cations in the ordered monoclinic fluorite-related superstructure of Bi\\(_9\\)ReO\\(_{17}\\) are also explored. All materials synthesised in this thesis have structures related to that of \\(\\delta\\)-Bi\\(_2\\)O\\(_3\\), which is known to have high oxide ion conducting properties at elevated temperatures. Oxide ion conducting properties are therefore also described."],"dc:format":["application/pdf"],"dc:identifier.uri":["http://etheses.bham.ac.uk//id/eprint/1185/1/Thompson10PhD.pdf","http://etheses.bham.ac.uk//id/eprint/1185/2/Decl_IS_Thompson10PhD.pdf"],"dc:publisher.department":["College of Engineering & Physical Sciences","School of Chemistry"],"dc:publisher.institution":["University of Birmingham"],"dc:relation.isreferencedby":["http://etheses.bham.ac.uk//id/eprint/1185/"],"dc:subject":["QD Chemistry"],"dc:title":["Synthesis and characterisation of d-Bi2O3 related materials stabilised by substitutions of Ca, Ga, Nb and Re."],"dc:type":["Thesis"],"dc:type.qualificationlevel":["d_ph"],"dc:type.qualificationname":["d_ph"]},"updated_at":"2026-07-24T01:11:23Z"}