Investigations on sodium tin phosphate and tin pyrophosphate glasses

Glasses of the alkali tin phosphate system have been investigated. The infrared absorption and fluorescence spectra of the glasses have been examined. It is found that tin is present in both + 2 and + 4 oxidation states. Also tin ions occupy four- or six-coordinated sites in the glass.

New open-framework phosphate and phosphite compounds of gallium

Five new open-framework compounds of gallium have been synthesized by hydrothermal methods and their structures determined by single crystal X-ray diffraction studies. The compounds, C8N4H26]Ga6F4(PO4)(6)], I, C5N3H11]Ga3F2(PO4)(3)]center dot H2O, II, C6N3H19]Ga-4(C2O4)(PO4)(4)(H2PO4)]center dot 2H(2)O, III, Ga2F3(HPO4)(PO4)]center dot 2H(3)O, IV, and C3N2H5](2)Ga-4(H2O)(3)(HPO3)(7)], V, possess three-dimensional structures. All the compounds are formed by the connectivity between the Ga polyhedra and phosphite/phosphate units. The observation of SBU-6 (I and II) and spiro-5 (IV) secondary building units (SBUs) are noteworthy. The flexibility of the formation of gallium phosphate frameworks has been established by the isolation of two related structures (I and II) from the same SBU units but different organic amines. Some of the present structures have close resemblance to the gallium phosphate phases known earlier. The compounds have been characterized by CHN analysis, powder XRD, IR, and TGA. (C) 2011 Elsevier B. V. All rights reserved.

Laboratory studies on the volume change characteristics of kaolinite contaminated with sodium phosphate/sulfate

Reported distress to an industrial structure from phosphate/sulfate contamination of kaolinitic foundation soil at an industrial location in Southern India prompted this laboratory study. The study examines the short-term effect of sodium sulfate/phosphate contamination on the swell/compression characteristics of a commercial kaolinite. Experimental results showed that the unsaturated contaminated kaolinite specimens exhibited slightly higher swell potentials and lower compressions than the unsaturated uncontaminated kaolinite specimens. It is suggested that the larger double layer promoted by the increased exchangeable sodium ion concentration is responsible for the slightly higher swell potentials and lower compressions of the unsaturated contaminated kaolinite specimens.

Polyethylene stibinite phosphate esters: Novel flame-retardant plasticizers for PVC

A new series of multielement flame-retardant plasticizers containing polyethylene stibinite phosphate esters have been prepared by bulk polymerization from ethylene glycol with various antimony (III) aryloxydichlorides and arylphosphorodichloridates possessing various combinations of substituent [Cl,Br,NO2]. All the polymers are pink-coloured viscous fluids. They were characterized by inherent viscosity, density, IR, H-1, C-13 and P-31 NMR spectroscopy. The thermal behaviour of the polymers was compared by thermogravimetric analysis and correlated with their structures. The flammability studies were carried out by the limiting oxygen index test. The polymers containing P, Sb, N and Pr elements in their backbone show superior thermal-and flame-retardant characteristics than the other polymers. A comparative study was carried out with one of the synthesized polymers as a polymeric flame-retardant additive to plasticized PVC. The results showed improved LOI and mechanical properties to that of the conventional flame-retardant additive composition. (C) 1997 Elsevier Science Ltd.

Preliminary studies on the synthesis and characterisation of hydroxyapatites

Synthesis of calcium hydroxyapatite Ca-10(PO4)(6)(OH)(2) ceramic powders by a solid state reaction between commercially available tricalcium phosphate and calcium hydroxide powders has been attempted in the range 700-1000 degrees C. Reaction of tricalcium phosphate and calcium hydroxide in 3:2 molar ratio at 1000 degrees C leads to the formation of pure calcium hydroxyapatite phase. The sample has been characterised by XRD and IR spectral studies. The compacted powder is sintered to 93% of theoretical density when fired in air at 1300 degrees C for 2 hours.

Strontium and calcium zirconyl citrates as precursors for the low-temperature synthesis of SrZrO3 and CaZrO3 fine powders

Synthesis and the thermal decomposition behavior of new molecular precursors, strontium, and calcium zirconyl citrates are presented. The pathway to the metazirconate formation has been found to proceed through a multistep process. The precursors yield SrZrO3 and CaZrO3 fine powders at temperatures as low as 650 degrees C. Physico-chemical, spectroscopic, thermoanalytical, and microscopic techniques have enabled the identification of the sequence of events leading to the perovskite formation and proposition of a thermolysis scheme. Retention of the molecular level mixing of the metal ions during the course of the precursor decomposition is supported by these techniques. Prior to the formation of MZrO3 (M = Sr and Ca) an ionic oxycarbonate, M2Zr2O5CO3 (M = SI. and Ca), intermediate is produced by the thermal decomposition of the citrate precursors.

Mesoporous MnO2 synthesized by using a tri-block copolymer for electrochemical supercapacitor studies

Mesoporous MnO2 is prepared from KMnO4 by using a tri-block copolymer, namely, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEG-PPG-PEG) as a reducing as well as a structure-directing agent. The as synthesized MnO2 samples are poorly crystalline with mesoporosity having pore diameter between 8 and 40 nm. BET surface area as high as 273 m(2) g(-1) is obtained. By heating, the poorly crystalline MnO2 turns into a well crystalline form at 400 degrees C with nanorod morphology. However, the surface area decreases for the heated samples. Samples of MnO2 prepared by varying the ratio of KMnO4 and the copolymer, and also the heated samples are subjected to electrochemical characterization for supercapacitor studies. High specific capacitance values on mass basis are obtained for the as prepared mesoporous MnO2 samples. (C) 2011 Elsevier Inc. All rights reserved.

Micellar structures of dimeric surfactants with phosphate head groups and wettable spacers: A small-angle neutron scattering study

Dimeric or gemini surfactants consist of two hydrophobic chains and two hydrophilic head groups covalently connected by a hydrophobic or hydrophilic spacer. This paper reports the small-angle neutron scattering (SANS) measurements from aqueous micellar solutions of two different recently developed types of dimeric surfactants: (i) bis-anionic C16H33PO4--(CH2)(m)-PO4-C16H33,2Na(+) dimeric surfactants composed of phosphate head groups and a hydrophobic polymethylene spacer, referred to as 16-m-16,2Na(+), for spacer lengths m = 2, 4, 6, and 10, (ii) bis-cationic C16H33N+(CH3)(2)-CH2-(CH2-O-CH2)(p)-CH2-N+ (CH3)(2)C16H33,2Br(-) dimeric surfactants composed of dimethylammonium head groups and a wettable polyethylene oxide spacer, referred to as 16-CH2-p-CH2-16,2Br(-), for spacer lengths p = 1 - 3. The micellar structures of these surfactants are compared with the earlier studied bis-cationic C16H33N+ (CH3)(2)-(CH2)(m)-N+ (CH3)(2)C16H33,2Br(-) dimeric surfactants composed of dimethylammonium head groups and a hydrophobic polymethylene spacer, referred to as 16-m-16,2Br(-). It is found that 16-m-16,2Na(+), similar to 16-m-16,2Br(-), form various micellar structures depending on the spacer length. Micelles an disklike for rn = 2, rodlike for m = 4, and prolate ellipsoidal fur m = 6 and 10. The micelles of 16-CH2-p-CH2-16,2Br(-) are prolate ellipsoidal for all the values of p = 1 - 3. It is also found that micelles of 16-m-16,2Na(+) and 16-CH2-p-CH2-16,2Br(-) are large in comparison to those of 16-in-16,2Br(-) for similar spacer lengths. This is connected with the fact that both in 16-m-16,2Na(+) and 16-CH2-p-CH2-16,2Br(-), the head group or the spacer is more hydrated as compared to that in the 16-m-16,2Br(-). An increase in the hydration of the spacer or the head group increases the screening of the Coulomb repulsion between the charged head groups. This effect has been found to be more pronounced in the dimeric surfactants having wettable spacers. [S1063-651X(99)00303-7].

Potassium titanyl phosphate and its isomorphs: Growth, properties, and applications

Potassium titanyl phosphate (KTP) and its isomorphs have received enormous attention in the last 2 decades. In particular, KTP assumes importance due to its large nonlinear optic and electrooptic coefficients together with the broad thermal and angular acceptance for second harmonic generation. This article provides an overview of the material aspects, structural, physical, and chemical properties and device feasibility of the KTP family of crystals. Some of the current areas of research and development along with their significance in understanding the physical properties as well as device applications are addressed. Optical waveguide fabrication processes and characteristics with their relevance to the present-day technology are highlighted. Studies performed so far have enabled us to understand the fundamental aspects of these materials and what needs to be pursued vigorously is the exploitation of their device applications to the maximum extent.

Structures of the catalytic site mutants D99A and H48Q and the calcium-loop mutant D49E of phospholipase A(2)

Crystal structures of the active-site mutants D99A and H48Q and the calcium-loop mutant D49E of bovine phospholipase A(2) have been determined at around 1.9 Angstrom resolution. The D99A mutant is isomorphous to the orthorhombic recombinant enzyme, space group P2(1)2(1)2(1), The H48Q and the calcium-loop mutant D49E are isomorphous to the trigonal recombinant enzyme, space group P3(1)21, The two active-site mutants show no major structural perturbations. The structural water is absent in D99A and, therefore, the hydrogen-bonding scheme is changed. In H48Q, the catalytic water is present and hydrogen bonded to Gln48 N, but the second water found in native His48 is absent. In the calcium-loop mutant D49E, the two water molecules forming the pentagonal bipyramid around calcium are absent and only one O atom of the Glu49 carboxylate group is coordinated to calcium, resulting in only four ligands.

Studies on grinding media wear and its effect on flotation of ferrugenous phosphate ore

Marked ball grinding rests were carried out in the laboratory with a low grade phosphate ore under different experimental conditions. Two types of balls were used, namely high carbon low alloy (HCLA) cast steel and high chrome cast iron. Results of marked ball grinding tests indicated that ball wear increased with time and showed a sharp increase for wet grinding over dry grinding. Ball wear under wet grinding conditions was also influenced by the gaseous atmosphere in the mill. The grinding ball materials could be arranged in the following order with respect to their overall wear resistance: High chrome cast iron > HCLA cast steel balls Methods to minimize ball wear through control of mill atmosphere and addition of flotation reagents are discussed. Effect of grinding media and additions of flotation reagents during grinding on phosphate ore flotation are also discussed. (C) 1999 Elsevier Science Ltd. All rights reserved.

The molecular dynamics study of lithium ion conduction in phosphate glasses and the role of non-bridging oxygen

Molecular dynamics (MD) simulation of lithium phosphate (Li2O-P2O5) glasses with varying Li2O content has been carried out. Two different P-O distances corresponding to phosphorus coordination with bridging oxygen (BO) and non-bridging oxygen (NBO) were identified in the simulated glasses. NBO-BO interconversion or bond switching was noted, which results in a dynamic equilibration of the tetrahedral phosphate units (P-n, n = 1,3 indicates the number of bridging oxygen atoms in the coordination of phosphorus). The NBO-BO bond switching is mildly activated with an effective activation barrier of 0.03-0.05 eV. Lithium ion jumps do not appear to be strongly coupled to bond switching. But the number of Li+ ions coordinated to an optimum number of NBOs and the number of Li+ ions jumping out of their sites appear to be correlated. Detailed analysis was made of the dynamics of P-n species and new insights have been obtained regarding ion migration in network-modified phosphate glasses.

Thermodynamic properties of the calcium ferrites CaFe2O4 and Ca2Fe2O5

The chemical potentials of CaO in the two-phase fields Fe2O3 + CaFe2O4 and CaFe2O4 + Ca2Fe2O5 of the pseudobinary system CaO - Fe2O3 have been measured in the temperature range from 975 to 1275 K, relative to pure CaO as the reference state, using solid state galvanic cells incorporating single-crystal CaF2 as the solid electrolyte. The cell was operated under pure oxygen at ambient pressure. The standard Gibbs energies of formation of calcium ferrites, CaFe2O4 and Ca2Fe2O5, were derived from the reversible emfs. The results can be summarized by the following equations:CaO + Fe2O3 --> CaFe2O4;Delta G degrees = - 37,480 + 1.16 T (+/- 250) J/mol 2 CaO + Fe2O3 --> Ca2Fe2O5;Delta G degrees = - 45, 280 - 13.51 T (+/- 275) J/mol These values are compared with thermodynamic data reported in the literature. The results of this study are in excellent agreement with heat capacity data, and in reasonable agreement with earlier measurements of enthalpy and Gibbs energy of formation, but suggest significant revision of enthalpies of formation of calcium ferrites given in current thermodynamic compilations.

A Layered Zinc Phosphate, [C6N4H22][Zn6(PO4)4(HPO4)2], Formed by One-Dimensional Tubes

An open-framework zinc phosphate, [C6N4H22][Zn6(PO4)4(HPO4)2] (I), with alternating inorganic and organic layers has been synthesized hydrothermally from a starting mixture of ZnO, HCl, H3PO4, H2C2O4, and triethylenetetramine. Single-crystal data for I: monoclinic, space GROUP =P21/c (No. 14), a=9.881(1), b=16.857(1), c=8.286(1) Å, β=96.7(1)°, V=1370.8(1) Å3, Z=2, R1=0.06, and wR2=0.13 [1408 observed reflections with I>2σ(I)]. The structure of I comprises a network of ZnO4, PO4, and PO3(OH) tetrahedra forming one-dimensional tubes. The tubes, in turn, are linked via oxygen atoms forming macroanionic inorganic layers with eight-membered apertures. The one-dimensional tube-like architecture in I is a novel feature worthy of note.

Calcium-Decorated Carbyne Networks as Hydrogen Storage Media

Among the carbon allotropes, carbyne chains appear outstandingly accessible for sorption and very light. Hydrogen adsorption on calcium-decorated carbyne chain was studied using ab initio density functional calculations. The estimation of surface area of carbyne gives the value four times larger than that of graphene, which makes carbyne attractive as a storage scaffold medium. Furthermore, calculations show that a Ca-decorated carbyne can adsorb up to 6 H(2) molecules per Ca atom with a binding energy of similar to 0.2 eV, desirable for reversible storage, and the hydrogen storage capacity can exceed similar to 8 wt %. Unlike recently reported transition metal-decorated carbon nanostructures, which suffer from the metal clustering diminishing the storage capacity, the clustering of Ca atoms on carbyne is energetically unfavorable. Thermodynamics of adsorption of H(2) molecules on the Ca atom was also investigated using equilibrium grand partition function.