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Phase relations for the bulk compositions 3CaO·2FeOx·3SiO2+excessH2O and CaO·FeOx·2SiO2+excess H2O were determinedusing conventional hydrothermal techniques with solid phaseoxygen buffers to control fO2. Andradite, Ca3Fe3+2Si3O12, synthesized above 550 °C hasan average unit cell edge, ao, of 12.055±0.001 Å,and an index of refraction, n, of 1.887±0.003. Belowthis temperature, ao increases whereas n decreases, indicatingthe formation of a member of the andradite-hydroandradite solidsolution. At 2000 bars Pfluid andradite is stable above an fO2of 1015 bar at 800 °C and 10-32 bar at 400 °C. At lowerfO2 andradite+fluid gives way at successively lower temperaturesto the condensed assemblages magnetite+wollastonite, kirschsteinite(CaFe2+SiO4)+ wollastonite and kirschsteinite+xonotlite (Ca6Si6O17(OH)2). Synthetic hedenbergite, CaFe2+Si2O6, has average unit cell dimensionsof ao = 9.857± 0.004 Å, bo = 9.033±0.002Å, co = 5.254±0.002 Å and ß = 104.82°±0.03°,and refractive indices of n = 1.731±0.003 and n = 1.755±0.005.At 2000 bars Pfiuid, hedenbergite is stable below an fO2 of10-13 bar at 800 °C and 10-28 bar at 400 °C. Above thesefO2 values, hedenbergite+O2 breaks down to andradite+magnetite+quartz. The mineral pair andradite +hedenbergite thus limit the fO2range possible for their joint formation under equilibrium conditions. The hydration of wollastonite to xonotlite occurs at much lowertemperatures than previous experimental work indicated. A tentativehigh temperature limit for this reaction is set at 185°±15°C and 5000±25 bars and 210°±15 °Cand 2000±20 bars. Inasmuch as the growth of xonotlitefrom wollastonite + H2O was never accomplished, this high temperaturelimit does not represent an equilibrium univariant curve. Nine phases were encountered in the study of andradite and hedenbergite.They are andradite, hedenbergite, magnetite, wollastonite, kirschsteinite,xonotlite, quartz, ilvaite, and vapor (fluid). An invariantpoint analysis using the method of Schreinemakers shows thetopologic relations of the reactions involved. The resultinggrid can be used to interpret natural occurrences.  相似文献   
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