Pseudocubic Parameter Research Articles

Ionic network analysis of tectosilicates: the example of coesite at variable pressure.

The method of ionic network analysis [Thomas (2017). Acta Cryst. B73, 74-86] is extended to tectosilicates through the example of coesite, the high-pressure polymorph of SiO2. The structural refinements of Černok et al. [Z. Kristallogr. (2014), 229, 761-773] are taken as the starting point for applying the method. Its purpose is to predict the unit-cell parameters and atomic coordinates at (p-T-X) values in-between those of diffraction experiments. The essential development step for tectosilicates is to define a pseudocubic parameterization of the O4 cages of the SiO4 tetrahedra. The six parameters aPC, bPC, cPC, αPC, βPC and γPC allow a full quantification of the tetrahedral structure, i.e. distortion and enclosed volume. Structural predictions for coesite require that two separate quasi-planar networks are defined, one for the silicon ions and the other for the O4 cage midpoints. A set of parametric curves is used to describe the evolution with pressure of these networks and the pseudocubic parameters. These are derived by fitting to the crystallographic data. Application of the method to monoclinic feldspars and to quartz and cristobalite is discussed. Further, a novel two-parameter quantification of the degree of tetrahedral distortion is described. At pressures in excess of ca 20.45 GPa it is not possible to find a self-consistent solution to the parametric curves for coesite, pointing to the likelihood of a phase transition.

Anomalous optical variations in the grossular garnet from the Eden Mills, Belvidere Mountain (Vermont, USA)

The optical anomalies, and surface and lamellar textures of a birefringent grossular garnet crystal from the Eden Mills, Belvidere Mountain, Vermont, USA, have been investigated by optical polarizing microscope, electron-probe micro-analyzer, back-scattered electron imaging, infrared spectroscopy, and single-crystal X-ray diffractometer from the standpoint of crystal growth. This grossular shows one-to-one correlation between natural surface features and its internal textures under crossed polarizers. Electron-probe micro-analyzer (EPMA) gave average chemical composition in (110) thin section, of bright lamella {Ca2.97Mn0.06}∑3.03 [Al1.59Fe0.37Ti0.01]∑1.97(Si3.00)∑3.00 (Gros79.5And18.9Sps1.6) and of dark host {Ca2.99Mn 0.06}∑3.05 [Al1.73Fe0.26 Ti0.01]∑2.00(Si2.97OH0.03)∑3.00 (Gros85.4And13Sps1.6). The correspondence of surface features and the internal textures with spiral or pyramidal growth mechanism suggest that the internal textures of the Eden Mills grossular are formed during growth process. The optical vibrational orientations and the growth steps inclination along [001] and \( \left[\overset{-}{1}10\right] \) directions predict monoclinic symmetry. With X-ray diffractometer (XRD) method, pseudocubic parameters are a = 11.839(2) A, b = 11.855(1) A, and c = 11.868(2) A with interaxial angles α = 90.00(1)°, β = 89.99(1)°, and γ = 90.02(2)° that show orthorhombic symmetry of this crystal. Lamellar texture of Al3+-rich host with Fe3+-rich lamella infers cation ordering at octahedral site of the garnet structure. IR data favors the non-cubic orientation of [(OH) 4] at tetrahedral position in this grossular structure.

Structural and dielectric studies of the Na 0.5Bi 0.5TiO 3–BiFeO 3 system

Solid solutions (1 − x)NBT– xBF, between rhombohedral compounds Na 0.5Bi 0.5TiO 3 (NBT) and BiFeO 3 (BF) were studied and a continuous R3 c solid solution was evidenced. Lattice parameters and rhombohedral distortion evolution with BF content were studied. The “ a” pseudo-cubic parameter ( a p) increases linearly with BF rate, as the “ α” pseudo-cubic one ( α p) presents a more complex behaviour. The study of the dielectric properties evidenced two different ranges, with a limit composition around 50% of BF. TEM studies of the reciprocal space showed that the relaxor behaviour of NBT-rich samples is correlated both with superstructure spots and diffusion rows along some particular directions.

Strain relaxation in the epitaxy of La2/3Sr1/3MnO3 grown by pulsed-laser deposition on SrTiO3(001)

With a Curie point at 370 K, the half-metal (La0.7Sr0.3)MnO3 (LSMO) is one of the most interesting candidates for electronic devices based on tunnel magnetoresistance. SrTiO3 (STO) is up to now the best substrate for the epitaxy of suitable thin films of LSMO. The pseudocubic unit cell of rhombohedral LSMO has a parameter a LSMO such that (a STO − a LSMO)/a LSMO = + 0.83% (where a STO is the parameter of cubic STO) and an angle of 90.26°. As strained growth is tetragonal, relaxation implies recovery of both the pseudocubic parameter and of the original angle. In the LSMO layers that we prepare by pulsed-laser deposition, we show that these two processes are quite independent. The angular distortion is partially recovered by twinning in films 25 nm thick, while recovery of the parameter never occurs in the thickness range that we explored (up to 432 nm). A relaxation, however, takes place above a thickness of 100 nm, associated with a transition from two-dimensional to three-dimensional columnar growth. It is accompanied by chemical fluctuations. Our magnetic measurements exhibit Curie temperatures and magnetic moments very close to the bulk values in those layers where the crystal parameter is strained but the angle partially relaxed.