Hydrothermal phase equilibria studies in Ln2O3---H2O systems and synthesis of cubic lanthanide oxides

Phase diagrams for the systems Ln2O3---H2O (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu and Y) studied at 5000 to 10,000 psi and temperature range of 200–900°C, show that Ln(OH)3 hexagonal and LnOOH monoclinic are the only stable phases from Nd to Ho. The cubic oxide phase (C---Ln2O3) is stable for systems of Er, Tm, Yb and Lu, with no evidence of its equilibrium in the systems of lighter lanthanides. Using strong acids, HNO3 and HCOOH, as mineralisers the cubic oxides could be stabilised from Eu down to Lu. Solid solution phases of CeO2---Y2O3 and Eu2O3---Y2O3 have also been synthesised with HNO3 as mineraliser, since these compounds have promising use as solid electrolyte and phosphor materials respectively.

Preparation of CaTiO3 fine powders by the hydrothermal method

Fine powders consisting of 0.1–0.5 μm size crystallites of CaTiO3 are prepared at 150–200°C by the hydrothermal method starting from hydrated titania gel and reactive calcium oxide suspended as an aqueous slurry in an autoclave. The resulting high-purity CaTiO3 is characterised by TEM, X-ray powder diffraction, chemical analyses and sintering characteristics. The hydrothermally prepared CaTiO3 powders are sinterable to high-density ceramics below 1400°C. The dc conductivity behaviour of the chemically reduced ceramics is presented.

Cinnamate toxicity expression on phenylalanine ammonia-lyase activity, germination and growth of cucumber (Cucumis sativis) seedlings

Cinnamate is the product of phenylalanine ammonialyase (PAL). This compound, a precursor of phenolics in plants, has been shown to be phytotoxic. Cinnamate inhibits PAL activity in cucumber seedlings. DL-phenylalanine has the same effect on the enzyme but does not affect growth. Actinomycin D and cycloheximide are phytotoxic and inhibit PAL. Production of a double-peg has been noticed in the seedlings, grown in the presence of actinomycin D. Light stimulates PAL activity in the seedling.

Hydrothermal synthesis of Ba(Ti, Sn)O3 fine powders and dielectric properties of the corresponding ceramics

Fine powders of submicron-sized crystallites of BaTiO3 were prepared at 85–130°C by the hydrothermal method, starting from TiO2.ξH2O gel and Ba(OH)2 solution. The products obtained below 110°C incorporated considerable amounts of H2O and OH− in the lattice. As-prepared BaTiO3 is cubic and converts to the tetragonal phase after heat treatment at 1200°C, accompanied by the loss of residual OH− ions. Hydrothermal reaction of SnO2.ξH2O gel with Ba(OH)2 at 150–260°C gives rise to the hydrated phase, BaSn(OH)6.3H2O, due to the amphoteric nature of SnO2.ξH2O which stabilises Sn(OH)62− anions in basic media. On heating in air or releasing the pressure in situ at 260°C, BaSn(OH)6.3H2O converts to BaSnO3 through an intermediate, BaSnO(OH)4. Solid solutions of Ba(Ti,Sn)O3 are directly formed from (TiO2 + SnO2)..ξH2O gel up to 35 mol% SnO2. At higher Sn contents, the hydrothermal products are mixtures of BaSn(OH)6.3H2O and BaTiO3, which on annealing at 1000°C result in monophasic Ba(Ti,Sn)O3. The sintering characteristics and the dielectric properties of the ceramics prepared out of these fine powders are presented. The dielectric properties of fine-grained Ba(Ti,Sn)O3 ceramics are explained on the basis of the prevailing diffuse phase transition behaviour.

Correlation Between The Stability Of Carbonates In Ternary Ln2o3-H2o-Co2 Hydrothermal Systems And Lanthanide Systematics

Phase diagrams for ternary Ln2O3-H2O-CO2 systems for the entire lanthanide series (except promethium) were studied at temperatures in the range 100–950 °C and pressures up to 3000 bar. The phase diagrams obtained for the heavier lanthanides are far more complex, with the appearance of a number of stable carbonate phases. New carbonates isolated from lanthanide systems (Ln ≡ Tm, Yb, Lu) include Ln6(OH)4(CO3)7, Ln4(OH)6-(CO3)3, Ln2O(OH)2CO3, Ln6O2(OH)8(CO3)3 and Ln12O7(OH)10(CO3)6. Stable carbonate phases common to all the lighter lanthanides are hexagonal LnOHCO3 and hexagonal Ln2O2CO3. Ln2(CO3)3• 3H2O is stable from samarium onwards and orthorhombic LnOHCO3 is stable from gadolinium onwards. On the basis of the appearance of stable carbonates, four different groups of lanthanides were established: lanthanum to neodymium, promethium to europium, terbium to erbium and thulium to lutetium. Gadolinium is the connecting element between groups II and III. This is in accordance with the tetrad classification for f transition elements.

On the kinetics of crystal growth from a supercooled melt

We present a theoretical analysis of the dynamics of crystal growth from a supercooled melt. A molecular theory of crystal growth that pays proper attention to the structure at the liquid-solid interface is discussed.

Precipitation of rutile and anatase (Tio12) fine powders and their conversion to MTiO3 (M = Ba, Sr, Ca) by the hydrothermal method

Fine powders of TiO2 (rutile) with high degree of crystallinity are formed from aqueous titanium oxychloride solution under hydrothermal conditions at 160–230°C and 15–100 kg/cm2 for 1–2 hours. The anatase phase is produced from the same medium when sulfate ion impurity is present, with Image . Both these fine powders are converted to BaTiO3, SrTiO3 or CaTiO3 when suspended in Ba(OH)2 or Sr(OH)2 solution or in an aqueous slurry of carbonate-free CaO with Image , at 180–280°C and 12–65 kg/cm2 for 4–8 hours. The resulting fine powders contain monocrystallites of the perovskite phase with 0.1–1.5 μm particle size.

Sacrificial photolysis of water on TiO2 fine powders prepared by the hydrothermal method

The often discussed role of surface hydroxylation of TiO2 particles as an essential characterestics for their photocatalytic activity can be verified by preparing TiO2 powders by hydrothermal method since hydroxylated surface layers will be better retained on these particles formed in superheated water. Thus, fine powders of TiO2 (rutile) with high degree of crystallinity are formed from titanium oxychloride in the mixed solvent of water and 2-propanol at 160–230°C and 20–120 atm. The anatase phase is produced from the same medium when sulfate ion impurity is present, with Image . TiO2 powders are washed free of anions and 2-propanol by ultrafiltration and are Pt mounted by a photochemical method. Aqueous suspensions of both forms of TiO2 neither as such nor after Pt-loading, do not produce H2 on band gap illumination whereas, H2 is generated in presence of hole scavengers such as EDTA, TEOA, sulfite or hypophosphite. The effects of hole scavenger concentration, Pt : TiO2 ratio, particulate suspension density and the nature of hole scavengers on H2 production are presented. Platinised rutile powders are equally active as anatase in sacrificial systems.

Spore and crystal formation in Bacillus thuringiensis var thuringiensis during growth in cystine and cysteine.

The effect of the addition of different concentratons of cystine and cysteine on sporulation and parasporal crystal formation in Bacillus thuringiensis var. thuringiensis was studied. The effect was well pronounced when the systine/cysteine additions were made after the stationary phase. Heat stable spores and crystals were formed when the culture was provided with a low concentration of cystine/cysteine (0.05 per cent w/v). At a moderate concentration of cystine or cysteine (0.15%), only heat labile spores were formed without the production of the crystal. When the cystine/cysteine concentration was high (0.25%), spore and crystal formation were completely inhibited. Partial reversal of inhibition of sporulation was brought about by sodium sulphate or zinc sulphate and lead, copper, cadmium or cobalt acetate at 0.2 mM or at 0.2% of sodium or potassium pyruvate, citrate, isaconitate, oxalosuccinate, ∝ -keto-glutarate, succinate, fumarate, malate, or oxalacetate. Glutamate (0.2%) overcame the inhibitory effect of cystine/cysteine completely. The structural changes observed using phase contrast microscopy were dependent upon the concentration of cystine/cysteine.

Growth of Mycobacterium smegmatis in minimal and complete media

The growth patterns of Mycobacterium smegmatis SN2 in a minimal medium and in nutrient broth have been compared. The growth was monitored by absorbancy (Klett readings), colony forming units, wet weight and content of DNA, RNA and protein. During the early part of the growth cycle, the bacteria had higher wet weight and macromolecular content in nutrient broth than in minimal media. During the latter half of the growth cycle however, biosynthesis stopped much earlier in nutrient broth and the bacteria had a much lower content of macromolecules than in the minimal medium. In both the media, a general pattern of completing biosynthesis rapidly in the initial phase and a certain amount of cell division at a later time involving the distribution of preformed macromolecules was seen. The possible adaptive significance of this observation has been discussed.

Phase field study of precipitate growth: Effect of misfit strain and interface curvature

We have used phase field simulations to study the effect of misfit and interfacial curvature on diffusion-controlled growth of an isolated precipitate in a supersaturated matrix. Treating our simulations as computer experiments, we compare our simulation results with those based on the Zener–Frank and Laraia–Johnson–Voorhees theories for the growth of non-misfitting and misfitting precipitates, respectively. The agreement between simulations and the Zener–Frank theory is very good in one-dimensional systems. In two-dimensional systems with interfacial curvature (with and without misfit), we find good agreement between theory and simulations, but only at large supersaturations, where we find that the Gibbs–Thomson effect is less completely realized. At small supersaturations, the convergence of instantaneous growth coefficient in simulations towards its theoretical value could not be tracked to completion, because the diffusional field reached the system boundary. Also at small supersaturations, the elevation in precipitate composition matches well with the theoretically predicted Gibbs–Thomson effect in both misfitting and non-misfitting systems.

A Huge Effect of Weak dc Electrical Fields on Grain Growth in Zirconia

We show that the application of a modest dc electrical field, about 4 V/cm, can significantly reduce grain growth in yttria-stabilized polycrystalline zirconia. These measurements were made by annealing samples, for 10 h at 1300°C, with and without an electrical field. The finding adds a new dimension to the role of applied electrical fields in sintering and superplasticity, phenomena that are critical to the net-shape processing of ceramics. Grain-growth retardation will considerably enhance the rates of sintering and superplasticity, leading to significant energy efficiencies in the processing of ceramics.

Time- and Temperature-Dependent Study in the Three-Component Zinc-Triazolate-Oxybis(benzoate) System: Stabilization of New Topologies

Three new three-dimensional zinc-triazolate-oxybis(benzoate) compounds. [{Zn-3(H2O)(2)}{C12H8O(COO)(2)}(2)-{C2H2N3}(2)]center dot 2H(2)O(I), [Zn-7{C12H8O(COO)(2)}(4){C2H2N3}(6)]center dot H2O, (II), and[{Zn-5(OH)(2)}{C12H8O(COO)(2)}(3){C2H2N3}(2)] (III), synthesized by a hydrothermal reaction of a mixture of Zn(OAc)(2)center dot 2H(2)O, 4,4'-oxybis(benzoic acid), 1,2,4-triazole, NaOH, and water. Compound I has an interpenetrated diamond structure and II and III have pillared-layer related structures. The formation of a hydrated phase (I) at low temperature and a completely dehydrated phase (III) at high temperature suggests the importance of thermodynamic factors in the formation of three compounds. Transformation studies of I in the presence of water shows the formation of a simple Zn-OBA compound, [Zn(OBA)(H2O)] (IV), at 150 and 180 degrees C and compound III at 200 degrees C. The compounds have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction. thermogravimetric analysis, IR, and photoluminescence studies.

Prediction of bubble growth rates and departure volumes in nucleate boiling at isolated sites

A model has been developed to predict heat transfer rates and sizes of bubbles generated during nucleate pool boiling. This model assumes conduction and a natural convective heat transfer mechanism through the liquid layer under the bubble and transient conduction from the bulk liquid. The temperature of the bulk liquid in the vicinity of the bubble is obtained by assuming a turbulent natural convection process from the hot plate to the liquid bulk. The shape of the bubble is obtained by equilibrium analysis. The bubble departure condition is predicted by a force balance equation. Good agreement has been found between the bubble radii predicted by the present theory and the ones obtained experimentally.