Effect of charge asymmetry and charge screening on structure of superlattices formed by oppositely charged colloidal particles

Colloidal suspensions made up of oppositely charged particles have been shown to self-assemble into substitutionally ordered superlattices. For a given colloidal suspension, the structure of the superlattice formed from self-assembly depends on its composition, charges on the particles, and charge screening. In this study we have computed the pressure-composition phase diagrams of colloidal suspensions made up of binary mixtures of equal sized and oppositely charged particles interacting via hard core Yukawa potential for varying values of charge screening and charge asymmetry. The systems are studied under conditions where the thermal energy is equal or greater in magnitude to the contact energy of the particles and the Debye screening length is smaller than the size of the particles. Our studies show that charge asymmetry has a significant effect on the ability of colloidal suspensions to form substitutionally ordered superlattices. Slight deviations of the charges from the stoichiometric ratio are found to drastically reduce the thermodynamic stability of substitutionally ordered superlattices. These studies also show that for equal-sized particles, there is an optimum amount of charge screening that favors the formation of substitutionally ordered superlattices. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.3700226]

Experimental and simulation studies on the performance of standing wave thermoacoustic prime mover for pulse tube refrigerator

The thermoacoustic prime mover (TAPM) has gained considerable attention as a pressure wave generator to drive pulse tube refrigerator (PTR) due to no moving parts, reasonable efficiency, use of environmental friendly working fluids etc. To drive PTCs, lower frequencies (f) with larger pressure amplitudes (Delta P) are essential, which are affected by geometric and operating parameters of TAPM as well as working fluids. For driving PTRs, a twin standing wave TAPM is built and studied by using different working fluids such as helium, argon, nitrogen and their binary mixtures. Simulation results of DeltaEc are compared with experimental data wherever possible. DeltaEc predicts slightly increased resonance frequencies, but gives larger Delta P and lower temperature difference Delta T across stack. High mass number working fluid leads to lower frequency with larger Delta P, but higher Delta T. Studies indicate that the binary gas mixture of right composition with lower Delta T can be arrived at to drive TAPM of given geometry. (C) 2013 Elsevier Ltd and IIR. All rights reserved.

Combined toxicity of two crystalline phases (anatase and rutile) of Titania nanoparticles towards freshwater microalgae: Chlorella sp

In view of the increasing usage of anatase and rutile crystalline phases of titania NPs in the consumer products, their entry into the aquatic environment may pose a serious risk to the ecosystem. In the present study, the possible toxic impact of anatase and rutile nanoparticles (individually and in binary mixture) was investigated using freshwater microalgae, Chlorella sp. at low exposure concentrations (0.25, 0.5 and 1 mg/L) in freshwater medium under UV irradiation. Reduction of cell viability as well as a reduction in chlorophyll content were observed due to the presence of NPs. An antagonistic effect was noted at certain concentrations of binary mixture such as (0.25, 0.25), (0.25, 0.5), and (0.5, 0.5) mg/L, and an additive effect for the other combinations, (0.25, 1), (0.5, 0.25), (0.5, 1), (1, 0.25), (1, 0.5), and (1, 1) mg/L. The hydrodynamic size analyses in the test medium revealed that rutile NPs were more stable in lake water than the anatase and binary mixtures at 6 h, the sizes of anatase (1 mg/L), rutile NPs (1 mg/L), and binary mixture (1, 1 mg/L) were 948.83 +/- 35.01 nm, 555.74 +/- 19.93 nm, and 1620.24 +/- 237.87 nm, respectively]. The generation of oxidative stress was found to be strongly dependent on the crystallinity of the nanoparticles. The transmission electron microscopic images revealed damages in the nucleus and cell membrane of algal cells due to the interaction of anatase NPs, whereas rutile NPs were found to cause chloroplast and internal organelle damages. Mis-shaped chloroplasts, lack of nucleus, and starch-pyrenoid complex were noted in binary-treated cells. The findings from the current study may facilitate the environmental risk assessment of titania NPs in an aquatic ecosystem. (C) 2015 Elsevier B.V. All rights reserved.

Spatio-temporal correlations in aqueous systems: computational studies of static and dynamic heterogeneity by 2D-IR spectroscopy

Local heterogeneity is ubiquitous in natural aqueous systems. It can be caused locally by external biomolecular subsystems like proteins, DNA, micelles and reverse micelles, nanoscopic materials etc., but can also be intrinsic to the thermodynamic nature of the aqueous solution itself (like binary mixtures or at the gas-liquid interface). The altered dynamics of water in the presence of such diverse surfaces has attracted considerable attention in recent years. As these interfaces are quite narrow, only a few molecular layers thick, they are hard to study by conventional methods. The recent development of two dimensional infra-red (2D-IR) spectroscopy allows us to estimate length and time scales of such dynamics fairly accurately. In this work, we present a series of interesting studies employing two dimensional infra-red spectroscopy (2D-IR) to investigate (i) the heterogeneous dynamics of water inside reverse micelles of varying sizes, (ii) supercritical water near the Widom line that is known to exhibit pronounced density fluctuations and also study (iii) the collective and local polarization fluctuation of water molecules in the presence of several different proteins. The spatio-temporal correlation of confined water molecules inside reverse micelles of varying sizes is well captured through the spectral diffusion of corresponding 2D-IR spectra. In the case of supercritical water also, we observe a strong signature of dynamic heterogeneity from the elongated nature of the 2D-IR spectra. In this case the relaxation is ultrafast. We find remarkable agreement between the different tools employed to study the relaxation of density heterogeneity. For aqueous protein solutions, we find that the calculated dielectric constant of the respective systems unanimously shows a noticeable increment compared to that of neat water. However, the `effective' dielectric constant for successive layers shows significant variation, with the layer adjacent to the protein having a much lower value. Relaxation is also slowest at the surface. We find that the dielectric constant achieves the bulk value at distances more than 3 nm from the surface of the protein.

Suspensions of polymer-grafted nanoparticles with added polymers-Structure and effective pair-interactions

We present the results of combined experimental and theoretical (molecular dynamics simulations and integral equation theory) studies of the structure and effective interactions of suspensions of polymer grafted nanoparticles (PGNPs) in the presence of linear polymers. Due to the absence of systematic experimental and theoretical studies of PGNPs, it is widely believed that the structure and effective interactions in such binary mixtures would be very similar to those of an analogous soft colloidal material-star polymers. In our study, polystyrene-grafted gold nanoparticles with functionality f = 70 were mixed with linear polystyrene (PS) of two different molecular weights for obtaining two PGNP: PS size ratios, xi = 0.14 and 2.76 (where, xi = M-g/M-m, M-g and M-m being the molecular weights of grafting and matrix polymers, respectively). The experimental structure factor of PGNPs could be modeled with an effective potential (Model-X), which has been found to be widely applicable for star polymers. Similarly, the structure factor of the blends with xi = 0.14 could be modeled reasonably well, while the structure of blends with xi = 2.76 could not be captured, especially for high density of added polymers. A model (Model-Y) for effective interactions between PGNPs in a melt of matrix polymers also failed to provide good agreement with the experimental data for samples with xi = 2.76 and high density of added polymers. We tentatively attribute this anomaly in modeling the structure factor of blends with xi = 2.76 to the questionable assumption of Model-X in describing the added polymers as star polymers with functionality 2, which gets manifested in both polymer-polymer and polymer-PGNP interactions especially at higher fractions of added polymers. The failure of Model-Y may be due to the neglect of possible many-body interactions among PGNPs mediated by matrix polymers when the fraction of added polymers is high. These observations point to the need for a new framework to understand not only the structural behavior of PGNPs but also possibly their dynamics and thermo-mechanical properties as well. (C) 2015 AIP Publishing LLC.

Impurity effects on the critical behaviour of the electrical resistance of binary liquid mixtures

The electrical resistance of the binary liquid system cyclohexane + acetic anhydride is measured, in the critical region, both in the pure mixture and when the mixture is doped with small amounts (≈ 100 ppm) of H2O/D2O impurities.T c was approached to aboutt=3×10−6 wheret=(T −T c )/T c . The critical exponentb ≈ 0.35 in the fit of the resistance data to the equationdR/dT ∼t −b does not seem to be affected appreciably by the impurities. There is a sign reversal ofdR/dt in the non-critical region. Binary liquid systems seem to violate the universality of the critical resistivity.

Critical resistivity in impurity doped binary liquid mixtures

The electrical resistance of the critical binary liquid system C6H12+(CH3CO)2O is measured both in the pure form and when the system is doped with small amounts (≈ 100 ppm) of H2O impurities. Near Tc, the resistance varies as dR/dT = A1+A2 (T-Tc)-b with b ≈ 0.35. Neither the critical exponent b nor the amplitude ratio A1/A2 are affected by the impurities. A sign reversal of dR/dT is noticed at high temperatures T much greater-than Tc.

Brownian dynamics simulation of dense binary colloidal mixtures. II. Translational and bond-orientational order

We report the Brownian dynamics simulation results on the translational and bond-angle-orientational correlations for charged colloidal binary suspensions as the interparticle interactions are increased to form a crystalline (for a volume fraction phi = 0.2) or a glassy (phi = 0.3) state. The translational order is quantified in terms of the two- and four-point density autocorrelation functions whose comparisons show that there is no growing correlation length near the glass transition. The nearest-neighbor orientational order is determined in terms of the quadratic rotational invariant Q(l) and the bond-orientational correlation functions g(l)(t). The l dependence of Q(l) indicates that icosahedral (l = 6) order predominates at the cost of the cubic order (l = 4) near the glass as well as the crystal transition. The density and orientational correlation functions for a supercooled liquid freezing towards a glass fit well to the streched-exponential form exp[-(t/tau)(beta)]. The average relaxation times extracted from the fitted stretched-exponential functions as a function of effective temperatures T* obey the Arrhenius law for liquids freezing to a crystal whereas these obey the Vogel-Tamman-Fulcher law exp[AT(0)*/(T* - T-0*)] for supercooled Liquids tending towards a glassy state. The value of the parameter A suggests that the colloidal suspensions are ''fragile'' glass formers like the organic and molecular liquids.

Combustion and Thermal Decomposition of a Binary Oxidiser System: Ammonium Perchlorate-Potassium Perchlorate

Combustion behaviour of ammonium perchlorate-potassium perchlorate pellets is studied using Crawford strand burners. At low concentrations of potassium perchlorate (up to 30 percent potassium perchlorate) the burning rate of ammonium perchlorate-potassium perchlorate condensed mixtures increases with potassium perchlorate content. Above 40 percent potassium perchlorate content, combustion sustenance becomes difficult. Decomposition products of ammonium perchlorate sensitize the melting and subsequent decomposition of potassium perchlorate. The results are explained in terms of the melt layer thickness, flame temperature and the resultant surface temperature, and heat wave penetration into the solid. The study suggests the importance of melt layer on the burning surface in the deflagration behaviour of ammonium perchlorate-potassium perchlorate condensed mixtures

Critical point phenomena in the electrical resistivity of binary liquid systems: Cs2 + CH3CN and CS2 + CH3NO2

Electrical resistance measurements are reported on the binary liquid mixtures CS2 + CH3CN and CS2 + CH3NO2 with special reference to the critical region. Impurity conduction seems to be the dominant mechanism for charge transport. For the liquid mixture filled at the critical composition, the resistance of the system aboveT c follows the relationR=R c−A(T−T c) b withb=0·6±0·1. BelowT c the conductivities of the two phases obey a relation σ2−σ1=B(T c−T)β with β=0·34±0·02, the exponent of the transport coefficient being the same as the exponent of the order parameter, an equilibrium property.

Dynamic viscosity of gas mixtures

The viscosity of five binary gas mixtures - namely, oxygen-hydrogen, oxygen-nitrogen, oxygen-carbon dioxide, carbon dioxide-nitrogen, carbon dioxide-hydrogen - and two ternary mixtures - oxygen-nitrogen-carbon dioxide and oxygen-hydrogen-carbon dioxide - were determined at ambient temperature and pressure using an oscillating disk viscometer. The theoretical expressions of several investigators were in good agreement with the experimental results obtained with this viscometer. In the case of the ternary gas mixture oxygen-carbon dioxide-nitrogen, as long as the volumetric ratio of oxygen to carbon dioxide in the mixture was maintained at 11 to 8, the viscosity of the ternary mixture at ambient temperature and pressure remained constant irrespective of the percentage of nitrogen present in the mixture.

Critical behavior of electrical resistivity in polar + nonpolar binary liquid systems

The behavior of electrical resistivity in the critical region of three polar + nonpolar binary liquid systems CS2 +(CH3CO)2O, C6H12+(CH3CO)2O, and n‐C7H16+(CH3CO)2O is studied. For the mixtures with critical composition, the two phase region shows a conductivity behavior with σ1−σ2∼ (−ϵ)β with β?0.35. In the one phase region dR/dT has a singularity ϵ−b with b?0.35. A possible theory of the impurity conduction is given, which broadly explains these results. The possibility of dR/dT being positive or negative is also discussed.

Calorimetry In Vapor Absorption And Binary Mixture Vapor Compression Refrigeration And Heatpump Systems

The use of binary fluid systems in thermally driven vapour absorption and mechanically driven vapour compression refrigeration and heatpump cycles has provided an impetus for obtaining experimental date on caloric properties of such fluid mixtures. However, direct measurements of these properties are somewhat scarce in spite of the calorimetric techniques described in the literature being quite adequate. Most of the design data are derived through calculations using theoretical models and vapour-liquid equilibrium data. This article addresses the choice of working fluids and the current status on the data availability vis-a-vis engineering applications. Particular emphasis is on organic working fluid pairs.

Wet chemical formation of nanoparticles of binary perovskites through isothermal gel to crystallite conversion

Coarse BO2·xH2O (2 < x < 80) gels, free of anion contaminants react with A(OH)2 under refluxing conditions at 70�100°C giving rise to crystallites of single phased, nanometer size powders of ABO3 perovskites (A = Ba, Sr, Ca, Mg, Pb; B = Zr, Ti, Sn). Solid solutions of perovskites could be prepared from compositionally modified gels or mixtures of A(OH)2. Donor doped perovskites could also be prepared from the same method so that the products after processing are often semiconducting. Faster interfacial diffusion of A2+ ions into the gel generates the crystalline regions whose composition is controllable by the A/B ratio as well as the A(OH)2 concentration.