Pressure driven polymorphic transitions in nanocrystalline Lu2O3, Tm2O3 and Eu2O3.

The crystallite size of the materials considerably influences the material properties, including their compressibility and resistance to external forces and the stability of the crystalline structure; a corresponding study for which, so far, has been limited for the important class of nanocrystalline Rare Earth Sesquioxides (REOs). In the present study, we report the crystallographic structural transitions in nanocrystalline Rare Earth Oxides (REOs) under the influence of pressure, investigated via high-energy X-Ray Diffraction (XRD) measurements. The study has been carried out on three of the REOs, namely Lutetium oxide (Lu2O3), Thulium oxide (Tm2O3) and Europium oxide (Eu2O3) up to the pressures of 33, 22 and 11 GPa, respectively. The diffraction data of Lu2O3 and Tm2O3 suggests the occurrence of irreversible structural transitions from cubic to monoclinic phase, while Eu2O3 showed a transition from the cubic to hexagonal phase. The transitions were found to be accompanied by a collapse in the volume and the resulting Pressure-Volume (P-V) graphs are fitted with the 3rd order Birch-Murnaghan (BM) equation of state (EOS) to estimate the bulk moduli and their pressure derivatives. Our study establishes a qualitative relationship between the crystallite size and various material properties such as the lattice parameters, transition pressure, bulk modulus etc., and strengthens the knowledge regarding the behaviour of this technologically important class of materials.

Influence of pressure on the transport, magnetic, and structural properties of superconducting Cr0.0009NbSe2 single crystal.

We investigate the superconducting critical current density (J c), transition temperature (T c), and flux pinning properties under hydrostatic pressure (P) for Cr0.0009NbSe2 single crystal. The application of P enhances T c in both electrical resistivity (∼0.38 K GPa-1: 0 ≤ P ≤ 2.5 GPa) and magnetization (∼0.98 K GPa-1: 0 ≤ P ≤ 1 GPa) measurements, which leads to a monotonic increase in J c and flux pinning properties. The field-dependent J c at various temperatures under P is analyzed within the collecting pinning theory and it shows that δT c pinning is the crossover to δl pinning above the critical pressure (P c ∼0.3 GPa). Our systematic analysis of the flux pinning mechanism indicates that both the density of pinning centers and pinning forces greatly increase with the application of P, which leads to an enhancement in the vortex state. Structural studies using synchrotron X-ray diffraction under pressure illustrate a stable hexagonal phase without any significant impurity phase and lattice parameter reduction with P shows highly anisotropic nature.

Competing Interactions: Evolution of Inter and Intramolecular Hydrogen Bonds in Salicylic Acid at High Pressures.

Benzoic acid derivatives are important molecular systems in the pharmaceutical industry. Salicylic acid is distinct among the derivatives of benzoic acid due to the presence of an intramolecular hydrogen bond. With a view to study the evolution of inter and intramolecular hydrogen bonding at shorter length scales, in situ high pressure Raman spectroscopic measurements, angle dispersive X-ray diffraction experiments, and density functional theory (DFT) based first principle calculations have been carried out on crystalline salicylic acid. Subtle structural modifications are noted across ∼1 GPa leading to structural phase transition to a new crystalline phase above 7 GPa which is reversible. Substantial softening of the OH stretching Raman mode associated with intramolecular hydrogen bond is observed prior to the transition pressure. Possible molecular configurations associated with tautomerization are discussed with the aid of DFT calculations.

Augmentation of the step-by-step Energy-Scanning EXAFS beamline BL-09 to continuous-scan EXAFS mode at INDUS-2 SRS.

An innovative scheme to carry out continuous-scan X-ray absorption spectroscopy (XAS) measurements similar to quick-EXAFS mode at the Energy-Scanning EXAFS beamline BL-09 at INDUS-2 synchrotron source (Indore, India), which is generally operated in step-by-step scanning mode, is presented. The continuous XAS mode has been implemented by adopting a continuous-scan scheme of the double-crystal monochromator and on-the-fly measurement of incident and transmitted intensities. This enabled a high signal-to-noise ratio to be maintained and the acquisition time was reduced to a few seconds from tens of minutes or hours. The quality of the spectra (signal-to-noise level, resolution and energy calibration) was checked by measuring and analysing XAS spectra of standard metal foils. To demonstrate the energy range covered in a single scan, a continuous-mode XAS spectrum of copper nickel alloy covering both Cu and Ni K-edges was recorded. The implementation of continuous-scan XAS mode at BL-09 would expand the use of this beamline in in situ time-resolved XAS studies of various important systems of current technological importance. The feasibility of employing this mode of measurement for time-resolved probing of reaction kinetics has been demonstrated by in situ XAS measurement on the growth of Ag nanoparticles from a solution phase.