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Synthesis of α-cristobalite-type CO2-SiO2under extreme conditions
- Source :
- Acta Crystallographica Section A Foundations and Advances. 70:C753-C753
- Publication Year :
- 2014
- Publisher :
- International Union of Crystallography (IUCr), 2014.
-
Abstract
- Extreme conditions change the behavior and reactivity of elements and compounds and permit the synthesis of novel materials. In the case of group IV oxides, molecular CO2and a network solid silica, which were considered to be incompatible, are found to react under HP-HT conditions. A crystalline CO2-SiO2solid solution was synthesized from molecular CO2and microporous silicalite SiO2at 16-22 GPa and temperatures above 4000 K in a laser heated diamond anvil cell [1]. Synchrotron X-ray diffraction data show that the crystal adopts a densely packed α-cristobalite structure (space group P41212) with carbon and silicon in 4-fold coordination. This occurs at pressures at which SiO2normally adopts a 6-fold coordinated rutile-type stishovite structure. The P-T conditions used in this study represent a compromise between the respective stabilities of 3- and 4-fold coordination in CO2and 4- and 6-fold coordination in SiO2. This solid solution can be recovered at ambient pressure at which the unit cell volume is 26% lower than that of α-cristobalite SiO2. This is due to the incorporation of much smaller carbon atoms, resulting in the collapse of the oxygen sublattice. The unit cell volume and the different C and Si sites identified in Raman spectroscopy are consistent with a C:Si ratio of 6(1):4(1). The tetragonal c/a ratio increases from 1.283 at 16 GPa to 1.303 at ambient pressure and is lower than that of SiO2due to the more compact structure of the new material and essentially corresponds to that of the dense rutile-type oxygen sublattice. This can explain the small variation in volume observed for this phase corresponding to a bulk modulus of about 240 GPa. Due to the incorporation of silicon atoms, this hard solid based on CO4tetrahedra can be retained as a metastable phase. This strongly modifies standard oxide chemistry and shows that carbon can enter silica giving rise to a new class of hard, light, carbon-rich oxide materials with novel physical properties.
- Subjects :
- Materials science
Silicon
Oxide
chemistry.chemical_element
Condensed Matter Physics
Biochemistry
Cristobalite
Diamond anvil cell
Inorganic Chemistry
Crystal
Crystallography
chemistry.chemical_compound
chemistry
Structural Biology
Phase (matter)
General Materials Science
Physical and Theoretical Chemistry
Stishovite
Solid solution
Subjects
Details
- ISSN :
- 20532733
- Volume :
- 70
- Database :
- OpenAIRE
- Journal :
- Acta Crystallographica Section A Foundations and Advances
- Accession number :
- edsair.doi...........00170f2b8a632fa38c6daa0b30209c08