Gibbs energies of formation of UMoC1.7 and UMoC2

The chemical potentials oi carbon associated with two three-phase fields in the system U-Mo-C were measured by using the methane-hydrogen gas equilibration technique in the temperature range 973 to 1173K. The technique was validated by measuring the standard Gibbs energy of formation of Mo2C. From the experimentally measured values of the chemical potential of carbon in the ternary phase fields UC+Mo+UMoC1.7 and UC+UMoC1.7+UMoC2 and data for UC from the literature, the Gibbs energies of formation of the two ternary carbides were derived:

Phase equilibria in the system CaO-CoO-SiO2 and Gibbs energies of formation of the quaternary oxides CaCoSi2O6, Ca2CoSi2O7, and CaCoSiO4

Phase relations in the pseudoternary system CaO-CoO-SiO2 have been established at 1323 K. Three quaternary oxides were found to be stable: CaCoSi2O6 with clinopyroxene (Cpx), Ca2CoSi2O7 with melilite (Mel), and CaCoSiO4 with olivine (Ol) structures. The Gibbs energies of formation of the quaternary oxides from their component binary oxides were measured using solid-state galvanic cells incorporating yttria-stabilized zirconia as the solid electrolyte in the temperature range of 1000-1324 K. The results can be summarized as follows: CoO (rs) + CaO (rs) + 2SiO(2) (Qtz) --> CaCoSi2O6 (Cpx), Delta G(f)(0) = -117920 + 11.26T (+/-150) J/mol CoO (rs) + 2CaO (rs) + 2SiO(2) (Qtz) --> Ca2CoSi2O7 (Mel), Delta G(f)(0) = -192690 + 2.38T (+/-130) J/mol CoO (rs) + CaO (rs) + SiO2 (Qtz) --> CaCoSiO2 (Ol), Delta G(f)(0) = -100325 + 2.55T (+/-100) J/mol where rs = rock salt (NaCl) structure and Qtz = quartz. The uncertainty limits correspond to twice the standard error estimate. The experimentally observed miscibility gaps along the joins CaO-CoO and CaCoSiO4-Co2SiO4 were used to calculate the excess free energies of mixing for the solid solutions CaxCo1-xO and (CayCo1-y)CoSiO4:Delta G(E) = X(1 - X)[31975X + 26736 (1 - X)] J/mol and Delta G(E) = 23100 (+/-250) Y(1 - Y) J/mol. A T-X phase diagram for the binary CaO-CoO was computed from the thermodynamic information; the diagram agrees with information available in the literature. The computed miscibility gap along the CaCoSiO4-Co2SiO4 join is associated with a critical temperature of 1389 (+/-15) K. Stability fields for the various solid solutions and the quaternary compounds are depicted on chemical-potential diagrams for SiO2, CaO, and CoO at 1323 K.

Self-consistent microscopic treatment of the effects of self-motion of the probe on ionic and dipolar solvation dynamics

A simple but self-consistent microscopic theory for the time dependent solvation energy of both ions and dipoles is presented which includes, for the first time, the details of the self-motion of the probe on its own solvation dynamics. The theory leads to several interesting predictions. The most important of them is that, for dipolar solvation, both the rotational and the translational motions of the dipolar solute probe can significantly accelerate the rate of solvation. In addition, the rotational self-motion of the solute can also give rise to an additional mechanism of nonexponentiality in solvation time correlation functions in otherwise slow liquids. A comparison between the present theoretical predictions and the recent experimental studies of Maroncelli et al. on solvation dynamics of aniline in l-propanol seems to indicate that the said experiments have missed the initial solvent response up to about 45 ps. After mapping the experimental results on the redefined time scale, the theoretical results can explain the experimental results for solvation of aniline in 1-propanol very well. For ionic solvation, the translational motion is significant for light solutes only. For example, for Li+ in water, translational motion speeds up the solvation by about 20%. The present theory demonstrates that in dipolar solvation the partial quenching of the self-motion due to the presence of specific solute-solvent interactions (such as H-bonding) may lead to a much slower solvation than that when the self-motion is present. This point has been discussed. In addition, we present the theoretical results for solvation of aniline in propylene carbonate, Here, the solvation is predicted to be complete within 15-20 ps.

Self-similar solutions of laser produced blast waves

The aerodynamics of the blast wave produced by laser ablation is studied using the piston analogy. The unsteady one-dimensional gasdynamic equations governing the flow an solved under assumption of self-similarity. The solutions are utilized to obtain analytical expressions for the velocity, density, pressure and temperature distributions. The results predict. all the experimentally observed features of the laser produced blast waves.

Shear-induced enhancement of self-diffusion in interacting colloidal suspensions

We set up the generalized Langevin equations describing coupled single-particle and collective motion in a suspension of interacting colloidal particles in a shear how and use these to show that the measured self-diffusion coefficients in these systems should be strongly dependent on shear rate epsilon. Three regimes are found: (i) an initial const+epsilon(.2), followed by (ii) a large regime of epsilon(.1/2) behavior, crossing over to an asymptotic power-law approach (iii) D-o - const x epsilon(.-1/2) to the Stokes-Einstein value D-o. The shear dependence is isotropic up to very large shear rates and increases with the interparticle interaction strength. Our results provide a straightforward explanation of recent experiments and simulations on sheared colloids.

Variation of Cu-O charge-transfer energies in YBa2Cu3O7-x thin films studied by photoemission spectroscopy

It is pointed out that the change in the oxidation state of Cu in YBa2CU3O7-x with increasing x vitiates the trend in the Cu(2p) satellite intensity and hence the Cu-O charge-transfer energy. When Y is partly replaced by Ca, however, the satellite intensity and T(c) decrease with the increase in Ca content or hole concentration, just as in other cuprates.

Effect of substrate on particle arrangement in arrays formed by self-assembly of polymer grafted nanoparticles

We show that the substrate affects the interparticle spacing in monolayer arrays with hexagonal order formed by self-assembly of polymer grafted nanoparticles. Remarkably, arrays with square packing were formed due to convective shearing at a liquid surface induced by miscibility of colloidal solution with the substrate.

Potentiometric determination of the gibbs energies of formation of SrZrO3 and BaZrO3

The Gibbs free energies of formation of strontium and barium zirconates have been determined in the temperature range 960 to 1210 K using electrochemical cells incorporating the respective alkaline-earth fluoride single crystals as solid electrolytes. Pure strontium and barium monoxides were used in the reference electrodes. During measurements on barium zirconate, the oxygen partial pressure in the gas phase over the electrodes was maintained at a low value of 18.7 Pa to minimize the solubility of barium peroxide in the monoxide phase. Strontium zirconate was found to undergo a phase transition from orthorhombic perovskite to) with space group Cmcm; D-2h(17) to tetragonal perovskite (t) having the space group 14/mcm; D-4h(18) at 1123 (+/- 10) K. Barium zirconate does not appear to undergo a phase transition in the temperature range of measurement. It has the cubic perovskite (c) structure. The standard free energies of formation of the zirconates from their component binary oxides AO (A = Sr, Ba) with rock salt (rs) and ZrO2 with monoclinic (m) structures can be expressed by the following relations:SrO (rs) + ZrO2 (m) --> SrZrO3 (o) Delta G degrees = -74,880 - 14.2T (+/-200) J mol(-1) SrO (rs) + ZrO2 (m) --> SrZrO3 (t) Delta G degrees = -73,645 - 15.3T (+/-200) J mol(-1) BaO (rs) + ZrO2 (m) --> BaZrO4 (c) Delta G degrees = -127,760 - 1.79T (+/-250) J mol(-1) The results of this study are in reasonable agreement with calorimetric measurements reported in the literature. Systematic trends in the stability of alkaline-earth zirconates having the stoichiometry AZrO(3) are discussed.

Coordination driven self-assembly of metallamacrocycles using ambidentate linkers and self-selection of single linkage isomer

Nicotinate-N-oxide and isonicotinate-N-oxide have been employed to synthesize four heterometallic metallamacrocycles (dppf)(2)Pd-2(nicotinate-N-oxide)(2)](OTf)(2) (1), (dppf)(2)Pt-2(nicotinate-N-oxide)(2)](OTf)(2) (2), (dppf) 2Pd2(isonicotinate-N-oxide)(2)](OTf)(2) (3) and (dppf)(2)Pt-2(isonicotinate-N-oxide)(2)](OTf)(2) (4). The complexes represent the first examples of metallamacrocycles driven by solely Pd(II)/Pt(II)-O coordination using carboxylate-N-oxide donor. All the complexes 1-4 are characterized by IR, UV-Vis, multinuclear NMR spectroscopic and ESI-MS studies. The molecular structures of the complexes 1 and 3 are unambiguously determined by single crystal X-ray diffraction analysis. Despite the possibility of formation of several linkage isomers due to ambidentate nature of the donors, exclusive formation of 2 + 2] self-assembled single isomeric metallamacrocycle in each case is interesting observation. (C) 2011 Elsevier B.V. All rights reserved.

Amorphous, Monoclinic, and Tetragonal Porous Zirconia Through a Controlled Self-Sustained Combustion Route

Porous, large surface area, metastable zirconias, are of importance to catalytic, electrochemical, biological, and thermal insulation applications. Combustion synthesis is a very commonly used method for producing such zirconias. However, its rapid nature makes control difficult. A simple modification has been made to traditional solution combustion synthesis to address this problem. It involves the addition of starch to yield a starting mixture with a ``dough-like'' consistency. Just 5 wt% starch is seen to significantly alter the combustion characteristics of the ``dough.'' In particular, it helps to achieve better control over reaction zone temperature that is significantly lower than the one calculated by the adiabatic approximation typically used in self-propagating high-temperature synthesis. The effect of such control is demonstrated by the ability to tune dough composition to yield zirconias with different phase compositions from the relatively elusive ``amorphous'' to monoclinic (> 30 nm grain size) and tetragonal pure zirconia (< 30 nm grain size). The nature of this amorphous phase has been investigated using infrared spectroscopy. Starch content also helps tailor porosity in the final product. Zirconias with an average pore size of about 50 mu m and specific surface area as large as 110 m2/g have been obtained.

Guest-Assisted Self-assembly of Organostannoxane Nanotubules on a Mica Surface

The reaction of n-BuSn(O)OH](n), and 9-hydroxy-9-fluorenecarboxylic acid in the presence of p-X-C6H4-OH (X = F, Br) afforded hydroxyl-rich hexameric organostannoxane prismanes. The crystal structures of these prismanes reveal guest-assisted supramolecular structures. Self-assembly of these compounds on a mica surface affords organooxotin nanotubules.

Pronounced hydrogel formation by the self-assembled aggregates of N-alkyl disaccharide amphiphiles

Six disaccharide amphiphiles were synthesized and their hydrogel-forming behavior was extensively studied. These amphiphiles were based on maltose and lactose. Since the gels formed from some of these systems showed the ability to "trap" water molecules upon gelation, these gels were described as "hydrogels". When these gels were heated to similar to 70 degrees C, the samples turned into clear, isotropic fluids, and upon gradual cooling, the hydrogels could be reproduced. Thus these systems were also "thermoreversible". The low molecular mass (MW 565) of the gelators compared to that of a typical polymeric gelator forming substance implies pronounced aggregation of the disaccharide amphiphiles into larger microstructures during gelation. To discern the aggregate textures and morphologies, the specimen hydrogel samples were examined by high-resolution scanning electron microscopy (SEM). A possible reason for the exceptionally high water gelating capacities (>6000 molecules of water per gelator molecule) exhibited by these N-alkyl disaccharide amphiphiles is the presence of large interlamellar spaces into which the water molecules get entrapped due to surface tension. In contrast to their single-chain counterparts, the double-chain lactosyl and maltosylamine amphiphiles upon solubilization in EtOH-H2O afforded hydrogels with reduced mechanical strengths. Interestingly, the corresponding microstructures were found to be quite different from the corresponding hydrogels of their single-chain counterparts. Rheological studies provided further insights into the behavior of these hydrogels. Varying the chain length of the alcohol cosolvent could modulate the gelation capacities, melting temperatures, and the mechanical properties of these hydrogels. To explain the possible reasons of gelation, the results of molecular modeling and energy minimization studies were also included.

Molecular self-assembly of cadmium-triazolate complexes via hydrogen bonding: Synthesis, structures and photoluminescent properties

Two new cadmium coordination polymers namely Cd(HAmTrz-COO)(4)(NH4+)(2)] 1; and Cd(HAmTrz)(2)I-2](n) 2; (HAmTrz-COOH = 3-amino-1,2,4-triazole-5-carboxylic acid), have been prepared based on HAmTrz-COOH as ligand. The crystal structures of 1 and 2 have been determined by single-crystal X-ray diffraction technique. In coordination-complex 1 four triazole ligands coordinate via N1 nitrogen leading to a tetrahedral geometry around cadmium ion, while in 2 the ligand prefers to coordinate to the metal in a bidentate bridging mode. The structures of both the coordination polymers can be envisaged as 3D hydrogen bonded networks. Thermogravimetric analysis shows that 2 is more stable than 1 owing to different coordination numbers of cadmium atoms. Photoluminescence properties of both the compounds have been investigated in the solid state. (C) 2011 Elsevier B.V. All rights reserved.