Stabilization and characterization of colloidal gas aphron dispersions

Colloidal gas aphrons (CGAs) are finding increasing application in water processing, bioseparation, bubble-entrained floc flotation, separation of oil from sand, etc. This article proposes an effective method of encapsulation to stabilize the CGA bubbles with silicic sol solution for their characterization. The stabilized CGA bubbles can keep shapes and sizes for at least 12 h; even the bubbles smaller than 25 mum can also be stabilized and exist for very long times. Effects of concentration and pH of silicic sol solution on CGA stabilization were studied. The optimal ranges of concentration and pH of silicic sol solution are 0.15-0.25 mol/dm(3) and 7-10, respectively. The bubble distortion behavior in disturbance and size distribution of CGAs were examined by using the stabilization method and photographic techniques.     

The critical gas saturation in a porous medium in the presence of gravity

The critical gas saturation, S(gc), denotes the volume fraction of the gas phase at the onset of bulk gas flow during the depressurization of a supersaturated liquid in a porous medium. In the absence of gradients due to viscous or gravity forces, S(gc) is controlled by nucleation, capillary forces, and the rate of decline of the supersaturation. In this paper we address one important additional effect, that of buoyancy. We use 2-D pore-network simulations, based on invasion percolation in a gradient (IPG), and corresponding scaling relations to obtain the dependence of S(gc) on the gravity Bond number, B, under conditions of slow growth, namely when mass transfer is sufficiently fast. The critical gas saturation approaches two plateau values at low and high Bond numbers. In the in-between region it scales as a power law of B, which for a 2-D lattice is S(gc) approximately B(-0.91).     

Synthesis of mesoporous TiO2 with colloidal gas aphrons,colloidal liquid aphrons,and colloidal emulsion aphrons for dye-sensitized solar cells

High surface area mesoporous titanium dioxide (TiO₂) particles have been prepared by three different kinds of colloidal aphrons: colloidal gas aphrons, colloidal liquid aphrons, and colloidal emulsion aphrons (CEAs). The precipitate of amorphous TiO₂ was prepared by hydrolysis, condensation, and polycondensation reaction of the precursor. The reaction took place under the effect of coulombic repulsion and electrostatic layers of multilayer surfactant molecules. TiO₂ particles with various sizes were prepared with different molar ratio of titanium ion to surfactants, which were sodium lauryl sulfate (SDS), cetyltrimetyhlammonium bromide, triblock copolymer Pluronic P123, and triblock copolymer Pluronic F127. The synthesized samples were characterized by X-ray diffraction, Brunauer-Emmett-Teller analysis, N₂ adsorption/desorption, and transmission electron microscopy. The mesoporous TiO₂ prepared by CEAs method showed a high specific surface area of 224 m²/g with the total pore volume of 0.7751 cm³/g by using SDS as the membrane phase surfactant due to electrostatic attraction favors of anionic surfactant. The solar conversion efficiency of the cell made from TiO₂ increases with the combination of increased surface area and total pore volume for higher amount of dye wetting and loading.     

Brownian Dynamics, Molecular Dynamics, and Monte Carlo modeling of colloidal systems

This paper serves as an introductory review of Brownian Dynamics (BD), Molecular Dynamics (MD), and Monte Carlo (MC) modeling techniques. These three simulation methods have proven to be exceptional investigative solutions for probing discrete molecular, ionic, and colloidal motions at their basic microscopic levels. The review offers a general study of the classical theories and algorithms that are foundational to Brownian Dynamics, Molecular Dynamics, and Monte Carlo simulations. Important topics of interest include fundamental theories that govern Brownian motion, the Langevin equation, the Verlet algorithm, and the Metropolis method. Brownian Dynamics demonstrates advantages over Molecular Dynamics as pertaining to the issue of time-scale separation. Monte Carlo methods exhibit strengths in terms of ease of implementation. Hybrid techniques that combine these methods and draw from these efficacies are also presented. With their rigorous microscopic approach, Brownian Dynamics, Molecular Dynamics, and Monte Carlo methods prove to be especially viable modeling methods for problems with challenging complexities such as high-level particle concentration and multiple particle interactions. These methods hold promising potential for effective modeling of transport in colloidal systems.     

Measuring the diffusion of noble gases through a porous medium using prompt gamma activation analysis

Detection of anthropogenic noble gas isotopes in the atmosphere is an important indication that a below ground nuclear-test has taken place. Diffusion plays a critical role in the transport of these gases through the geological media to the surface where they can be detected. Better techniques are need with which to study the diffusion of noble gases through porous systems. Here we demonstrate the suitability of using prompt gamma activation analysis to measure the time dependent concentration of argon as a result of its diffusion through a porous medium that is saturated with nitrogen at atmospheric pressure. The experiments were conducted in a 1 m long tube, 10 cm diameter, and packed with fine SiO₂ sand. Prompt gamma activation analysis was used to measure the concentration of argon within the experimental system as a function of time.     

Mathematical modeling of low-frequency oscillations observed in the diffusion of a substance through a membrane

In the diffusion process of a substance through a membrane under external steady-state conditions, low-frequency oscillations in its concentration are observed experimentally. A theoretical explanation for this phenomenon is given, and the results of mathematical modeling are presented. Models based on local membrane conductivity as a function of solution concentration are examined. It is shown in this case that positive feedback develops between changes in the flows and concentrations, and this determines the development of oscillations in the diffusion process of a substance.     

Effect of viscous dissipation on MHD water-Cu and EG-Cu nanofluids flowing through a porous medium

This paper provides a comparative analysis of two different types of nanofluids for Stokes second problem. Additional effects of MHD, porosity and viscous dissipation are also considered. Two types of Newtonian liquids (water and ethylene glycol) are considered as base fluids with suspended nanosized Cu particles. A homogenous model of Newtonian nanofluids over a flat plate is used to describe this phenomenon with Stokes boundary conditions such that the ambient fluid is static and with uniform temperature. The problem is first written in terms of nonlinear partial differential equations with physical conditions; then after non-dimensional analysis, the Laplace transform method is used for its closed-form solution. Exact expressions are determined for the dimensionless temperature, velocity field, Nusselt number and skin friction coefficient and arranged in terms of exponential and complementary error functions satisfying the governing equations and boundary conditions. They are also reduced to the known solutions of Stokes second problem for Cu-water nanofluids. Results are computed using Maple software. The results showed that both skin friction and rate of heat transfer increase with increasing solid volume fraction of nanoparticles. MHD and porosity had an opposite effect on velocity for both types of nanofluids. The dimensionless temperature increases by increasing the Eckert and Hartmann numbers.

     

Predispersed solvent extraction of dilute products using colloidal gas aphrons and colloidal liquid aphrons: Aphron preparation,stability and size

Early work on colloidal gas aphrons (CGAs) and Colloidal liquid aphrons (CLAs) has shown that they have considerable potential in the field of predispersed solvent extraction (PDSE). While their area of application is potentially very broad, their most promising use is in downstream separation in biotechnology where products are very dilute and occur in complex mixtures. Since little work has been done in this area, this preliminary study examined the influence of a range or solvents, varying from non-polar to mildly polar, and a variety of ionic and non-ionic surfactants, on CLA size, stability and phase volume ratio (PVR, volume ratio of the dispersed oil phase to the continuous aqueous phase). In addition, the effect of surfactant type, stirring speed and time, on the formation of CGAs was also studied. The results show that CLAs can be formulated with quite polar solvents (e.g. pentanol), and their stability increases as the HLB (hydrophilic/lipophilic balance) number of the non-ionic surfactant increases. CLAs could be formulated with PVRs as high as 20 without coalescence, which is markedly higher than with microemulsions, and seems to indicate that the liquid aphrons are stabilised by more than a surfactant monolayer. Finally, it was found that CGAs could be formulated as a foam with a half-life of 6 min, and that they could be used to separate dispersed CLAs effectively from a bulk solution.     

Mathematical modeling of the graft reaction between polystyrene and polyethylene

Polystyrene (PS) and polyethylene (PE) are two major components of household plastic waste whose blends are immiscible. Recycling them together is an attractive option that requires a compatibilization process to improve the blend mechanical properties. If a PE/PS copolymer is added or formed in situ, it may act as compatibilizer. The structure and molecular properties of this copolymer are key factors to assure its effectivity as a compatibilizer. In this work, we study the graft copolymerization reaction between polystyrene and polyethylene using the catalytic system composed of AlCl₃ and styrene. We develop a model of this process which considers that PE/PS grafting and PS degradation occur simultaneously. We propose a kinetic mechanism for the whole process and apply the method of moments to solve the mass balance equations. The model is able to calculate average molecular weights as well as the amount of grafted PS. It accurately describes the available experimental data, constituting a valuable tool for simulation and optimization purposes.     

Diffusion of a passive impurity through a porous media: fractal model in an unsaturated medium

The theory of fractal sets is used to describe convective diffusion of a passive impurity in a partly-saturated porous medium.     

Analysis of pulsed laser plasmon-assisted photothermal heating and bubble generation at the nanoscale

A study is presented of photothermal effects associated with nanosecond-pulsed laser-illuminated subwavelength metallic nanoparticles in aqueous solutions. Computational electromagnetic and fluid analysis are used to model fundamental aspects of the photothermal process taking into account energy conversion within the nanoparticle at plasmon resonance, heat transfer to the fluid, homogeneous bubble nucleation, and the dynamic behaviour of the bubble and surrounding fluid. Various nanoparticle geometries are modelled including spheres, nanorods and tori. The analysis demonstrates that the laser intensity and pulse duration can be tuned to achieve controllable bubble generation without exceeding the melting temperature of the particle. The analysis also shows that the particle geometry can be tuned to optimize photothermal energy conversion for bubble generation at wavelengths that span the UV to NIR spectrum. Multiparticle systems are studied and a cooperative heating effect is demonstrated for particles that are within a few radii of each other. This provides more robust bubble generation using substantially reduced laser energy as compared to single-particle systems. The modelling approach is discussed in detail and should be of considerable use in the development of new photothermal applications.     

Mathematical modeling of the myosin light chain kinase activation

The mathematical model presented here describes the interactions among Ca2+, calmodulin (CaM), and myosin light chain kinase (MLCK) and consists of a kinetic scheme taking into account 7 reactions instead of 12 as proposed previously. We derive a system of 5 nonlinear ordinary differential equations. Solving it yields the prediction of active MLCK as a function of [Ca2+] whereby the active MLCK is defined to be proportional to the Ca4CaM.MLCK complex concentration. The model predictions are compared with other theoretical and experimental predictions of active MLCK as well as with the results of our previously proposed complex model.     

Determination of pore sizes and volumes of porous materials by 129Xe NMR of xenon gas dissolved in a medium

In our previous paper (J. Phys. Chem. B 2005, 109, 757) it was illustrated that the 129Xe NMR spectra of xenon dissolved in acetonitrile confined into mesoporous materials give detailed information on the system, especially about the pore sizes. A resonance signal originating from xenon atoms sited in very small cavities built up inside the pores during the freezing transition (referred to as signal D) turned out to be highly sensitive to the pore size. The emergence of this signal reveals the phase transition temperature of acetonitrile inside the pores, which can also be used to determine the size of the pores. In addition, the difference in the chemical shifts of two other signals arising from xenon dissolved in bulk and confined acetonitrile (B and C) provides another method for determining the pore sizes. In the present work, the observed correlations have been investigated using an extensive set of measurements with a variety of porous materials (silica gels and controlled pore glasses) with the mean pore diameters ranging from 43 to 2917 A. The usefulness of the correlations has been demonstrated by calculating the pore size distributions from the spectral data. The distributions are in agreement with those reported by the manufacturers, when the mean pore diameter is smaller than approximately 500 A. In addition, it has been shown that the porosity of the materials can be determined by comparing the intensities of the signals arising from the bulk and confined liquid. When acetonitrile is replaced by cyclohexane in the sample, the dependence of the chemical shift difference between the B and C signals on the pore size becomes more sensitive, but no D signal appears below the freezing point. In addition, the influence of xenon gas on the melting points of bulk and confined acetonitrile has been studied by 1H NMR cryoporometry. The measurements show that the temperature of the latter transition lowers slightly more, and consequently affects the pore sizes calculated by means of the difference in the phase transition temperatures. Hysteresis in the phase transitions in a cooling-warming cycle has also been studied as a function of the temperature stabilization time by 129Xe NMR of xenon dissolved in acetonitrile.     

Self-sustaining peristaltic motion on the surface of a porous gel

We report the structural color behavior of a periodic ordered mesoporous gel synchronized with the Belousov-Zhabotinsky (BZ) reaction. The structural colored concentric rings which were spatiotemporally spread out on the porous gel were observed during the BZ reaction. The color tone of the structural color, which is determined by the swelling ratio of the gel, was periodically changed. This is the first evidence that a self-sustaining peristaltic motion occurs on the surface of a gel.     

On the influence of size, zeta potential, and state of motion of dispersed particles on the conductivity of a colloidal suspension

The dependence of the DC conductivity of diluted colloidal suspensions on the size, zeta potential, and state of motion of the dispersed particles is analyzed both theoretically and numerically. It is shown that the simple formula that represents the conductivity as a sum of products: charge times mobility, taken over all the carriers present in the suspension, is only valid for exceedingly low values of the product kappaa. In contrast, the formulation based on the value of the dipolar coefficient of the suspended particles seems to be valid for all the range of particle sizes. This assertion is only true if the dipolar coefficient is calculated taking into account the electrophoretic motion of the particles. For very low values of the product kappaa, the dipolar coefficient of particles free to move can be several orders of magnitude larger than that of immobile particles.     

The effect of ph and gas composition on the bubble fractionation of proteins

Studies were conducted to establish the effect of the variation of environmental factors on the separation occurring in protein systems, resulting from bubble fractionation in a bioreactor. The measure of separation was selected to be the separation ratio. This is defined to be the ratio of either the top or the middle position concentration in the vessel to the bottom concentration of the vessel. Invertase and α-amylase were the two “model” enzymes considered. It was observed that, under certain conditions, i.e., a combination of the nature of the sparging gas and the medium pH, varying degrees of protein separation were achieved. The pH of the system dramatically influenced the separation. It was found that the best separation occurred at a certain pH, assumed to be at or close to thepI of the protein in question. Furthermore, it was observed that systems sparged with CO₂ exhibited greater separation than systems sparged with air. In fact, in the case of invertase, almost threefold separation was observed at the top port when the solution was sparged with CO₂.     

A double layer model of the gas bubble/water interface

Zeta potential is a physico-chemical parameter of particular importance to describe sorption of contaminants at the surface of gas bubbles. Nevertheless, the interpretation of electrophoretic mobilities of gas bubbles is complex. This is due to the specific behavior of the gas at interface and to the excess of electrical charge at interface, which is responsible for surface conductivity. We developed a surface complexation model based on the presence of negative surface sites because the balance of accepting and donating hydrogen bonds is broken at interface. By considering protons adsorbed on these sites followed by a diffuse layer, the electrical potential at the head-end of the diffuse layer is computed and considered to be equal to the zeta potential. The predicted zeta potential values are in very good agreement with the experimental data of H₂ bubbles for a broad range of pH and NaCl concentrations. This implies that the shear plane is located at the head-end of the diffuse layer, contradicting the assumption of the presence of a stagnant diffuse layer at the gas/water interface. Our model also successfully predicts the surface tension of air bubbles in a KCl solution.     

Mathematical modeling and simulation of the reaction environment in electrochemical reactors

An electrochemical reactor, enabling controlled flow and capable of including a varied range of forms of electrodes, is important in the studies of electrochemical processes, such as energy production and storage, electrosynthesis of chemicals, electrowinning of metals, purification of water, wastewater treatment, remediation of soils, and so on, before the process development and scale-up. Here, we reviewed recent advances in modeling and simulation of the reaction environment in many electrochemical reactors used in multiple applications. The importance of computational fluid dynamics simulations to study existing reactors and to design novel reactor geometries and some components of existing cells is discussed. Aspects include the effect of electrolyte velocity on the flow dispersion, mass transport rates, and current distribution.     

Theory of nonstationary diffusion growth of gas bubble in the supersaturated solution of gas in liquid

General theory of nonstationary diffusion growth of gas bubble in the supersaturated solution of gas in liquid is constructed using the ideas of similarity and self-similar solutions. The balance between the number of gas molecules in solution and in the bubble that displaces incompressible liquid solvent with an increase in bubble size is taken into account at the material isolation of the solution and the bubble. The dependences of the rate of growth of bubble radius on the solubility of gas and the supersaturation of solution are found. The nonstationary effect of a rapid increase in the rate of bubble growth with an increase in the product of gas solubility and solution supersaturation is elucidated. The upper limit of this product at which bubble growth can be considered as isothermal process is established. The theory is constructed at the arbitrary gas solubility.