Advances in Colloid and Interface Science (v.159, #2)

Gerard Fleer by Hans Lyklema; Martien Cohen Stuart; Frans Leermakers (95-98).

This review is an extended version of the Overbeek lecture 2009, given at the occasion of the 23rd Conference of ECIS (European Colloid and Interface Society) in Antalya, where I received the fifth Overbeek Gold Medal awarded by ECIS.I first summarize the basics of numerical SF-SCF: the Scheutjens–Fleer version of Self-Consistent-Field theory for inhomogeneous systems, including polymer adsorption and depletion. The conformational statistics are taken from the (non-SCF) DiMarzio–Rubin lattice model for homopolymer adsorption, which enumerates the conformational details exactly by a discrete propagator for the endpoint distribution but does not account for polymer–solvent interaction and for the volume-filling constraint. SF-SCF corrects for this by adjusting the field such that it becomes self-consistent. The model can be generalized to more complex systems: polydispersity, brushes, random and block copolymers, polyelectrolytes, branching, surfactants, micelles, membranes, vesicles, wetting, etc. On a mean-field level the results are exact; the disadvantage is that only numerical data are obtained. Extensions to excluded-volume polymers are in progress.Analytical approximations for simple systems are based upon solving the Edwards diffusion equation. This equation is the continuum variant of the lattice propagator, but ignores the finite segment size (analogous to the Poisson–Boltzmann equation without a Stern layer). By using the discrete propagator for segments next to the surface as the boundary condition in the continuum model, the finite segment size can be introduced into the continuum description, like the ion size in the Stern–Poisson–Boltzmann model. In most cases a ground-state approximation is needed to find analytical solutions. In this way realistic analytical approximations for simple cases can be found, including depletion effects that occur in mixtures of colloids plus non-adsorbing polymers.In the final part of this review I discuss a generalization of the free-volume theory (FVT) for the phase behavior of colloids and non-adsorbing polymer. In FVT the polymer is considered to be ideal: the osmotic pressure Π follows the Van 't Hoff law, the depletion thickness δ equals the radius of gyration. This restricts the validity of FVT to the so-called colloid limit (polymer much smaller than the colloids). We have been able to find simple analytical approximations for Π and δ which account for non-ideality and include established results for the semidilute limit. So we could generalize FVT to GFVT, and can now also describe the so-called protein limit (polymer larger than the ‘protein-like’ colloids), where the binodal polymer concentrations scale in a simple way with the polymer/colloid size ratio. For an intermediate case (polymer size ≈ colloid size) we could give a quantitative description of careful experimental data.
Keywords: Polymer adsorption; Polymer depletion; Scheutjens–Fleer theory; Continuum theory with finite segment size; Boundary condition in Edwards equation; Crossover from dilute to semidilute limits; Depletion thickness; Phase diagrams; Generalized free-volume theory;

Extended space charge in concentration polarization by Isaak Rubinstein; Boris Zaltzman (117-129).
This paper is concerned with ionic currents from an electrolyte solution into a charge-selective solid, such as, an electrode, an ion-exchange membrane or an array of nano-channels in a micro-fluidic system, and the related viscous fluid flows on the length scales varying from nanometers to millimeters. All systems of this kind have characteristic voltage–current curves with segments in which current nearly saturates at some plateau values due to concentration polarization — formation of solute concentration gradients under the passage of a DC current. A number of seemingly different phenomena occurring in that range, such as anomalous rectification in cathodic copper deposition from a copper sulfate solution, super-fast vortexes near an ion-exchange granule, overlimiting conductance in electrodialysis and the recently observed non-equilibrium electroosmotic instability, result from the formation of an additional extended space charge layer next to that of a classical electrical double layer at the solid/liquid interface. In this paper we review the peculiar features of the non-equilibrium electric double layer and extended space charge and the possibility of their direct probing by harmonic voltage/current perturbations through a linear and non-linear system's response, by the methods of electrical impedance spectroscopy and via the anomalous rectification effect. On the relevant microscopic scales the ionic transport in the direction normal to the interface is dominated by drift–diffusion; hence, the extended space charge related viscous flows remain beyond the scope of this paper.
Keywords: Extended space charge; Concentration polarization; Overlimiting conductance; Non-equilibrium electroosmotic instability;

Water scarcity and pollution rank equal to climate change as the most urgent environmental turmoil for the 21st century. To date, the percolation of textile effluents into the waterways and aquifer systems, remain an intricate conundrum abroad the nations. With the renaissance of activated carbon, there has been a steadily growing interest in the research field. Recently, the adoption of titanium dioxide, a prestigious advanced photo-catalyst which formulates the new growing branch of activated carbon composites for enhancement of adsorption rate and discoloration capacity, has attracted stern consideration and supports worldwide. Confirming the assertion, this paper presents a state of art review of titanium dioxide/activated carbon composites technology, its fundamental background studies, and environmental implications. Moreover, its major challenges together with the future expectation are summarized and discussed. Conclusively, the expanding of activated carbons composites material represents a potentially viable and powerful tool, leading to the plausible improvement of environmental conservation.
Keywords: Activated carbon; Adsorption; Composites; Textile; Titanium dioxide;

Droplet impact has been studied for over a hundred years dating back to the pioneering work of Worthington [1]. In fact, much of his ingenuity contributed to modern day high speed photography. Over the past 40 years significant contributions in theoretical, numerical, and experimental work have been made. Droplet impact is a problem of fundamental importance due to the wealth of applications involved, namely, spray coating, spray painting, delivery of agricultural chemicals, spray cooling, inkjet printing, soil erosion due to rain drop impact, and turbine wear. Here we highlight one specific application, spray coating. Although most studies have focused their efforts on low viscosity Newtonian fluids, many industrial applications such as spray coating utilize more viscous and complex rheology liquids. Determining dominant effects and quantifying their behavior for colloidal suspensions and polymer solutions remains a challenge and thus has eluded much effort. In the last decade, it has been shown that introducing polymers to Newtonian solutions inhibits the rebounding of a drop upon impact, Bergeron et al. [2]. Furthermore Bartolo et al. [3] concluded that the normal stress component of the elongational viscosity was responsible for the rebounding inhibition of polymer based non-Newtonian solutions. We aim to uncover the drop impact dynamics of highly viscous Newtonian and complex rheology liquids used in pharmaceutical coating processes. The generation and impact of drops of mm and μm size drops of coating liquids and glycerol/water mixtures on tablet surfaces are systematically studied over a range of We  ∼  O (1–300), Oh  ∼  O (10− 2–1), and Re  ∼  O (1–700). We extend the range of Oh to values above 1, which are not available to previous studies of droplet impacts. Outcomes reveal that splashing and rebounding are completely inhibited and the role of wettability is negligible in the early stages of impact. The maximum spreading diameter of the drop is compared with three models demonstrating reasonable agreement.
Keywords: Impact; Spreading; Colloidal dispersions; Tablet Spray coating;

A new method, based upon semi-empirical kinetic approach, for the determination of ion exchange constant for ion exchange processes occurring between counterions at the cationic micellar surface is described in this review article. Basically, the method involves a reaction kinetic probe which gives observed pseudo-first-order rate constants (kobs) for a nucleophilic substitution reaction between the nonionic and anionic reactants (R and S) in the presence of a constant concentration of both reactants as well as cationic micelles and varying concentrations of an inert inorganic or organic salt (MX). The observed data (kobs, versus [MX]) fit satisfactorily (in terms of residual errors) to an empirical equation which could be derived from an equation explaining the mechanism of the reaction of the kinetic probe in terms of pseudophase micellar (PM) model coupled with another empirical equation. This (another) empirical equation explains the effect of [MX] on cationic micellar binding constant (KS) of the anionic reactant (say S) and gives an empirical constant, KX/S. The magnitude of KX/S is the measure of the ability of X to expel S from a cationic micellar pseudophase to the bulk aqueous phase through ion exchange X/S. The values of KX/S and KY/S (where Y is another inert counterion) give the ion exchange constant, KX Y (= KX/KY where KX and KY represent cationic micellar binding constants of X and Y, respectively). The suitability of this method is demonstrated by the use of three different reaction kinetic probes and various MX.
Keywords: Ionic micelles; Spherical; Rodlike; Threadlike; Ion exchange constants, KX Y; Determination of KX Y; New semi-empirical kinetic method;

Selective recognition of organic pollutants in aqueous solutions with composite imprinted membranes by Victor Kochkodan; Nidal Hilal; Volodimir Melnik; Olga Kochkodan; Olexandr Vasilenko (180-188).
In this work, thin-layer composite membranes imprinted with desmetryn or ibuprofen were prepared and studied for selective recognition of the template compounds in aqueous solutions. The imprinted membranes were developed using photoinitiated copolymerization of 2-acrylamido-2-methyl-1-propane sulphonic acid and N,N'-methylene-bis-acrylamide, in the presence of desmetryn or via copolymerization of dimethylaminoethyl methacrylate, and trimethylopropane trimethacrylate, in the presence of ibuprofen, followed by deposition of the imprinted layers on the surface of porous microfiltration supports of various chemical nature. Atomic force microscopy was used to study the surface morphological characteristics of the developed membranes. Molecularly recognition properties of imprinted membranes were evaluated by measuring their capability to bind the template molecules from polycomponent aqueous solutions. It was shown that obtained membranes may be used as selective recognising elements of portative differential capacitor sensor device for express monitoring of the target molecules in water. The sensor performance is based on registration of the alteration of dielectric permeability of composite imprinted membrane at selective binding of template molecules, when the analyzed feed solution is filtered through the membrane sample.
Keywords: Composite imprinted membrane; Molecular recognition; Desmetryn; Ibuprofen; Sensor device; Atomic force microscopy;

Natural organic matter removal by coagulation during drinking water treatment: A review by Anu Matilainen; Mikko Vepsäläinen; Mika Sillanpää (189-197).
Natural organic matter (NOM) is found in all surface, ground and soil waters. An increase in the amount of NOM has been observed over the past 10–20 years in raw water supplies in several areas, which has a significant effect on drinking water treatment. The presence of NOM causes many problems in drinking water and drinking water treatment processes, including (i) negative effect on water quality by causing colour, taste and odor problems, (ii) increased coagulant and disinfectant doses (which in turn results in increased sludge volumes and production of harmful disinfection by-products), (iii) promoted biological growth in distribution system, and (iv) increased levels of complexed heavy metals and adsorbed organic pollutants. NOM can be removed from drinking water by several treatment options, of which the most common and economically feasible processes are considered to be coagulation and flocculation followed by sedimentation/flotation and sand filtration. Most of the NOM can be removed by coagulation, although, the hydrophobic fraction and high molar mass compounds of NOM are removed more efficiently than hydrophilic fraction and the low molar mass compounds. Thus, enhanced and/or optimized coagulation, as well as new process alternatives for the better removal of NOM by coagulation process has been suggested. In the present work, an overview of the recent research dealing with coagulation and flocculation in the removal of NOM from drinking water is presented.
Keywords: NOM; Natural organic matter; Coagulation; Drinking water; Water treatment;

Surface tension of liquid metals and alloys — Recent developments by I. Egry; E. Ricci; R. Novakovic; S. Ozawa (198-212).
Surface tension measurements are a central task in the study of surfaces and interfaces. For liquid metals, they are complicated by the high temperatures and the consequently high reactivity characterising these melts. In particular, oxidation of the liquid surface in combination with evaporation phenomena requires a stringent control of the experimental conditions, and an appropriate theoretical treatment. Recently, much progress has been made on both sides. In addition to improving the conventional sessile drop technique, new containerless methods have been developed for surface tension measurements. This paper reviews the experimental progress made in the last few years, and the theoretical framework required for modelling and understanding the relevant physico-chemical surface phenomena.
Keywords: Surface tension; Liquid metals; Butler equation; Oxygen partial pressure; Surface segregation;

There is a need for edible delivery systems to encapsulate, protect and release bioactive and functional lipophilic constituents within the food and pharmaceutical industries. These delivery systems could be used for a number of purposes: controlling lipid bioavailability; targeting the delivery of bioactive components within the gastrointestinal tract; and designing food matrices that delay lipid digestion and induce satiety. Emulsion technology is particularly suited for the design and fabrication of delivery systems for lipids. In this article we provide an overview of a number of emulsion-based technologies that can be used as edible delivery systems by the food and other industries, including conventional emulsions, nanoemulsions, multilayer emulsions, solid lipid particles, and filled hydrogel particles. Each of these delivery systems can be produced from food-grade (GRAS) ingredients (e.g., lipids, proteins, polysaccharides, surfactants, and minerals) using relatively simple processing operations (e.g., mixing, homogenizing, and thermal processing). The structure, preparation, and utilization of each type of delivery system for controlling lipid digestion are discussed. This knowledge can be used to select the most appropriate emulsion-based delivery system for specific applications, such as encapsulation, controlled digestion, and targeted release.
Keywords: Nutraceuticals; Pharmaceuticals; Functional foods; Delivery systems; Structural design; Hydrogel particles; Coacervates; Emulsions; Nanoemulsions; Satiety;