Stability of the flow in a soft tube deformed due to an applied pressure gradient

A linear stability analysis is carried out for the flow through a tube with a soft wall in order to resolve the discrepancy of a factor of 10 for the transition Reynolds number between theoretical predictions in a cylindrical tube and the experiments of Verma and Kumaran J. Fluid Mech. 705, 322 (2012)]. Here the effect of tube deformation (due to the applied pressure difference) on the mean velocity profile and pressure gradient is incorporated in the stability analysis. The tube geometry and dimensions are reconstructed from experimental images, where it is found that there is an expansion and then a contraction of the tube in the streamwise direction. The mean velocity profiles at different downstream locations and the pressure gradient, determined using computational fluid dynamics, are found to be substantially modified by the tube deformation. The velocity profiles are then used in a linear stability analysis, where the growth rates of perturbations are calculated for the flow through a tube with the wall modeled as a neo-Hookean elastic solid. The linear stability analysis is carried out for the mean velocity profiles at different downstream locations using the parallel flow approximation. The analysis indicates that the flow first becomes unstable in the downstream converging section of the tube where the flow profile is more pluglike when compared to the parabolic flow in a cylindrical tube. The flow is stable in the upstream diverging section where the deformation is maximum. The prediction for the transition Reynolds number is in good agreement with experiments, indicating that the downstream tube convergence and the consequent modification in the mean velocity profile and pressure gradient could reduce the transition Reynolds number by an order of magnitude.

Synthesis and Characterization of Au@Pt Nanoparticles with Ultrathin Platinum Overlayers

Gold-core platinum-shell (Au@Pt) nanoparticles with ultrathin platinum overlayers, ranging from submonolayer to two monolayers of platinum atoms, were prepared at room-temperature using a scalable, wet-chemical synthesis route. The synthesis involved the reduction of chloroauric acid with tannic acid to form 5 nm (nominal dia.) gold nanoparticles followed by addition of desired amount of chloroplatinic acid and hydrazine to form platinum overlayers with bulk Pt/Au atomic ratios (Pt surface coverages) corresponding to 0.19 (half monolayer), 0.39 (monolayer), 0.58 (1.5 monolayer) and 0.88 (2 monolayers). The colloidal particles were coated with octadecanethiol and phase-transferred into chlroform-hexane mixture to facilitate sample preparation for structural characterization. The structure of the resultant nanoparticles were determined to be Au@Pt using HRTEM, SAED, XPS, UV-vis and confirmed by cyclic voltammetry (CV) studies. Monolayers of octadecanethiol coated Au@Pt nanoparticles were self-assembled at an air-water interface and transfer printed twice onto a gold substrate to form bilayer films for electrochemical characterization. Electrochemical activity on such films was observed only after the removal of the octadecanethiol ligand coating the nanoparticles, using a RF plasma etching process. The electrochemical activity (HOR, MOR studies) of Au@Pt nanoparticles was found to be highest for particles having a two atom thick platinum overlayer. These nanoparticles can significantly enhance platinum utilization in electrocatalytic applications as their platinum content based activity was three times higher than pure platinum nanoparticles.

Porous membranes designed from bi-phasic polymeric blends containing silver decorated reduced graphene oxide synthesized via a facile one-pot approach

In this work, porous membranes were designed by selectively etching the PEO phase, by water, from a melt-mixed PE/PEO blend. The pure water flux and the resistance across the membrane were systematically evaluated by employing an indigenously developed cross flow membrane setup. Both the phase morphology and the cross sectional morphology of the membranes was assessed by scanning electron microscopy and an attempt was made to correlate the observed morphology with the membrane performance. In order to design antibacterial membranes for water purification, partially reduced graphene oxide (rGO), silver nanoparticles (Ag) and silver nanoparticles decorated with rGO (rGO-Ag) were synthesized and incorporated directly into the blends during melt mixing. The loss of viability of bacterial cells was determined by the colony counting method using E. coli as a model bacterium. SEM images display that the direct contact with the rGO-Ag nanoparticles disrupts the cell membrane. In addition, the rGO-Ag nanoparticles exhibited a synergistic effect with respect to bacterial cell viability in comparison to both rGO and Ag nanoparticles. The possible mechanism associated with the antibacterial activity in the membranes was discussed. This study opens new avenues in designing antibacterial membranes for water purification.

A Surlyn/magnesium oxide nanocomposite as an effective water vapor barrier for organic device encapsulation

A reactive polymer nanocomposite system was proposed as an effective water vapor barrier material for organic device encapsulation. Nanosized magnesium oxide (MgO) was synthesized by the solution combustion technique using two different fuels, lactose and alanine. The purity and crystallite size of MgO were determined from X-ray diffraction studies. The surface areas and porosity measurements were used to determine the water adsorption capacities of MgO. Nanocomposites with various concentrations (wt% = 0.25, 0.5, 1 and 2.5) of MgO were prepared using Surlyn as the base polymer. The permeation rate of moisture through the fabricated films was calculated using calcium degradation test and these rates were further used to calculate the diffusivities. Accelerated aging experiments were conducted to study the performance of organic photovoltaic devices encapsulated with synthesized films under accelerated weathering conditions. The performance of the barrier materials with synthesized MgO was also compared to that obtained with commercial MgO. The films containing MgO obtained from lactose exhibited better barrier properties compared to other films made with commercial MgO and MgO synthesized using alanine as well as other nanocomposites reported in the literature.

Polyvinylidene fluoride based lightweight and corrosion resistant electromagnetic shielding materials

Various NixCo1-x alloys (with x varying from 0-60 wt%, Ni: nickel, Co: cobalt) were prepared by vacuum arc melting and mixed with polyvinylidene fluoride (PVDF) to design lightweight, flexible and corrosion resistant materials that can attenuate electromagnetic radiation. The saturation magnetization scaled with the fraction of Co in the alloy. Two key properties such as high-magnetic permeability and high-electrical conductivity were targeted. While the former was achieved using a Ni-Co alloy, multiwalled carbon nanotubes (CNTs) in the composites accomplished the latter. A unique approach was adopted to prepare the composites wherein PVDF powder along with CNTs and Ni-Co flakes were made into a paste, using a solvent, followed by hot pressing. Interestingly, CNTs facilitated in uniform dispersion of the Ni-Co alloy in PVDF, as manifested from synergistic improvement in the electrical conductivity. A significant improvement in the shielding effectiveness (41 dB, >99.99% attenuation) was achieved with the addition of 50 wt% of Ni40Co60 alloy and 3 wt% CNTs. Intriguingly, due to the unique processing technique adopted here, the flexibility of the composites was retained and more interestingly, the composites were resistant to corrosion as compared to only Ni-Co alloy.

Kinetics of CO oxidation on palladium using microkinetics coupled with reaction route analysis

A plausible microkinetic model has been proposed for the CO oxidation reaction catalysed by palladium (Pd) with the kinetic parameters obtained from the literature. A robust rate expression using the reaction route analysis has been developed for the presented microkinetic scheme and the obtained rate expressions have been validated against the experimental data presented in the literature. A wide range of experimental conditions ranging from single Pd crystals under ultra-high vacuum conditions and impregnated Pd used for fixed bed experiments under atmospheric pressure has been used to validate the reaction mechanism. (C) 2015 Elsevier Ltd. All rights reserved.

Effect of viscosity and surface tension on breakup and coalescence of bicomponent sprays

This work deals with an experimental study of the breakup characteristics of liquids with different surface tension and viscosity from a hollow cone hydraulic injector nozzle induced by pressure-swirl. The experiments were conducted at Reynolds numbers Re-p=9500-23,000. The surface tension and viscosity of the surrogate fuels were altered from 72 to 30 mN/m and 1.1 to 1.6 mN s/m(2), respectively. High speed photography and Phase Doppler Particle Anemometry were utilized to study the atomization process. Velocity and drop size measurements of the spray using PDPA in both axial and radial directions indicate a dependency on surface tension. However, these effects are dominant only at low Reynolds numbers and are negligible at high Reynolds number. Downstream of the nozzle, coalescence of droplets due to collision was also found to be significant and the diameters were compared for different liquids. For viscous fluids up to 1.6 cP, the independent effects of viscosity and injection pressure are studied. In general, the spray cone angle increases with increase in pressure. At high pressures, an increase in viscosity leads to higher drop sizes following primary and secondary breakup compared to water. This study will extend our understanding of surrogate fuel film breakup and highlight the importance of long and short wavelength instabilities. (C) 2013 Elsevier Ltd. 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.

Markov chain splitting methods in structural reliability integral estimation

Monte Carlo simulation methods involving splitting of Markov chains have been used in evaluation of multi-fold integrals in different application areas. We examine in this paper the performance of these methods in the context of evaluation of reliability integrals from the point of view of characterizing the sampling fluctuations. The methods discussed include the Au-Beck subset simulation, Holmes-Diaconis-Ross method, and generalized splitting algorithm. A few improvisations based on first order reliability method are suggested to select algorithmic parameters of the latter two methods. The bias and sampling variance of the alternative estimators are discussed. Also, an approximation to the sampling distribution of some of these estimators is obtained. Illustrative examples involving component and series system reliability analyses are presented with a view to bring out the relative merits of alternative methods. (C) 2015 Elsevier Ltd. All rights reserved.

Copolyesters from Soybean Oil for Use as Resorbable Biomaterials

A family of soybean oil (SO) based biodegradable cross-linked copolyesters sourced from renewable resources was developed for use as resorbable biomaterials. The polyesters were prepared by a melt condensation of epoxidized soybean oil polyol and sebacic acid with citric acid (CA) as a cross-linker. D-Mannitol (M) was added as an additional reactant to improve mechanical properties. Differential scanning calorimetry revealed that the polyester synthesized using only CA as the cross-linker was semicrystalline and elastomeric at physiological temperature. The polymers were hydrophobic in nature. The water wettability, elongation at break and the degradation rate of the polyesters decreased with increase in M content or curing time. Modeling of release kinetics of dyes showed a diffusion controlled mechanism underlies the observed sustained release from these polymers. The polyesters supported attachment and proliferation of human stem cells and were thus cytocompatible. Porous scaffolds induced osteogenic differentiation of the stern cells suggesting that these polymers are well suited for bone tissue engineering. Thus, this family of polyesters offers a low cost and green alternative as biocompatible, bioresobable polymers for potential use as resorbable biomaterials for tissue engineering and controlled release.

Unusual Fragility and Cooperativity in Glass-Forming and Crystalline PVDF/PMMA Blends in the Presence of Multiwall Carbon Nanotubes

Poly(vinylidene fluoride) (PVDF) and poly(methyl methacrylate) (PMMA) are completely miscible below 50 wt % PVDF in the blends. In this work, an attempt was made to understand the fragility/cooperativity relation in glass-forming and crystalline blends of PVDF/PMMA and in the presence of a heteronucleating agent, multiwall carbon nanotubes (CNTs). Hence, three representative blends were chosen: a completely amorphous (10/90 by wt, PVDF/PMMA), on the verge of amorphous miscibility (50/50 by wt, PVDF/PMMA), and crystalline (60/40 by wt, PVDF/PMMA) blends. The intermolecular cooperativity/coupling, fragility, and configurational entropy near the glass transition temperature (T-g) were studied using differential scanning calorimetry (DSC) and broadband dielectric relaxation spectroscopy (DRS). It was observed that the blends with higher concentration of PMMA were more fragile (fragility index m = 141) and those with higher concentration of PVDF were more strong (m = 78). Interestingly, the coupling was less in the glass-forming blends (10/90 by wt, PVDF/PMMA) than the crystalline blends as manifested from DRS. This observation was also supported by DSC measurements which reflected that the cooperative rearranging region (CRR) existed over a smaller length scales in fragile blends as compared to strong blends, possibly due to restricted amorphous mobility. This effect was more prominent in the presence of CNTs, in particular for 50/50 (by wt) and 60/40 (by wt) PVDF/PMMA blends. Further, the configurational entropy, as manifested from DRS, decreased significantly in the strong blends in striking contrast to the fragile blends, supported by DSC, which manifested in an increase in the volume of cooperativity in the strong blends. The higher coupling in the crystalline blends can be attributed to good packing of the amorphous regions. While this is understood for crystalline blends (60/40 by wt, PVDF/PMMA), it is envisaged that enhanced dynamic heterogeneity is accountable for increased coupling in the case of blends which are on the verge of amorphous miscibility (50/50 by wt, PVDF/PMMA). The latter is also supported by broad relaxations near the T-g in DRS. Interestingly, the intermolecular coupling in the blends in the presence of CNTs has reduced, though the potential energy barrier hindering the rearrangement of CRR is lower than the blends without CNTs. In addition, the amorphous packing is not as effective as the blends without CNTs. This is manifested from reduced volume of cooperativity in particular, for 50/50 (by wt) and 60/40 (by wt) blends.

Improving the Rigor and Consistency of the Thermodynamic Theory for Clathrate Hydrates through Incorporation of Movement of Water Molecules of Hydrate Lattice

Current applications of statistical thermodynamic theories for clathrate hydrates do not incorporate the translational and rotational movement of water molecules of the hydrate lattice,in a rigorous manner. Previous studies have shown that the movement of water molecules has a significant effect on the properties of clathrate hydrates. In this Article, a method is presented to incorporate the effect of water movement with as much rigor as possible. This method is then used to calculate the Langmuir constant of the guest species in a clathrate hydrate. Unlike previous studies on modeling of clathrate hydrate thermodynamics, the method presented in this paper does not regress either the intermolecular potentials or the properties of the empty hydrate from clathrate phase equilibria data. Also the properties of empty hydrate used in the theory do not depend on the nature and composition of the guest molecules. The predicted phase equilibria from the resulting theory are shown to be highly accurate and thermodynamically consistent by comparing them with the phase equilibria computed directly from molecular simulations.

Dendron conjugation to graphene oxide using click chemistry for efficient gene delivery

Owing to its large surface area and rapid cellular uptake, graphene oxide (GO) is emerging as an attractive candidate material for delivery of drugs and genes. The inherent sp(2) pi-pi interaction of GO helps to carry drugs and single stranded RNA (ssRNA) but there is no such interaction with double stranded DNA (dsDNA). In this work, a polyamidoamine (PAMAM) dendron was conjugated with nano GO (nGO) through ``click'' chemistry to improve the DNA complexation capability of GO as well as its transfection efficiency. The DNA complexation capability of GO was significantly enhanced after dendronization of GO yielding spherical nanosized (250-350 nm) particles of the dendronized GO (DGO)/pDNA complex with a positive zeta potential. The transfection efficiency of GO dramatically increased after conjugation of the PAMAM dendron. Transfection efficiency of 51% in HeLa cells with cell viability of 80% was observed. The transfection efficiency was significantly higher than that of polyethyleneimine 25 kDa (27% efficiency) and also surpassed that of lipofectamine 2000 (47% efficiency). The uptake of the DGO/pDNA complex by the caveolae mediated endocytosis pathway may significantly contribute to the high transfection efficiency. Thus, dendronized GO is shown to be an efficient gene carrier with minimal toxicity and is a promising candidate for use as a nonviral carrier for gene therapy.

Photocatalytic inactivation of E-Coli by ZnO-Ag nanoparticles under solar radiation

Porous and fluffy ZnO photocatalysts were successfully prepared via simple solution based combustion synthesis method. The photocatalytic inactivation of Escherichia coli bacteria was studied separately for both Ag substituted and impregnated ZnO under irradiation of natural solar light. A better understanding of substitution and impregnation of Ag was obtained by Raman spectrum and X-ray photoelectron analysis. The reaction parameters such as catalyst dose, initial bacterial concentration and effect of hydroxyl radicals via H2O2 addition were also studied for ZnO catalyst. Effective inactivation was observed with 0.25 g L-1 catalyst loading having 10(9) CFU mL(-1) bacterial concentration. With an increase in molarity of H2O2, photocatalytic inactivation was enhanced. The effects of different catalysts were studied, and highest bacterial killing was observed by Ag impregnated ZnO with 1 atom% Ag compared to Ag substituted ZnO. This enhanced activity can be attributed to effective charge separation that is supported by photoluminescence studies. The kinetics of reaction in the presence of different scavengers showed that reaction is significantly influenced by the presence of hole and hydroxyl radical scavenger with high efficiency.

Thermally flexible epoxy/cellulose blends mediated by an ionic liquid

Blends between the widely used thermoset resin, epoxy, and the most abundant organic material, natural cellulose are demonstrated for the first time. The blending modification induced by charge transfer complexes using a room temperature ionic liquid, leads to the formation of thermally flexible thermoset materials. The blend materials containing low concentrations of cellulose were optically transparent which indicates the miscibility at these compositions. We observed the existence of intermolecular hydrogen bonding between epoxy and cellulose in the presence of the ionic liquid, leading to partial miscibility between these two polymers. The addition of cellulose improves the tensile mechanical properties of epoxy. This study reveals the use of ionic liquids as a compatible processing medium to prepare epoxy thermosets modified with natural polymers.