Structural and dielectric properties of Pb5(Ge,Si)O11

The ferroelectric lead germanate (Pb₅Ge₃O₁₁) and its isomorphous compounds are important because of their uses as pyroelectric and electro-optic devices. Comparison of inter-planar d-spacings of Pb₅Ge_3−x Si _x O₁₁ (x=0, 0.3, 0.7 and 1.00) suggests that there is no change in basic structure of Pb₅Ge_3−x Si _x O₁₁ when Si is substituted for Ge in small quantity (x<1). The dielectric properties of the Si-substituted compounds have been studied as a function of temperature (30 to 200°C). The ferroelectric-paraelectric phase transition has been observed at 185°C. The Si doping causes (a) Curie point to shift towards low temperature, (b) peak value of the dielectric constant to decrease and (c) phase transition diffuse. The fast increase in dielectric constant of pure Pb₅Ge₃O₁₁ with temperature (beyond transition temperature) may be attributed to the development of space charge polarization in the system.     

High pressure physics research at BARC

Abstract

High pressure physics research at BARC spans a period of more than two decades and covers the area of both static and dynamic pressures on the one hand and both theoretical and experimental aspects on the other. The experimental facilities available include Diamond Anvil Cells for X-ray diffraction and Raman spectroscopy and a light gas gun. Phase transformations investigated in metallic systems includethose in Cd-Hg, transition metals, rare earths and actinides and these investigations have been supported by detailed band structure calculations and studies of the mechanismof phase transformations. Extensive equation of state studies over a wide range of pressures include a new model for the intermediate pressure range between 0.5 and 10 TPa and interpretation of experimental shock Hugoniots.     

Phase transitions in LiKSO4: Low-temperature neutron diffraction results

Results of a detailed crystallographic study of the structural phase transitions in LiKSO₄, carried out using single crystal neutron diffraction at ambient and below-ambient temperatures (300–100 K), are presented. The study indicates two clear phase transitions at 205 K (from space group P6₃ to space group P31c), at 189 K (to space group Cc) and a third transition at about 130 K in the cooling cycle. The corresponding temperatures are 250 K, 200 K and 138 K in the heating cycle. The existence of twins, mixed phases, and extremely sluggish kinetics for the various phase transitions, as well as the structural details of the various phases in this mixed salt, can explain the apparent inconsistencies in the results of several experimental investigations reported in the literature.     

Radical copolymerization of chlorotrifluoroethylene with 4‐bromo‐3,3,4,4‐tetrafluorobut‐1‐ene

The radical copolymerization of chlorotrifluoroethylene (CTFE) with 3,3,4,4‐tetrafluoro‐4‐bromobut‐1‐ene (BTFB) initiated by tert‐butylperoxypivalate is presented. The microstructures of the obtained copolymers are determined by means of NMR spectroscopies and elemental analysis and show that random copolymers were obtained. A wide range of poly(CTFE‐co‐BTFB) copolymers is synthesized, containing from 17 to 89 mol % of CTFE. In all the cases, CTFE is the less reactive of both comonomers. T_d^10% values, ranging from 163 up to 359 °C, are dependent on the BTFB content. These variations of thermal property are attributed to the increase in the number of C‐H and C‐Br bonds breakdown when the BTFB molar percentage in the copolymer is higher. T_g values range from 19 to 39 °C and a decreasing trend is observed when increasing the amount of BTFB in the copolymer. This observation arises from the higher flexibility of the copolymer when increasing the number of fluorobrominated lateral chains. These original fluoropolymers bearing reactive pendant bromo groups are suitable candidates for various applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1714–1720     

Radon isotope assessment of submarine groundwater discharge (SGD) in Coleroon River Estuary,Tamil Nadu,India

Submarine groundwater discharge is the fresh groundwater discharge to sea that impacts the coastal regions. Radon (²²²Rn) isotope has been used to quantify SGD in coleroon river estuary, India. Continuous ²²²Rn analyses were attempted for 10 days in groundwater and pore water samples at three different locations. ²²²Rn in groundwater ranges between 35.0 and 222.0 Bq m^?3 and in pore water between 14.0 and 150.0 Bq m^?3 irrespective of locations. The radon mass balance estimated total SGD rate ranges between 2.37 and 7.47 m days^?1. The SGD increases with distance from coast, influenced by tides and hydrological features.     

Low-temperature phase transitions in LiKSO4: A neutron study

A single crystal neutron diffraction study of the low temperature structural phase transitions in LiKSO₄ has been carried out. Detailed temperature dependence of the Bragg peak profiles and integrated intensities for a group of about 20 reflections has been investigated upon cooling and heating in the temperature range 300 K to 96 K. The crystal undergoes three clear phase transitions at 205 K (from sp. gr. P6₃ to sp. gr. P31c), at 189 K and at about 135 K on cooling. The corresponding temperatures are 250 K, 190 K and 138 K on the heating cycle. These transitions are extremely sluggish, the kinetics depending on the thermal treatment of the crystal.     

Cobalt(II), nickel(II) and copper(II) complexes of 1-hydroxy-2-naphthyl(4-X-styryl)ketones

Summary Metal(II) bis-chelates of the type ML₂nB [M=Co^II, Ni^II, and Cu^II, L=1-hydroxy-2-naphthyl(4-X-styryl)ketone, (X=H, Me, Cl, MeO), B=H₂O, Py; n=0, 2] have been prepared and characterised by element analyses, i.r., ligand field spectra, magnetic moments and thermal studies. The copper(II) chelates are anhydrous monomers oftrans-square-planar configuration. The cobalt(II) and nickel(II) chelates, obtained as dihydrates, possess a high-spintrans-octahedral structure. Their anhydrides are polymeric. All the pyridine adducts have high-spintrans-octahedral geometry. The (M–O), order, namely Cu >Ni>Co, parallels the Irving-Williams order. The weak ligand field strength of 1-hydroxy-2-naphthyl(4-X-styryl)ketones is ascribed to inhibition of extensive conjugation arising from deviation of the naphthoyl group from planarity.     

Neutron elastic scattering studies of biological molecules and complexes

Neutron diffraction can provide very precise stereochemical information about hydrogen bonds and other features involving hydrogen atoms in crystals. This is because, unlike for x rays, the hydrogen atom has a significant scattering amplitude for neutrons relative to other atoms. High-precision studies of a class of molecules, like those on α-amino acids carried out at Brookhaven and Trombay, can provide important information on systematics of the structure, conformation, and hydrogen bonding parameters. Some attempts have also been made to extend these single-crystal studies to some proteins like myoglobin, lysozyme, and trypsin. The large anomalous scattering amplitudes for some stable isotopes like ¹¹³Cd and ¹⁴⁹Sm and the easy variability of neutron wavelength also provides, in principle, a method for solving the phase problem without crystallizing too many heavy atom derivatives. The combination of neutron and x-ray diffraction data, now being used to study charge density distributions in organic molecules and hydrogen bonds, may be extended in the future to larger molecules of biological importance. The small-angle scattering of neutrons is also a powerful technique for studying large biological particles in solution at low resolution to obtain information about sizes, shapes and distribution of constituents.     

Rare earth elements distribution in clay zones of sedimentary formation, Pondicherry, south India

Concentrations of five rare earth elements (REE) were measured in clay samples of a deep bore hole comprising major aquifers of Pondicherry region, south India in order to investigate the geochemical variations among various litho-units. Clay samples from Cretaceous formation show distinct gray to black color whereas Tertiary deposits have clays with color varying from pale yellow to brown to gray. All measured REEs exhibit lower concentrations than Upper Continental Crust (UCC) average values. Large variations in REEs contents were observed in different sedimentary formations (Tertiary and Cretaceous). Chondrite normalized ratio of La/Lu and Eu/Eu* indicate that the clays are derived from weathering of felsic rock and possibly under humid climate. All the samples showed positive Eu anomaly in North American Shale Composite (NASC) normalized plot which shows plagioclase feldspar as the major contributor to these clays. Positive Eu anomaly is also an indication of reduced condition of the formation.