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<jats:title>Abstract</jats:title> <jats:p>Zircon-class ternary oxide compounds have an ideal chemical formula of ATO4, where A is commonly a lanthanide and an actinide, with T = As, P, Si, or V. Their structure (I41/amd) accommodates a diverse chemistry on both A- and T-sites, giving rise to more than 17 mineral end-members of five different mineral groups, and in excess of 45 synthetic end-members. Because of their diverse chemical and physical properties, the zircon structure-type materials are of interest to a wide variety of fields and may be used as ceramic nuclear waste forms and as aeronautical environmental barrier coatings, to name a couple. To support advancement of their applications, many studies have been dedicated to the understanding of their structural and thermodynamic properties. The emphasis in this review will be on recent advances in the structural and thermodynamic studies of zircon structure-type ceramics, including pure end-members [e.g., zircon (ZrSiO4), xenotime (YPO4)] and solid solutions [e.g., ErxTh1–x(PO4)x(SiO4)1–x]. Specifically, we provide an overview on the crystal structure, its variations and transformations in response to non-ambient stimuli (temperature, pressure, and radiation), and its correlation to thermophysical and thermochemical properties.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>A natural intermediate member of the scapolite solid solution {Me47; chemical formula: (Na1.86Ca1.86K0.23Fe0.01)(Al4.36Si7.64)O24[Cl0.48(CO3)0.48(SO4)0.01]}, with the unusual I4/m space group, has been studied at various temperatures and combined high-T and high-P by means of in situ single-crystal and powder X-ray diffraction, using both conventional and synchrotron X-ray sources. In addition, single-crystal neutron diffraction data were collected at ambient-T and 685 °C. A fit of the experimental V-T data with a thermal equation of state yielded a thermal expansion coefficient at ambient conditions: αV25°C = 1/V0·(∂V/∂T)P,25°C = 1.74(3)·10–5 K–1. A comparative analysis of the elastic behavior of scapolite based on this study and previous high-T XRD data suggests that a thorough re-investigation of the different members of the marialite-meionite solid solution is needed to fully understand the role of crystal chemistry on the thermal behavior of these complex nonbinary solid solutions. The experimental data obtained within the full temperature range of analysis at ambient pressure confirm that the investigated sample always preserves the I4/m space group, and possible implications on the metastability of I4/m intermediate scapolite are discussed. Neutron diffraction data show that no significant Si and Al rearrangement among the T sites occurs between 25 and 685 °C. The combined high-T and high-P data show that at 650 °C and between 10.30(5) and 10.71(5) GPa a phase transition toward a triclinic polymorph occurs, with a positive Clapeyron slope (i.e., dP/dT &amp;gt; 0). A comprehensive description of the atomic-scale structure deformation mechanisms induced by temperature and/or pressure, including those leading to structural instability, is provided based on single-crystal structure refinements.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>The structural response to compression of the synthetic high-pressure hydroxide perovskite MgSi(OH)6, the so-called “3.65 Å phase,” has been determined to 8.4 GPa at room temperature using single-crystal XRD in the diamond-anvil cell. Two very similar structures have been determined in space groups P21 and P21/n, for which differences in oxygen donor-acceptor distances indicate that the non-centrosymmetric structure is likely the correct one. This structure has six nonequivalent H sites, of which two are fully occupied and four are half-occupied. Half-occupied sites are associated with a well-defined crankshaft of hydrogen-bonded donor-acceptor oxygens extending parallel to c. Half occupancy of these sites arises from the averaging of two orientations of the crankshaft H atoms (|| ±c) in equal proportions. The P21 and P21/n structures are compared. It is shown that the former is likely the correct space group, which is also consistent with recent spectroscopic studies that recognize six nonequivalent O-H. The structure of MgSi(OH)6 at pressures up to 8.4 GPa was refined in both space groups to see how divergent the two models are. There is a very close correspondence between the responses of the two structures implying that, at least to 8.4 GPa, non-centrosymmetry does not affect compressional behavior. The very different compressional behavior of MgO6 and SiO6 octahedra observed in this study suggests that structural phase transformations or discontinuities likely occur in MgSi(OH)6 above 9 GPa.</jats:p>