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Elastic behavior, phase transition, and pressure induced structural evolution of analcime

¹ Dipartimento di Scienze della Terra, Universita’ degli Studi di Milano, Via Botticelli 23, I-20133 Milano, Italy
² Bayerisches Geoinstitut, Universitaet Bayreuth, Universitaetsstrasse 30, D-95447 Bayreuth, Germany
³ Crystallography Laboratory, Department of Geosciences, Virginia Tech, Blacksburg, Virginia 24061, U.S.A.

Correspondence: ^* E-mail: diego.gatta{at}unimi.it

Elastic and structural behavior of a natural cubic analcime (space group: Iad) from Sardinia (Italy) was investigated at high pressure by in situ single-crystal X-ray diffraction. A first-order phase transition is observed in the pressure range between 0.91(5) and 1.08(5) GPa. Unit-cell constants and reflection conditions confirm that the space group of the HP-polymorph is P. No further phase-transition has been observed at least up to 7.14 GPa. Fitting the volume data of the cubic polymorph with a second-order BM-EoS we obtain: V₀ = 2571.2(4) ų, K_T0 = 56(3) GPa, and K' = 4 (fixed). For the triclinic polymorph, a third-order EoS gives: V₀ = 2607(9) ų, K_T0 = 19(2) GPa, and K' = 6.8(7). Axial bulk moduli of the triclinic polymorph, calculated with a linearized BM-EoS, are: K_T0(a) = 29(2) GPa, with K'(a) = 4.9(6) and a₀ = 13.727(10) Å; K_T0(b) = 20(1) GPa, with K'(b) = 5.2(5), and b₀ = 13.751(15) Å; K_T0(c) = 11(1) GPa, with K'(c) = 12.6(6) and c₀ = 13.822(31) Å. The elastic behavior of the HP-polymorph appears to be strongly anisotropic, being K_T0(a):K_T0(b):K_T0(c) = 2.64:1.82:1.00. The relevant structural variations in response to the cubic triclinic phase transition are due to tetrahedral tilting. The tetrahedral framework distortion gives rise to a change of the eight- and six-ring channels ellipticity and of the extra-framework topological configuration: it appears in fact that for the high-pressure triclinic polymorph the coordination number of some of the Na atoms is seven (2H₂O +five framework O atoms) instead of six (2H₂O + four framework O atoms).

Key Words: Analcime • zeolite • high-pressure • compressibility • phase transition

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