Structural Basis for the Anomalously Low Spontaneous Polarisation Values of the Polar Phase of Sr1-xCaxTiO3 (x=0.02, 0.04): Evidence for a Ferrielectric Ordering

Full pattern Le-Bail refinement using x-ray powder diffraction profiles of Sr1-xCaxTiO3 for x=0.02, 0.04 in the temperature range 12 to 300 K reveals anomalies in the unit cell parameters at 170, 225 K due to an antiferrodistortive (cubic to tetragonal I4/mcm) phase transition and at ~32, ~34 K due to a transition to a polar phase (tetragonal I4/mcm to orthorhombic Ic2m), respectively. The lower transition temperatures obtained by us are in excellent agreement with those reported on the basis of the dielectric studies by Bednorz and Muller, [10] who attributed these to ferroelectric transition. Rietveld analysis of the diffraction profiles of the polar phase reveals off-centre displacements of both Sr2+/Ca2+ and Ti4+ ions in the X-Y plane along pseudocubic directions, in agreement with the experimentally reported direction of easy polarization by Bednorz and Muller, but the resulting dipole moments are shown to be ferrielectrically coupled in the neighbouring (001) planes along the [001] direction leading to anomalously low values of the spontaneous polarization at 12K.Comment: 5 pages, 4 figures and 1 tabl

Evidence for two spin-glass transitions with magnetoelastic and magnetoelectric couplings in the multiferroic (Bi1−x_{1-x}Bax_x)(Fe1−x_{1-x}Tix_x)O3_3 system

For disordered Heisenberg systems with small single ion anisotropy, two spin glass transitions below the long range ordered phase transition temperature has been predicted theoretically for compositions close to the percolation threshold. Experimental verification of these predictions is still controversial for conventional spin glasses. We show that multiferroic spin glass systems can provide a unique platform for verifying these theoretical predictions via a study of change in magnetoelastic and magnetoelectric couplings, obtained from an analysis of diffraction data, at the spin glass transition temperatures. Results of macroscopic and microscopic (x-ray and neutron scattering) measurements are presented on disordered BiFeO3, a canonical Heisenberg system with small single ion anisotropy, which reveal appearance of two spin glass phases SG1 and SG2 in coexistence with the LRO phase below the A-T and G-T lines. It is shown that the temperature dependence of the integrated intensity of the antiferromagnetic peak shows dips with respect to the Brillouin function behaviour around the SG1 and SG2 transition temperatures. The ferroelectric polarisation changes significantly at the two spin glass transition temperatures. These results, obtained using microscopic techniques, clearly demonstrate that the SG1 and SG2 transitions occur on the same magnetic sublattice and are intrinsic to the system. We also construct a phase diagram showing all the magnetic phases in BF-xBT system. While our results on the two spin glass transitions support the theoretical predictions, it also raises several open questions which need to be addressed by revisiting the existing theories of spin glass transitions by taking into account the effect of magnetoelastic and magnetoelectric couplings as well as electromagnons.Comment: 59 pages 21 figure

Doug Ruthven and Jorg Karger: Their Individual and Collective Contributions to the Field of Zeolite Science and Engineering

Prof. Doug Ruthven and Prof. Jörg Kärger are two giants in the field of zeolite science and engineering. Over their academic careers encompassing almost forty years each, they have contributed significantly to the advancement of fundamental understanding of adsorption and diffusion in zeolites as well as their industrial applications. The author, in the beginning of his academic career, had an opportunity to spend two years as a post-doctoral fellow in Prof. Ruthven’s laboratory at the University of New Brunswick (1975–1977). This experience actually motivated me to spend my academic career in working in the field of zeolite adsorption and diffusion. Nearly thirty years later, I spent a year as a Gast Mercator Professor at the University of Leipzig in the laboratory of Prof. Kärger (2005–2006). These two opportunities at two different ends of my academic career provided me with unique perspectives to reflect on the important contributions made by Professors Ruthven and Kärger to the field of zeolite science and technology. This article summarizes my personal perspectives on the breadth and depth of their contributions

Structural Changes and Ferroelectric Properties of BiFeO₃-PbTiO₃ Thin Films Grown via a Chemical Multilayer Deposition Method

Thin films of (1-x)BiFeO3-xPbTiO3 (BF-xPT) with x ~ 0.60 were fabricated on Pt/Si substrates by chemical solution deposition of precursor BF and PT layers alternately in three different multilayer configurations. These multilayer deposited precursor films upon annealing at 700{\deg}C in nitrogen show pure perovskite phase formation. In contrast to the equilibrium tetragonal structure for the overall molar composition of BF:PT::40:60, we find monoclinic structured BF-xPT phase of MA type. Piezo-force microscopy confirmed ferroelectric switching in the films and revealed different normal and lateral domain distributions in the samples. Room temperature electrical measurements show good quality ferroelectric hysteresis loops with remanent polarization, Pr, of up to 18 {\mu}C/cm2 and leakage currents as low as 10-7 A/cm2.Comment: 14 Pages and 6 figure

Premartensite to martensite transition and its implications on the origin of modulation in Ni2MnGa ferromagnetic shape memory alloy

We present here results of temperature dependent high resolution synchrotron x-ray powder diffraction study of sequence of phase transitions in Ni2MnGa. Our results show that the incommensurate martensite phase results from the incommensurate premartensite phase, and not from the austenite phase assumed in the adaptive phase model. The premartensite phase transforms to the martensite phase through a first order phase transition with coexistence of the two phases in a broad temperature interval (~40K), discontinuous change in the unit cell volume as also in the modulation wave vector across the transition temperature and considerable thermal hysteresis in the characteristic transition temperatures. The temperature variation of the modulation wave vector q shows smooth analytic behaviour with no evidence for any devilish plateau corresponding to an intermediate or ground state commensurate lock-in phases. The existence of the incommensurate 7M like modulated structure down to 5K suggests that the incommensurate 7M like modulation is the ground state of Ni2MnGa and not the Bain distorted tetragonal L10 phase or any other lock-in phase with a commensurate modulation. These findings can be explained within the framework of the soft phonon model

High-resolution synchrotron XRD study of Zr-rich compositions of Pb(Zr_xTi_1-x)O_3 (0.525\leq x \leq 0.60): evidence for the absence of the rhombohedral phase

Results of Rietveld analysis of the synchrotron XRD data on Pb(Zr_xTi_1-x)O_3 (PZT) for 0.525\leqx\leq0.60 are presented to show the absence of rhombohedral phase on the Zr-rich side of the morphotropic phase boundary (MPB). Our results reveal that the structure of PZT is monoclinic in the Cm space group for 0.525\leq x\leq 0.60. The nature of the monoclinic distortion changes from pseudo-tetragonal for 0.525\leqx\leq0.54 to pseudo-rhombohedral for x>0.54.Comment: 12 pages, 5 figur