The β-γ phase transition in titanite and the isosymmetric analogue in malayaite

X-ray diffraction technique and hard mode infrared spectroscopy were used to study the thermal behaviour of synthetic titanite, CaTiSiO₅, two natural titanite samples and iso-structural malayaite, CaSnSiO₅. Both pure minerals show a thermal anomaly near 500 K. Specific heat measurements show an intermediate phase in synthetic titanite. Impurities in titanite tend to suppress the discontinuity near 500 K. The β-γ transition near 820 K is not affected by Fe and Al defects in the natural material. Infrared studies in malayaite show a change of the temperature dependence of the phonon frequencies. X-ray experiments show weak structural rearrangements with heating but no evidence of a symmetry breaking phase transition near 500 K The character of the 500 K anomaly in malayaite is more similar to the β-γ transition (825 K) than the α-β Mtransition (496 K) in synthetic titanite.     

Pressure-induced phase transition(s) in KMnF3 and the importance of the excess volume for phase transitions in perovskite structures

We report a pressure-dependent investigation of KMnF(3) by x-ray diffraction up to 30 GPa. The results are discussed in the framework of Landau theory and in relation to the isostructural phase transition in SrTiO(3). The phase transition temperature near 186 K in KMnF(3) shifts to room temperature at a critical pressure of P(c) = 3.4 GPa; the pressure dependence of the transition point follows ΔP(c)/ΔT(c) = 0.0315 GPa K(-1). The transition becomes second order under high pressure, close to the tricritical point. The phase transition is determined by the rotation of MnF(6) octahedra with their simultaneous expansion along the rotation axis. The rotation angle was found to increase to 10.5° at 24 GPa. An additional anomaly was observed at higher pressure around 25 GPa, suggesting a further phase transition.     

Absorption spectra and optical gap energies of WxMo1−xO3

Optical absorption spectra of single crystals and powder specimens of W_xMo_1-xO₃ reveal fundamental absorption edges with gap energies of 2.77 eV (WO₃) and 3.05 eV (MoO₃). A continuous shift of the absorption edge and a simultanous appearance of absorption tails was found for ternary oxides. A theoretical model is proposed, based on the Anderson-localisation model with potential fluctuations due to tungsten-molybdenum disorder.     

Theory and computer simulation of tweed texture

Abstract

An analytical theory of the ordering interaction J(R _ij ) in structural phase transitions mediated by elastic relaxation in the material is outlined. The ordering process in cell i sets up a local stress field due to the sizes, shapes or displacements of atoms or atomic groups, which is propagated elastically to a distant cell j. The atomistic theory for ferro- and antiferro-elastic transitions takes into account two types of singularity, one due to elastic anisotropy and the other to the Zener interaction J _z of infinite range in ferroelastic transitions. The form of J _k in Fourier space is highly anisotropic with a few “soft” directions coinciding with the orientation of twin boundaries. The asymptoptic J(R) at large R is shown to be very anisotropic as well and decays as R ^?3 in ferroelastic and R ^?5 in antiferroelastic systems.

Computer simulations for a three-dimensional model of about 29,000 particles show a strong tendency to form tweed texture, as observed experimentally. Well above the structural phase transition temperature, the strain fluctuations show well-developed embryos of the tweed texture. On quenching to below the transition temperature, a pronounced micro-twinning appears which follows almost exactly the shape of the embryos and then develops towards a stripe texture. After a certain time needle-shaped domains are formed and a peculiar step-wise process of generating new stripes is observed.     

On the thickness of ferroelastic twin walls in lead phosphate Pb3(PO4)2 an X-ray diffraction study

The effective thickness of ferroelastic twin-walls (W-walls) in Pb₃(PO₄)₂ at room temperature (≈ 0.7 T _c ) was determined by X-ray diffraction. The diffraction profiles were analysed using a wall profile e=eotanh x/w where W is the effective wall thickness including the effects of wall bending and surface relaxations. The experimental value W is around 10 unit cells which is larger than expected from standard renormalization arguments. The limitations of such experimental studies are discussed.     

Renormalization phenomena in Ba-diluted ferroelastic lead phosphate, (Pb1-x Ba x )3(PO4)2

Abstract

In the improper ferroelastic palmierite-type lead phosphate order parameter coupling with a defect induced conjugate field leads to the renormalization of the two different critical temperatures of three order parameter components {Q ₃} and {Q ₁ Q ₂}. The influence of the lead dilution by barium on the ferroelastic domain pattern, the critical temperature of the ferroelastic transformation R m–C2/c and the development of the intermediate regime in (Pb_1–x Ba _x )₃(PO₄)₂ is studied using optical birefringence measurements, Raman and infrared spectroscopy. At the ferroelastic transition temperature T _c the orientational contribution of the three-states Potts model becomes critical. T _c is reduced from 453 K (x = 0) to zero K at x? 0.12. Modifications of the shape of zigzag needle domains as well as the angle between the monoclinic binary axis and the W walls along [031] with temperature and increasing Ba-content are reported. Above the ferroelastic transition point the component Q ₃, which corresponds to the displacive part in the Gibbs free energy, leads to dynamic short-range monoclinic deformation in the trigonal matrix. The temperature where Q ₃ shows critical behaviour is renormalized to 720 K (x = 0.12) as compared with 563 K in pure lead phosphate. For x>0.13 no monoclinic precursor clusters were found.     

A high temperature diffraction study of synthetic titanite catiosio4

The results of a high temperature single crystal X-ray diffraction study of synthetic titanite within the stability field of the A2/a (C2/c) paraphase (T > 500 K) are reported. The structure has been refined using a conventional model and one in which the Ca atom is disordered over two positions. A break in thermal expansion near T _c = 825 K correlates with an effective volume contraction of the Ti octahedron. When refined with split Ca position a reorientation of the Ca displacement vector at T _c is found, resulting in a more symmetrical structural arrangement of the disordered Ca cations with respect to the surrounding Ti cations. In the conventional model this reorientation is seen as a break in the thermal elongation of the shortest Ti-Ca distance. The observed temperature of the isosymmetrical structural instability is in agreement with previous observations based on Hard Mode IR and Raman spectroscopic measurements. A possible mechanism causing the observed structural changes and similarities to the thermal behaviour of the iso-structural malayaite, CaSnSiO₅, are discussed.     

Twin walls in anorthoclase are enriched in alkali and depleted in Ca and Al

Abstract

Composition profiles have been measured in transformation twin walls of the albite type in anorthoclase. Regions close to the walls between two twin domains are enriched in K and Na and depleted in Ca and Al. Microanalysis experiments show high mobility of alkali cations close to twin boundaries. Twin walls are generated via the displacive phase transition C2/m?C[lbar] in Al, Si disordered feldspar, and the chemical heterogeneity is a fingerprint for the subsequent diffusion of alkali and earth alkali ions during the cooling history of the sample.