A new semi-empirical model for correlating the solubilities of solids in supercritical carbon dioxide with cosolvents

The equilibrium solubilities of the solids in supercritical carbon dioxide (SCCO(2)) are considerably enhanced in the presence of cosolvents. The solubilities of m-dinitrobenzene at 308 and 318 K over a pressure range of 9.5-14.5 MPa in the presence of 1.13-2.17 mol% methanol as cosolvent were determined. The average increase in the solubilities in the presence of methanol compared to that obtained in the absence of methanol was around 35%. A new semi-empirical equation in terms of temperature, pressure, density of SCCO(2) and cosolvent composition comprising of 7 adjustable parameters was developed. The proposed model was used to correlate the solubility of the solids in SCCO(2) for the 44 systems available in the literature along with current data. The average absolute relative deviation of the experimental data from the model equation was 3.58%, which is better than the existing models. (C) 2011 Elsevier B.V. All rights reserved.

Characterisation of microstructure and evaluation of optical and EPR properties of superhydrophobic copper dodecanoate films

Copper dodecanoate films prepared by emulsion method exhibit superhydrophobic property with water contact angle of 155 degrees and sliding angle of <2 degrees. The films have been characterised by using X-ray diffraction, field emission scanning electron microscopy and Fourier transform infrared spectroscopy techniques. Surface microstructure of copper dodecanoate consists of numerous microscale papillas of about 6-12 mu m in length with a diameter in the range of 360-700 nm. The superhydrophobicity of the films is due to their dual micronano surface morphology. The wetting behaviour of the film surface was studied by a simple water immersion test. The results show that copper dodecanoate film retained superhydrophobic property even after immersing in water for about 140 h. The optical absorption spectrum exhibits two broadbands centred at 388 and 630 nm that have been assigned to B-2(1g) -> E-2(g) and B-2(1g) -> B-2(2g) transitions of Cu2+ ions, respectively. The electron paramagnetic resonance spectrum exhibits two resonance signals with effective g values at g(parallel to)approximate to 2.308 and g(perpendicular to) approximate to 2.071, which suggests that the unpaired electron occupies d(x2-y2) orbital in the ground state. Copyright (C) 2011 John Wiley & Sons, Ltd.

Mixture solubilities of nitrobenzoic acid isomers in supercritical carbon dioxide

The ternary solubilities of solid isomers of nitrobenzoic acid (NBA) were experimentally determined at 308, 318 and 328K over a pressure range of 12-18 MPa in supercritical carbon dioxide (SCCO2). Compared to its binary solubility, the ternary solubilities of m-NBA increased at 308 K while it decreased at 328 K. However, the ternary solubilities of p-NBA increased at all temperatures and pressures except at 13 MPa and 328K. A new model was developed by applying solution model and activity coefficient model for the ternary solubilities of pharmaceutical and non-pharmaceutical solid mixtures in terms of temperature, density and cosolute composition. The model equation involves four temperature independent constraint-free parameters. The model equation correlates the ternary solubilities of seven pharmaceutical solid mixtures along with current data with an average AARD around 9.5% and sixteen non-pharmaceutical solid mixtures with 9% AARD. (C) 2012 Elsevier B.V. All rights reserved.

A 12 V Substrate-Integrated PbO2-Activated Carbon Asymmetric Hybrid Ultracapacitor with Silica-Gel-Based Inorganic-Polymer Electrolyte

A 12 V Substrate-Integrated PbO2-Activated Carbon hybrid ultracapacitor (SI-PbO2-AC HUCs) with silica-gel sulfuric acid electrolyte is developed and performance tested. The performance of the silica-gel based hybrid ultracapacitor is compared with flooded and AGM-based HUCs. These HUCs comprise substrate-integrated PbO2 (SI-PbO2) as positive electrodes and high surface-area activated carbon with dense graphite-sheet substrate as negative electrodes. 12 V SI-PbO2-AC HUCs with flooded, AGM and gel electrolytes are found to have capacitance values of 308 F, 184 F, and 269 F at C-rate and can be pulse charged and discharged for 100,000 cycles with only a nominal decrease in their capacitance values. The best performance is exhibited by gel-electrolyte HUCs.

Measurement and correlation of quaternary solubilities of dihydroxybenzene isomers in supercritical carbon dioxide

The equilibrium quaternary solubilities of dihydroxybenzene (resorcinol + pyrocatechol + hydroquinone + SCCO2) isomers were experimentally determined at 308, 318 and 328K over a pressure range of 9.8-15.7 MPa by using a saturation method. The effects of temperature, pressure and the components on each other have been thoroughly investigated. The selectivity of SCCO2 for ternary (resorcinol + pyrocatechol + SCCO2) and quaternary systems was discussed. A new model equation for quaternary solubilities of solids has been developed by accounting for non-idealities by combining the solution model with Wilson activity coefficient model. The model equation has five adjustable parameters and correlates the quaternary solubilities of current data along with two other quaternary data reported in the literature. (C) 2012 Elsevier B.V. All rights reserved.

Influence of strain localization on reliability based design of bridge abutments using pseudo-dynamic method

The paper focuses on reliability based design of bridge abutments when subjected to earthquake loading. Planar failure surface has been used in conjunction with pseudo-dynamic approach to compute the seismic active earth pressures on the bridge abutment. The proposed pseudo dynamic method, considers the effects of strain localization in the backfill soil and associated post-peak reduction in the shear resistance from peak to residual values along a previously formed failure plane, phase difference in shear waves and soil amplification along with the horizontal seismic accelerations. Four modes of stability viz. sliding, overturning, eccentricity and bearing capacity of the foundation soil are considered for the reliability analysis. The influence of various design parameters on the seismic reliability indices against four modes of failure is presented, following the suggestions of Japan Road Association, Caltrans Bridge Design Specifications and U.S Department of the Army.

Dispersion characteristics of paired waveguide modes in 2D photonic band gap structures

In this paper the case of a typical line defect in 2D Photonic crystal is analyzed. The 2D photonic crystals are of dielectric rods in air in square and triangular lattice configurations. This line defect serves as waveguide with a pair of modes having opposite dispersion characteristics.

Experimental determination and activity coefficient based models for mixture solubilities of nitrophenol isomers in supercritical carbon dioxide

The experimental solubilities of the mixture of nitrophenol (m- and p-) isomers were determined at 308, 318 and 328 K over a pressure range of 10-17.55 MPa. Compared to the binary solubilities, the ternary solubilities of m-nitrophenol increased at 308, 318 and 328 K. The ternary solubilities of p-nitrophenol increased at 308 K, while the ternary solubilities decreased at lower pressures and increased at higher pressure at 318 and 328 K. The solubilities of the solid mixtures in supercritical carbon dioxide (SCCO2) were correlated with solution models by incorporating the non-idealities using activity coefficient based models. The Wilson and NRTL activity coefficient models were applied to determine the nature of the interactions between the molecules. The equation developed by using the NRTL model has three parameters and correlates mixture solubilities of solid solutes in terms of temperature and cosolute composition. The equation derived from the Wilson model contains five parameters and correlates solubilities in terms of temperature, density and cosolute composition. These two new equations developed in this work were used to correlate the solubilities of 25 binary solid mixtures including the current data. The average AARDs of the model equations derived using the NRTL and Wilson models for the solid mixtures were found to be 7% and 4%, respectively. (C) 2012 Elsevier B.V. All rights reserved.

Conducting polymer-carbon black nanocomposite sensor for volatile organic compounds and correlating sensor response by molecular dynamics

Volatile organic compounds (VOCs) are present in our every day used products such as plastics, cosmetics, air fresheners, paint, etc. The determination of amount of VOC present in atmosphere can be carried out via various sensors. In this work a nanocomposite of a novel thiophene based conducting polymer and carbon black is used as a volatile organic compound sensor. The fabricated 2 lead chemiresistor sensor was tested for vapours of toluene, acetone, cylcohexane, and carbon tetrachloride. The sensor responds to all the vapours, however, exhibit maximum response to toluene vapours. The sensor was evaluated for various concentrations of toluene. The lower limit of detection of the sensor is 15 +/- 10 ppm. The study of the effect of humidity on senor response to toluene showed that the response decreases at higher humidity conditions. The surface morphology of the nanocomposite was characterized by scanning electron microscopy. Diffuse reflectance spectroscopy was used to investigate the absorption of vapours by the nanocomposite film. Contact angle measurements were used to present the effect of water vapour on the toluene response of nanocomposite film. Solubility parameter of the conducting polymer is predicted by molecular dynamics. The sensing behaviour of the conducting polymer is correlated with solubility parameter of the polymer. Dispersion interaction of conducting polymer with toluene is believed to be the reason for the selective response towards toluene. (C) 2014 Elsevier B.V. All rights reserved.

Solubilities of n-Butyl Esters in Supercritical Carbon Dioxide

The solubilities of butyl stearate and butyl laurate were determined in the temperature range of 308 K to 323 K and 313 K to 328 K, respectively, at pressures of 10 MPa to 16 MPa. The solubility of butyl laurate was higher than that of butyl stearate by almost an order in magnitude. Retrograde behavior was observed throughout the investigated pressure range. Semiempirical models such as Mendez-Teja, Chrastil, and other density-based models were used to correlate the experimental data of our work as well as several other liquid solutes.

Surface modification of textured silicon and its wetting behaviour

Textured silicon (Si) substrate were prepared using various texturing methods both chemical and physical and their water contact angle, surface topography and Raman spectra were studied and investigated. The effect of plasma and chemical treatment on micro/nanostructure and roughness of the surface with and without deposition of Octadecyltrichlorosilane (ODTS, Cl3Si (CH3)(17)), self-assembled monolayer (SAM) is investigated for achieving higher water contact angle (theta(c)). The importance of synergism of texturing with deposition of ODTS SAM in preparing superhydrophobic silicon surfaces has been discussed. It is shown that superhydrophobic silicon surfaces can be achieved on silicon surfaces by coating with ODTS, irrespective of whether it is textured or not, polished or unpolished, provided a chemical treatment is given to the surface prior to the ODTS coating.

Stress states in individual Si particles of a cast Al-Si alloy: Micro-Raman analysis and microstructure based modeling

The stress states in Si particles of cast Al-Si based alloys depend on its morphology and the heat treatment given to the alloy. The Si particles fracture less on modification and fracture more in the heat treated condition. An attempt has been made in this work to study the effect of heat treatment and Si modification on the stress states of the particles. Such understanding will be valuable for predicting the ductility of the alloy. The stress states of Si particles are estimated by Raman technique and compared with the microstructure-based FEM simulations. Combination of Electron Back-Scattered Diffraction (EBSD) and frequency shift, polarized micro-Raman technique is applied to determine the stress states in Si particles with (111) orientations. Stress states are measured in the as-received state and under uniaxial compression. The residual stress, the stress in the elastic-plastic regime and the stress which causes fracture of the particles is estimated by Raman technique. FEM study demonstrates that the stress distribution is uniform in modified Si, whereas the unmodified Si shows higher and more complex stress states. The onset of plastic flow is observed at sharp corners of the particles and is followed by localization of strain between particles. Clustering of particles generates more inhomogeneous plastic strain in the matrix. Particle stress estimated by Raman technique is in agreement with FEM calculations. (C) 2014 Elsevier B.V. All rights reserved.

Experimental determination and theoretical correlation for the solubilities of dicarboxylic acid esters in supercritical carbon dioxide

The synthesis of high molecular weight esters such as bis (2-ethylhexyl) sebacate is of significance for its use as a lubricant. This ester is synthesized by the transesterification of dimethyl sebacate with 2-ethylhexanol. Therefore, the solubilities of bis (2-ethylhexyl) sebacate and dimethyl sebacate were determined at 308-328 K at pressures of 10-18 MPa in supercritical carbon dioxide. The solubility of dimethyl sebacate was always higher than bis (2-ethylhexyl) sebacate at a given temperature and pressure. The Mendez-Teja model was used to verify the self-consistency of data. Further, a new semi-empirical model with three parameters was developed using the solution theory coupled with Wilson activity coefficient. This model was used to correlate the experimental data of this work and solubilities of many high molecular weight esters reported in the literature. (C) 2015 Elsevier B.V. All rights reserved.

In-plane effective shear modulus of generalized circular honeycomb structures and bundled tubes in a diamond array structure

Use of circular hexagonal honeycomb structures and tube assemblies in energy absorption systems has attracted a large number of literature on their characterization under crushing and impact loads. Notwithstanding these, effective shear moduli (G*) required for complete transverse elastic characterization and in analyses of hierarchical structures have received scant attention. In an attempt to fill this void, the present study undertakes to evaluate G* of a generalized circular honeycomb structures and tube assemblies in a diamond array structure (DAS) with no restriction on their thickness. These structures present a potential to realize a spectrum of moduli with minimal modifications, a point of relevance for manufactures and designers. To evaluate G* in this paper, models based on technical theories - thin ring theory and curved beam theory - and rigorous theory of elasticity are investigated and corroborated with FEA employing contact elements. Technical theories which give a good match for thin HCS offer compact expressions for moduli which can be harvested to study sensitivity of moduli on topology. On the other hand, elasticity model offers a very good match over a large range of thickness along with exact analysis of stresses by employing computationally efficient expressions. (C) 2015 Elsevier Ltd. All rights reserved.

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.