{"id":{"repo_id":"must-thes","oai_identifier":"oai:scholarsmine.mst.edu:doctoral_dissertations-1293"},"canonical_url":"https://search.dev.ndltd.org/etd/must-thes/oai:scholarsmine.mst.edu:doctoral_dissertations-1293","repository":{"repo_id":"must-thes","name":"Missouri University of Science and Technology","base_url":"https://scholarsmine.mst.edu/do/oai/"},"display":{"title":"Solid transformations and premelting phenomena in fluorite structures and the system SrCl₂BaCl₂","abstract":"<p>\"Thermal expansion and phase transformations in CaF<sub>2</sub>, BaF<sub>2</sub>, SrCl<sub>2</sub>, and BaCl<sub>2</sub> were studied by high temperature x-ray diffractometry, differential thermal analysis, and thermodilatometric analysis. Thermal expansion characteristics of CaF<sub>2</sub>, BaF<sub>2</sub> and SrCl<sub>2</sub> are very similar. The structures expand normally at lower temperatures and depart substantially from linearity at higher temperatures, because of formation of defects and disordering of anions. At high temperatures CaF<sub>2</sub> and BaF<sub>2</sub> react with water vapor, even at low humidities, forming oxides and emitting HF, leading to difficulty in observation of phase transformations. SrCl<sub>2</sub> undergoes the transformation from the cubic fluorite to a hexagonal structure in the temperature range 660°-750°C, with nucleation and grain growth. BaCl<sub>2</sub> occurs in three forms: cubic, orthorhombic, and hexagonal. The cubic form is stable below about 165°C and transforms irreversibly to the orthorhombic form; at 920°C the orthorhombic form is changed to a highly disordered hexagonal structure, similar to the hexagonal form of SrCl<sub>2</sub>.</p> <p>Cubic fluorite compounds can change to the orthorhombic PbCl<sub>2</sub> structure, to a hexagonal structure, or to a disordered structure, depending on pressure, temperature, and the chemistry of compound. The mechanism of the transformation is related to movement of anions in the open fluorite structure, followed by changes in first-coordination.</p> <p>The study of phase relationships of the system SrCl<sub>2</sub>-BaCl<sub>2</sub> shows that at high temperatures SrCl<sub>2</sub> forms a complete solid solution series with BaCl<sub>2</sub>, having hexagonal structure, with a freezing point minimum of 845°C at about 28 mole percent BaCl<sub>2</sub>. At lower temperatures the samples with more than 35 mole percent BaCl<sub>2</sub> form orthorhombic solid solutions and those with less than 25 mole percent BaCl<sub>2</sub> form cubic solid solutions. Orthorhombic solid solutions invariably persist at room temperature rather than inverting to the stable cubic structure\"--Abstract, pages ii-iii.</p>","abstract_html":"&lt;p&gt;&quot;Thermal expansion and phase transformations in CaF&lt;sub&gt;2&lt;/sub&gt;, BaF&lt;sub&gt;2&lt;/sub&gt;, SrCl&lt;sub&gt;2&lt;/sub&gt;, and BaCl&lt;sub&gt;2&lt;/sub&gt; were studied by high temperature x-ray diffractometry, differential thermal analysis, and thermodilatometric analysis. Thermal expansion characteristics of CaF&lt;sub&gt;2&lt;/sub&gt;, BaF&lt;sub&gt;2&lt;/sub&gt; and SrCl&lt;sub&gt;2&lt;/sub&gt; are very similar. The structures expand normally at lower temperatures and depart substantially from linearity at higher temperatures, because of formation of defects and disordering of anions. At high temperatures CaF&lt;sub&gt;2&lt;/sub&gt; and BaF&lt;sub&gt;2&lt;/sub&gt; react with water vapor, even at low humidities, forming oxides and emitting HF, leading to difficulty in observation of phase transformations. SrCl&lt;sub&gt;2&lt;/sub&gt; undergoes the transformation from the cubic fluorite to a hexagonal structure in the temperature range 660°-750°C, with nucleation and grain growth. BaCl&lt;sub&gt;2&lt;/sub&gt; occurs in three forms: cubic, orthorhombic, and hexagonal. The cubic form is stable below about 165°C and transforms irreversibly to the orthorhombic form; at 920°C the orthorhombic form is changed to a highly disordered hexagonal structure, similar to the hexagonal form of SrCl&lt;sub&gt;2&lt;/sub&gt;.&lt;/p&gt; &lt;p&gt;Cubic fluorite compounds can change to the orthorhombic PbCl&lt;sub&gt;2&lt;/sub&gt; structure, to a hexagonal structure, or to a disordered structure, depending on pressure, temperature, and the chemistry of compound. The mechanism of the transformation is related to movement of anions in the open fluorite structure, followed by changes in first-coordination.&lt;/p&gt; &lt;p&gt;The study of phase relationships of the system SrCl&lt;sub&gt;2&lt;/sub&gt;-BaCl&lt;sub&gt;2&lt;/sub&gt; shows that at high temperatures SrCl&lt;sub&gt;2&lt;/sub&gt; forms a complete solid solution series with BaCl&lt;sub&gt;2&lt;/sub&gt;, having hexagonal structure, with a freezing point minimum of 845°C at about 28 mole percent BaCl&lt;sub&gt;2&lt;/sub&gt;. At lower temperatures the samples with more than 35 mole percent BaCl&lt;sub&gt;2&lt;/sub&gt; form orthorhombic solid solutions and those with less than 25 mole percent BaCl&lt;sub&gt;2&lt;/sub&gt; form cubic solid solutions. Orthorhombic solid solutions invariably persist at room temperature rather than inverting to the stable cubic structure&quot;--Abstract, pages ii-iii.&lt;/p&gt;","abstract_has_math":false,"creators":["Sukhotanang, Damri"],"institution":"University of Missouri--Rolla","degree_name":"Ph. D. in Ceramic Engineering","degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2016,"date_issued":"2016-02-10T08:00:00Z","date_published":"2016-02-10T08:00:00Z","updated_at":"2026-07-24T03:20:12Z","subjects":["Ceramic Materials"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://scholarsmine.mst.edu/doctoral_dissertations/291","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Sukhotanang, Damri"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.available","label":"Dc Date Available","values":["2016-02-10T08:00:00Z"]},{"key":"dc:type","label":"Dc Type","values":["Dissertation - Open Access"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph. D. in Ceramic Engineering"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Missouri--Rolla"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Ceramic Materials"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://scholarsmine.mst.edu/doctoral_dissertations/291"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["<p>\"Thermal expansion and phase transformations in CaF<sub>2</sub>, BaF<sub>2</sub>, SrCl<sub>2</sub>, and BaCl<sub>2</sub> were studied by high temperature x-ray diffractometry, differential thermal analysis, and thermodilatometric analysis. Thermal expansion characteristics of CaF<sub>2</sub>, BaF<sub>2</sub> and SrCl<sub>2</sub> are very similar. The structures expand normally at lower temperatures and depart substantially from linearity at higher temperatures, because of formation of defects and disordering of anions. At high temperatures CaF<sub>2</sub> and BaF<sub>2</sub> react with water vapor, even at low humidities, forming oxides and emitting HF, leading to difficulty in observation of phase transformations. SrCl<sub>2</sub> undergoes the transformation from the cubic fluorite to a hexagonal structure in the temperature range 660°-750°C, with nucleation and grain growth. BaCl<sub>2</sub> occurs in three forms: cubic, orthorhombic, and hexagonal. The cubic form is stable below about 165°C and transforms irreversibly to the orthorhombic form; at 920°C the orthorhombic form is changed to a highly disordered hexagonal structure, similar to the hexagonal form of SrCl<sub>2</sub>.</p> <p>Cubic fluorite compounds can change to the orthorhombic PbCl<sub>2</sub> structure, to a hexagonal structure, or to a disordered structure, depending on pressure, temperature, and the chemistry of compound. The mechanism of the transformation is related to movement of anions in the open fluorite structure, followed by changes in first-coordination.</p> <p>The study of phase relationships of the system SrCl<sub>2</sub>-BaCl<sub>2</sub> shows that at high temperatures SrCl<sub>2</sub> forms a complete solid solution series with BaCl<sub>2</sub>, having hexagonal structure, with a freezing point minimum of 845°C at about 28 mole percent BaCl<sub>2</sub>. At lower temperatures the samples with more than 35 mole percent BaCl<sub>2</sub> form orthorhombic solid solutions and those with less than 25 mole percent BaCl<sub>2</sub> form cubic solid solutions. Orthorhombic solid solutions invariably persist at room temperature rather than inverting to the stable cubic structure\"--Abstract, pages ii-iii.</p>"]},{"key":"dc:title","label":"Title","values":["Solid transformations and premelting phenomena in fluorite structures and the system SrCl₂BaCl₂"]}]}],"canonical_facts":{"dc:creator":["Sukhotanang, Damri"],"dc:date.available":["2016-02-10T08:00:00Z"],"dc:description.abstract":["<p>\"Thermal expansion and phase transformations in CaF<sub>2</sub>, BaF<sub>2</sub>, SrCl<sub>2</sub>, and BaCl<sub>2</sub> were studied by high temperature x-ray diffractometry, differential thermal analysis, and thermodilatometric analysis. Thermal expansion characteristics of CaF<sub>2</sub>, BaF<sub>2</sub> and SrCl<sub>2</sub> are very similar. The structures expand normally at lower temperatures and depart substantially from linearity at higher temperatures, because of formation of defects and disordering of anions. At high temperatures CaF<sub>2</sub> and BaF<sub>2</sub> react with water vapor, even at low humidities, forming oxides and emitting HF, leading to difficulty in observation of phase transformations. SrCl<sub>2</sub> undergoes the transformation from the cubic fluorite to a hexagonal structure in the temperature range 660°-750°C, with nucleation and grain growth. BaCl<sub>2</sub> occurs in three forms: cubic, orthorhombic, and hexagonal. The cubic form is stable below about 165°C and transforms irreversibly to the orthorhombic form; at 920°C the orthorhombic form is changed to a highly disordered hexagonal structure, similar to the hexagonal form of SrCl<sub>2</sub>.</p> <p>Cubic fluorite compounds can change to the orthorhombic PbCl<sub>2</sub> structure, to a hexagonal structure, or to a disordered structure, depending on pressure, temperature, and the chemistry of compound. The mechanism of the transformation is related to movement of anions in the open fluorite structure, followed by changes in first-coordination.</p> <p>The study of phase relationships of the system SrCl<sub>2</sub>-BaCl<sub>2</sub> shows that at high temperatures SrCl<sub>2</sub> forms a complete solid solution series with BaCl<sub>2</sub>, having hexagonal structure, with a freezing point minimum of 845°C at about 28 mole percent BaCl<sub>2</sub>. At lower temperatures the samples with more than 35 mole percent BaCl<sub>2</sub> form orthorhombic solid solutions and those with less than 25 mole percent BaCl<sub>2</sub> form cubic solid solutions. Orthorhombic solid solutions invariably persist at room temperature rather than inverting to the stable cubic structure\"--Abstract, pages ii-iii.</p>"],"dc:identifier":["https://scholarsmine.mst.edu/doctoral_dissertations/291"],"dc:subject":["Ceramic Materials"],"dc:title":["Solid transformations and premelting phenomena in fluorite structures and the system SrCl₂BaCl₂"],"dc:type":["Dissertation - Open Access"],"thesis:degree_name":["Ph. D. in Ceramic Engineering"],"thesis:institution_name":["University of Missouri--Rolla"]},"updated_at":"2026-07-24T03:20:12Z"}