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Abstract Synthetic thorite and huttonite, two polymorphs of ThSiO4, were investigated by a combination of in situ high-pressure synchrotron X-ray powder diffraction and in situ high pressure Raman spectroscopy. The average onset pressure of the thorite-to-huttonite transition was determined to be 6.6 ± 0.2 GPa, using both techniques. The bulk moduli of thorite and huttonite were determined to be 139(9) and 246(11) GPa, respectively, by fitting their unit-cell volume data to a second order Birch-Murnaghan equation of state (EOS). Based on its bulk modulus, thorite is the most compressible zircon-structured orthosilicate, as it has the largest unit cell volume among tetravalent metal orthosilicates. The pressure derivatives of the vibrational modes of thorite were found to be consistent with those previously reported for other orthosilicates (e.g., zircon, hafnon, stetindite, and coffinite), while having the smallest Grüneisen parameter. A new P-T phase diagram for ThSiO4 is proposed, where the boundary of the thorite → huttonite transition is: P(T) = (7.8 ± 0.9 GPa) − (0.006 ± 0.002 GPa/K)T. Based on the new P-T phase diagram, we further estimated the enthalpy of formation of huttonite, ΔHf,ox, to be 0.6 ± 6.0 kJ/mol, suggesting its metastability and rare locality in nature. 

Abstract 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. 

The effects of dipole interactions on magnetic nanoparticle magnetization and relaxation dynamics were investigated using five nanoparticle (NP) systems with different surfactants, carrier liquids, size distributions, inter-particle spacing, and NP confinement. Dipole interactions were found to play a crucial role in modifying the blocking temperature behavior of the superparamagnetic nanoparticles, where stronger interactions were found to increase the blocking temperatures. Consequently, the blocking temperature of a densely packed nanoparticle system with stronger dipolar interactions was found to be substantially higher than those of the discrete nanoparticle systems. The frequencies of the dominant relaxation mechanisms were determined by magnetic susceptibility measurements in the frequency range of 100 Hz–7 GHz. The loss mechanisms were identified in terms of Brownian relaxation (1 kHz–10 kHz) and gyromagnetic resonance of Fe3O4 (~1.12 GHz). It was observed that the microwave absorption of the Fe3O4 nanoparticles depend on the local environment surrounding the NPs, as well as the long-range dipole–dipole interactions. These significant findings will be profoundly important in magnetic hyperthermia medical therapeutics and energy applications.