Thermodynamic activity of Na2O in Na beta-alumina

beta-alumina samples prepared by sintering Na2O-xAl(2)O(3) (5.5 < x < 19) a t T > 1900 K were subjected to XRD at room temperature. For all composition s from 5.5 < x < 19, both beta "-alumina and beta-alumina were observed and alpha-, beta "-, and beta-alumina could be found at x > 8.5. The proportio n of beta "-alumina is observed to reach a maximum value at x = 8.5, which is near the beta/alpha phase boundary and decreases to lower values for bot h x < 8.5 and x > 8.5. The c parameter for beta-alumina is observed to incr ease from 22.45 Angstrom at x = 5.5 to 22.75 Angstrom at x = 8.5 and then i s almost constant for x > 8.5. Emf measurements were made at higher tempera ture (973 K) using the following galvanic cell: (-) Na (reference) \ Pt \ N a beta-alumina \ Pt \ Na2O-xAl(2)O(3) (5.5 < x < 19) (+). Calculations from emf data show that the activity of Na2O in the Na2O-xAl(2)O(3) binary syst em, decreases with increasing value of x for 5.5 < x < 8.5 and is constant for 8.5 < x < 19. Both lattice parameter and emf data are in agreement with the phase diagram proposed by Y. Le Cars and coworkers, which shows only a single phase beta-alumina region within the composition range 5.5 < x < 8. 5 and a two-phase beta- and or-region from x > 8.5. These results suggest t hat beta "-alumina is not a. separate phase and provide new edvidence that beta "-alumina can be considered as a region of stacking disorder within th e beta-alumina phase, as reported by D. Gratias and coworkers. Although XRD can identify the presence of both structures, thermodynamic evidence is pr ovided to suggest that the microdomains of beta "-alumina and beta-alumina structures are part of one single beta-alumina phase, formed syntaxially as long-range stacking disorder. (C) 2000 Elsevier Science Ltd. All rights re served.