Solubilities of Pb+2, Bi+3, Sb+3 and Cu+1 sulphides in (NaCl KCl Na2S) melts

Solubilities of common metal sulfides have been determined in the (NaCl+KCl) eutectic melt with and without Na2S. A novel gas-phase equilibrium technique has been used for PbS, Bi2S3, and So2S3, and an improved liquid phase equilibrium technique for Cu2S, which eliminates the errors due to physical entrapment of the sulfide phase and segregation on quenching, enabling precise measurements to be made. Solubilities in the (NaCl+KCl) eutectic melt were determined as a function of temperature in the rante 700° to 950°C, and were found to be small. The partial molar heats of mixing of the sulfides in the eutectic melt have been calculated from the solubility measurements, to be 13.3, 31.4, 37.1, and 49.0 kcal for PbSs), Sb2S2(l), and Cu2S(s), respectively. Sodium sulfide addition was observed to enhance these solubilities, the effect being largest for Cu2S followed by Sb2S3, Bi2S3, and PbS. This effect is explained qualitatively. It was observed that PbS and Sb2S3 obey Henry's law up to saturation in (NaCl+KCl+Na2S) melts.

Gibbs energy of formation of lead zirconate

The Gibbs energy of formation of zirconia-saturated lead zirconate was determined by emf measurements on the solid state cells and at 800 to 1400 K. The results obtained differ significantly from those reported in the literature based on vapor-pressure measurements, using Knudsen effusion and transportation techniques and assuming that the vapor phase consisted entirely of monomeric PbO molecules. A reanalysis of the data obtained in the earlier vapor-pressure studies, using mass-spectrometric measurements on polymeric PbO species in the gas phase, gives Gibbs energies of formation of lead zirconate which are in better agreement with those obtained in this study. Recent electrochemical measurements using CaO-ZrO2 and PbF2 solid electrolytes are in good agreement with the present study. The results obtained in this study are also consistent with the phase diagram which shows decomposition of the zirconate to tetragonal zirconia and a liquid phase rich in PbO at 1843 K.

Spark plasma sintering of novel ZrB2-SiC-TiSi2 composites with better mechanical properties

We report here the development of ultrafine grained ZrB2-SiC composites using TiSi2 as the sintering aid and spark plasma sintering (SPS) as the processing technique. It was observed that the presence of TiSi2 improved the sinterability of the composites, such that near theoretical densification (99.9%) could be achieved for ZrB2-18 wt.% SiC-5 wt.% TiSi2 composites after SPS at 1600 degrees C for 10 min at 50 MPa. Use of innovative multi stage sintering (MSS) route, which involved holding the samples at lower (intermediate) temperatures for some time before holding at the final temperature, while keeping the net holding time to 10 min, allowed attainment of full densification of ZrB2-18 wt.% SiC-2.5 wt.% TiSi2 at a still lower final temperature of 1500 degrees C at 30 MPa. TEM observations, which revealed the presence of anisotropic ZrB2 grains with faceted grain boundaries and TiSi2 at the intergranular regions, suggested the occurrence of liquid phase sintering in the presence of TiSi2. No additional phase was detected in XRD as well as TEM, which confirmed the absence of any sintering reaction. The as developed composites possessed an excellent combination of Vickers hardness and indentation toughness, both of which increased with increase in TiSi2 content, such that the ZrBi2-18 wt.% SiC-5 wt.% TiSi2 (SPS processed at 1600 degrees C) possessed hardness of similar to 20 GPa and indentation toughness of similar to 5 MPa m(1/2). The use of MSS SPS at 1500 degrees C for ZrBi2-18 wt.% SiC-2.5 wt.% TiSi2 composite resulted in improvement in hardness of up to similar to 27 GPa and attainment of high flexural strength of similar to 455 MPa. (C) 2011 Elsevier B.V. All rights reserved.

Influence of nature of support on the catalytic activity of supported molybdenum-oxo species in benzyl alcohol conversion

Supported catalysts containing 15 wt.% of molybdenum have been prepared by the incipient wetness impregnation method. CaO, MgO, Al2O3, Zr(OH)4 and Al(OH)3 have been used as supports for the preparation of supported Mo catalysts. Characterisation of all the materials prepared has been carried out through BET surface area measurement, X-ray diffractometry and FT-IR spectroscopy. Catalytic activity measurements have been carried out with reference to structure-sensitive benzyl alcohol conversion in the liquid phase. The percentage conversion of benzyl alcohol to benzaldehyde and toluene varied over a large range depending on the support used for the preparation of catalysts, indicating the importance of the support on catalytic activity of Mo catalysts. Al(OH)3 has been found to be the best support for molybdenum among all the supports used. Support–metal interaction (SMI) has been found to play an important role in determining the catalytic activity of supported catalysts.

Modeling of agglomeration inside a droplet with nanosuspensions in an acoustic field

This short communication reports results of particle agglomeration details of an acoustically levitated nanosilica droplet. The droplet undergoes thermo-physical and morphological changes under external heating load (convective or radiative) forming different solid structures due to particle agglomeration. We report an agglomeration model based on population balance approach coupled with species and energy conservation equations in the liquid phase and compare it with the experimentally observed structure formations using high speed photography. The analysis is able to predict similar spherical bowl shaped morphologies as observed experimentally using scanning electron microscopy and laser induced fluorescence. (C) 2012 Elsevier Ltd. All rights reserved.

Charge transport and magnetic properties of coaxial composite fibrils of polypyrrole/multiwall carbon nanotubes at low temperature

We report the low temperature electrical and magnetic properties of polypyrrole (PPy)/multiwall carbon nanotube (MWNT) coaxial composite fibrils synthesized by the electro-polymerization method. The iron-filled MWNTs were first grown by chemical vapor deposition of a mixture of liquid phase organic compound and ferrocene by the one step method. Then the PPy/MWNT fibrils were prepared by the electrochemical polymerization process. Electron microscopy studies reveal that PPy coating on the surface of nanotube is quite uniform throughout the length. The temperature dependent electrical resistivity and magnetization measurements were done from room temperature down to 5 and 10 K, respectively. The room temperature resistivity (rho) of PPy/MWNT composite fibril sample is similar to 3.8 Omega m with resistivity ratio R-5 K/R-300 K] of similar to 300, and the analysis of rho(T) in terms of reduced activation energy shows that resistivity lies in the insulating regime below 40 K. The resistivity varies according to three dimensional variable range hopping mechanism at low temperature. The magnetization versus applied field (M-H loop) data up to a field of 20 kOe are presented, displaying ferromagnetic behavior at all temperatures with enhanced coercivities similar to 680 and 1870 Oe at room temperature and 10 K, respectively. The observation of enhanced coercivity is due to significant dipolar interaction among encapsulated iron nanoparticles, and their shape anisotropy contribution as well.

Anisotropy induced crossover from weakly to strongly first order melting of two dimensional solids

Melting and freezing transitions in two dimensional (2D) systems are known to show highly unusual characteristics. Most of the earlier studies considered atomic systems: the melting of 2D molecular solids is still largely unexplored. In order to understand the role of anisotropy as well as multiple energy and length scales present in molecular systems, here we report computer simulation studies of melting of 2D molecular systems. We computed a limited portion of the solid-liquid phase diagram. We find that the interplay between the strength of isotropic and anisotropic interactions can give rise to rich phase diagram consisting of isotropic liquid and two crystalline phases-honeycomb and oblique. The nature of the transition depends on the relative strength of the anisotropic interaction and a strongly first order melting turns into a weakly first order transition on increasing the strength of the isotropic interaction. This crossover can be attributed to an increase in stiffness of the solid phase free energy minimum on increasing the strength of the anisotropic interaction. The defects involved in melting of molecular systems are quite different from those known for the atomic systems.

Heat and mass transfer and chemical transformation in a cerium nitrate droplet

This paper deals with the thermo-physical changes that a droplet undergoes when it is radiatively heated in a levitated environment. The heat and mass transport model has been developed along with chemical kinetics within a cerium nitrate droplet. The chemical transformation of cerium nitrate to ceria during the process is predicted using Kramers' reaction mechanism which justifies the formation of ceria at a very low temperature as observed in experiments. The rate equation modeled by Kramers is modified suitably to be applicable within the framework of a droplet, and predicts experimental results well in both bulk form of cerium nitrate and in aqueous cerium nitrate droplet. The dependence of dissociation reaction rate on droplet size is determined and the transient mass concentration of unreacted cerium nitrate is reported. The model is validated with experiments both for liquid phase vaporization and chemical reaction. Vaporization and chemical conversion are simulated for different ambient conditions. The competitive effects of sensible heating rate and the rate of vaporization with diffusion of cerium nitrate is seen to play a key role in determining the mass fraction of ceria formed within the droplet. Spatially resolved modeling of the droplet enables the understanding of the conversion of chemical species in more detail.

Electric current-induced mass flow in very thin infinite metallic films

This paper reports on the mass transport behavior of infinitely extended, continuous, and very thin metallic films under the influence of electric current. Application of direct current of high densities (> 10(8) A/m(2)) results in visible melting of thin film at only one of the electrodes, and the melt then flows towards the other electrode in a circularly symmetric fashion forming a microscale ring pattern. For the two tested thin film systems, namely Cr and Al, of thicknesses ranging from 4 to 20 nm, the above directional flow consistently occurred from cathode to anode and anode to cathode, respectively. Furthermore, application of alternating electric current results in flow of the liquid material from both the electrodes. The dependence of critical flow behavior parameters, such as flow direction, flow velocity, and evolution of the ring diameter, are experimentally determined. Analytical models based on the principles of electromigration in liquid-phase materials are developed to explain the experimental observations.

Relation between the Isentropic Index and the Gruneisen Parameter for Saturated Liquids

We investigate the isentropic index along the saturated vapor line as a correlating parameter with quantities both in the saturated liquid phase and the saturated vapor phase. The relation is established via temperatures such as T-hgmax and T* where the saturated vapor enthalpy and the product of saturation temperature and saturated liquid density attain a maximum, respectively. We obtain that the saturated vapor isentropic index is correlated with these temperatures but also with the saturated liquid Gruneisen parameters at T-hgmax. and T*.

Effect of adsorbate loading on selectivity during adsorption of C/C and C/C n-alkane binary mixtures in silicalite

Adsorption experiments of mixtures of long chain alkanes into silicalite under liquid phase conditions show selectivity inversion and azeotrope formation. These effects are due to the subtle interplay between the size of the adsorbed molecules and pore topology of the adsorbent. In this study, the selective uptake of lighter component during liquid phase adsorption of C/C and C/C n-alkane binary mixtures in the zeolite silicalite is understood through configurational bias grand-canonical Monte Carlo molecular simulation technique and a coarse-grained siting analysis. The simulations are conducted under conditions of low and intermediate levels of loading. The siting pattern of the adsorbates inside the zeolite pores explain the selectivity as seen in experiments.

Growing dynamical facilitation on approaching the random pinning colloidal glass transition

Despite decades of research, it remains to be established whether the transformation of a liquid into a glass is fundamentally thermodynamic or dynamic in origin. Although observations of growing length scales are consistent with thermodynamic perspectives, the purely dynamic approach of the Dynamical Facilitation (DF) theory lacks experimental support. Further, for vitrification induced by randomly freezing a subset of particles in the liquid phase, simulations support the existence of an underlying thermodynamic phase transition, whereas the DF theory remains unexplored. Here, using video microscopy and holographic optical tweezers, we show that DF in a colloidal glass-forming liquid grows with density as well as the fraction of pinned particles. In addition, we observe that heterogeneous dynamics in the form of string-like cooperative motion emerges naturally within the framework of facilitation. Our findings suggest that a deeper understanding of the glass transition necessitates an amalgamation of existing theoretical approaches.

Role of degree of saturation in denitrification of unsaturated sand specimens

Nitrate contamination of groundwater arises from anthropogenic activities, such as, fertilizer and animal manure applications and infiltration of wastewater/leachates. During migration of wastewater and leachates, the vadose zone (zone residing above the groundwater table), is considered to facilitate microbial denitrification. Particle voids in vadose zone are deficient in dissolved oxygen as the voids are partially filled by water and the remainder by air. Discontinuities in liquid phase would also restrict oxygen diffusion and therefore facilitate denitrification in the vadose/unsaturated soil zone. The degree of saturation of soil specimen (S (r)) quantifies the relative volume of voids filled with air and water. Unsaturated specimens have S (r) values ranging between 0 and 100 %. Earlier studies from naturally occurring nitrate losses in groundwater aquifers in Mulbagal town, Kolar District, Karnataka, showed that the sub-surface soils composed of residually derived sandy soil; hence, natural sand was chosen in the laboratory denitrification experiments. With a view to understand the role of vadose zone in denitrification process, experiments are performed with unsaturated sand specimens (S (r) = 73-90 %) whose pore water was spiked with nitrate and ethanol solutions. Experimental results revealed 73 % S (r) specimen facilitates nitrate reduction to 45 mg/L in relatively short durations of 5.5-7.5 h using the available natural organic matter (0.41 % on mass basis of sand); consequently, ethanol addition did not impact rate of denitrification. However, at higher S (r) values of 81 and 90 %, extraneous ethanol addition (C/N = 0.5-3) was needed to accelerate the denitrification rates.

Solubilities of 10-undecenoic acid and geraniol in supercritical carbon dioxide

The solubilities of 10-undecenoic acid and geraniol in supercritical carbon dioxide were measured at 308, 313,323 and 333K, and at pressures of 10-18 MPa. Solubilities (in mole fraction),ranged from 0.4 x 10(-3) to 17.4 x 10(-3) for 10-undecenoic acid and 2.7 x 10(-3) to 25 x 10(-3) for geraniol, respectively. The AARD was around 11% and 5% for these models for 10-undecenoic acid and geraniol, respectively. The solubilities of both compounds showed retrograde behavior wherein the solubilities decrease with temperature at isobaric conditions. The solubility of geraniol was higher than 10-undecenoic acid at all investigated temperatures and pressures. The data were found to be self consistent based on the Mendez-Santiago model. New models based on association theory using van Laar and Margules activity coefficient models for solute in liquid phase were derived, and used to correlate the solubilities. (C) 2015 Elsevier B.V. All rights reserved.

Non-Gravitational Effects with Density-Matching in Evaluating the Influence of Sedimentation on Colloidal Coagulation

The method of density matching between the solid and liquid phases is often adopted to effectively eliminate the effect of sedimentation of suspensions in studies on dynamic behaviour of a colloidal system. However, the associated changes in the solvent composition may bring side effects to the properties investigated and therefore might lead to a faulty conclusion if the relevant correction is not made. To illustrate the importance of this side effect, we present an example of the sedimentation influence on the coagulation rate of suspensions of 2 μm (diameter) polystyrene. The liquid mixtures, in the proper proportions of water (H2O), deuterium oxide (D2O) and methanol (MeOH) as the liquid phase, density-matched and unmatched experiments are performed. Besides the influence of viscosity, the presence of methanol in solvent media, used to enhance the sedimentation effect, causes significant changes (reduction) in rapid coagulation rates compared to that in pure water. Without the relevant corrections for those non-gravitational factors it seems that gravitational sedimentation would retard the coagulation. The magnitude of the contribution from the non-gravitational factor is quantitatively determined, making the relevant correction possible. After necessary corrections for all factors, our experiments show that the influence of the sedimentation on coagulation rates at the initial stage of the coagulation is not observable.