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Advances in Colloid and Interface Science (v.122, #1-3)
Thermodynamic and kinetic aspects of fat crystallization by C. Himawan; V.M. Starov; A.G.F. Stapley (pp. 3-33).
Naturally occurring fats are multi-component mixtures of triacylglycerols (TAGs), which are triesters of fatty acids with glycerol, and of which there are many chemically distinct compounds. Due to the importance of fats to the food and consumer products industries, fat crystallization has been studied for many years and many intricate features of TAG interactions, complicated by polymorphism, have been identified. The melting and crystallization properties of triacylglycerols are very sensitive to even small differences in fatty acid composition and position within the TAG molecule which cause steric hindrance. Differences of fatty acid chain length within a TAG lead to packing imperfections, and differences in chain lengths between different TAG molecules lead to a loss of intersolubility in the solid phase. The degree of saturation is hugely important as the presence of a double bond in a fatty acid chain causes rigid kinks in the fatty acid chains that produce huge disruption to packing structures with the result that TAGs containing double bonds have much lower melting points than completely saturated TAGs. All of these effects are more pronounced in the most stable polymorphic forms, which require the most efficient molecular packing. The crystallization of fats is complicated not just by polymorphism, but also because it usually occurs from a multi-component melt rather than from a solvent which is more common in other industrial crystallizations. This renders the conventional treatment of crystallization as a result of supersaturation somewhat meaningless. Most studies in the literature consequently quantify crystallization driving forces using the concept of supercooling below a distinct melting point. However whilst this is theoretically valid for a single component system, it can only at best represent a rough approximation for natural fat systems, which display a range of melting points. This paper reviews the latest attempts to describe the sometimes complex phase equilibria of fats using fundamental relationships for chemical potential that have so far been applied to individual species in melts of unary, binary and ternary systems. These can then be used to provide a framework for quantifying the true crystallization driving forces of individual components within a multi-component melt. These are directly related to nucleation and growth rates, and are also important in the prediction of polymorphic occurrence, crystal morphology and surface roughness. The methods currently used to evaluate induction time, nucleation rate and overall crystallization rate data are also briefly described. However, mechanistic explanations for much of the observed crystallization behaviour of TAG mixtures remain unresolved.
Keywords: Nucleation; Crystal growth; Triacylglycerol; Melts; Polymorphism; Crystal morphology
Dynamically arrested states of matter by Kenneth A. Dawson; Paolo De Gregorio; Aonghus Lawlor (pp. 35-38).
We outline current developments in our understanding of dynamical arrest, that phenomenon in which many particles stop moving in a collective manner. However in addition to the question of true dynamical arrest itself, we emphasize the development of new tools that can describe relatively sharp changes in the way that ergodic systems may be explored. We discuss the concept of new order parameters (dynamically available volume), and indicate how they may be applied to understand dramatic slowing phenomena present in particle systems, and other arenas of soft and complex matter.
The Hofmeister series effect in adsorption of cationic surfactants—theoretical description and experimental results by G. Para; E. Jarek; P. Warszynski (pp. 39-55).
Interfacial properties of cationic surfactants show strong dependence on the type of surfactant counterion or on the type of anion of a salt added to the surfactant solution. In the paper, the models of ionic surfactant adsorption that can take into account ionic specific effects are reviewed. Model of ionic surfactant adsorption based on the assumption that the surfactant ions and counterions undergo nonequivalent adsorption within the Stern layer was selected to describe experimental surface tension isotherms of aqueous solutions of a number of cationic surfactants. The experimental isotherms for: n-alkyl trimethylammonium cationic surfactants, namely: C16TABr (CTABr or CTAB), C16TACl, C16TAHSO4, C10TABr and C12TABr as well as decyl- and dodecylpyridinium salts with and without various electrolyte anions as Cl−, Br−, F−, I−, NO3−, ClO4− and CH3COO− were described in terms of the model and a good agreement between the theory and experiment was obtained for a wide range of surfactants and added electrolyte concentrations. A very pronounced Hofmeister effect in dependence of surface tension of cationic surfactants on the type of anion was found. Analysing this dependence in terms of the proposed model of ionic surfactant adsorption, strong correlation between “anion surface activity� (the model parameter accounting for ion penetration into the Stern layer), and the ion polarizability was obtained. That suggests that the mechanism related to the dispersive interaction of polarized ion with electric field at interface is responsible for Hofmeister series effects in surface activity of cationic surfactants. The same mechanism was proposed recently to explain the dependence of surface tension increase with electrolyte concentration on anion and cation type.
Surface dilational rheology of mixed adsorption layers at liquid interfaces by E.V. Aksenenko; V.I. Kovalchuk; V.B. Fainerman; R. Miller (pp. 57-66).
The dilational rheology for mixed solutions of surface active compounds is easy to measure with existing methods, however, there are very few attempts only to analyse the resulting data on the basis of a theoretical model. Models by Jiang et al., Joos, and by Lucassen and van den Tempel (for single compounds) are compared here and applied to experimental data. The mentioned models converge to each other after some small modifications and represent a very good scientific background for studies of the mechanical behaviour of mixed adsorption layers. As example, the experimental results for mixed solutions containing a globular protein (β-lactoglobulin) and a non-ionic surfactant (alkyl dimethyl phosphine oxide) are analysed by the obtained dependencies, using some new proposed numerical procedures.
Fourier-transform rheology of polymer Langmuir monolayers: Analysis of the non-linear and plastic behaviors by Hani Hilles; Francisco Monroy; Laura J. Bonales; Francisco Ortega; Ramón G. Rubio (pp. 67-77).
The linear regime (LR) of viscoelastic behavior has been found to be limited to rather small values of strain, well below the strains found in many technological processes. A Fourier-transform method is described for analyzing the surface rheology data obtained in insoluble Langmuir polymer monolayers beyond the LR. In the concentrate regime, the monolayers show a transition from elastic to plastic behavior, which is characterized by high irreversibility. A simple 2-D rubber model is presented that describes the behavior of the monolayers in the non-linear region not too far from the end of the LR.
Keywords: Polymer monolayers; Surface rheology; FT-rheology; Non-linear regime; Elasto-plastic behavior
Modeling local flotation frequency in a turbulent flow field by Margaritis Kostoglou; Thodoris D. Karapantsios; Kostas A. Matis (pp. 79-91).
Despite the significance of turbulent fluid motion for enhancing the flotation rate in several industrial processes, there is no unified approach to the modeling of the flotation rate in a turbulent flow field. Appropriate modeling of the local flotation (bubble–particle attachment) rate is the basic constituent for global modeling and prediction of flotation equipment efficiency. Existing approaches for the local flotation rate are limited to specific set of conditions like high or low turbulence. In addition, the combined effects of buoyant bubble rise and/or particle gravity settling are usually ignored. The situation is even vaguer for the computation of collision and attachment efficiencies which are usually computed using the gravity induced velocities although the dominant mode of flotation is the turbulent one. The scope of this work is clear: the development of a general expression for the flotation rate in a turbulent flow field which will cover in a unified and consistent way all possible sets of the problem parameters. This is achieved by using concepts from statistical approach to homogeneous turbulence and gas kinetic theory.
Keywords: Flotation process; Mathematical modeling; Stochastic encounters; Turbulent flow field; Bubble–particle attachment frequency
Electrokinetic fingerprinting of grafted polyelectrolyte layers—a theoretical approach by Stanislav S. Dukhin; Ralf Zimmermann; Carsten Werner (pp. 93-105).
Electrokinetic fingerprinting (EF) was introduced by Marlow and Rowell [Marlow BJ, Rowel RL. Langmuir 1990;6:1088] for the comprehensive characterization of charged particle surfaces. Afterwards, EF was applied by many groups for the characterization of “hard� (i.e. non-swelling) surfaces. However, the advantages of EF could not yet utilized for the characterization of grafted polyelectrolyte layers (PL) since the theoretical background was not yet elaborated.A theory for the characterization of PL at complete dissociation of the functional groups was developed by Ohshima [Adv Colloid Interface Sci 1995;62:189] and later extended by Dukhin et al. [Dukhin S, Zimmermann R, Werner C. J Colloid Interface Sci 2005;286:761] for any degree of dissociation. Further progress in the characterization of soft surfaces may be achieved by combining EF and surface conductivity (SC) measurements. Both theory and experiment demonstrate that integrated measurements of SC and apparent zeta potential ζa in broad ranges of pH and ionic strength provide information about Donnan potential ΨD, surface charge, p K and surface potential Ψ0, while the interpretation is more uncertain, when only ζa is measured. This advanced method of PL characterization is established for PL grafted on flat surfaces. When PL are formed on spherical particles, the SC may be measured by means of conductometry and/or dielectric spectroscopy. However, the current theories can only be applied within a rather narrow range of the practically relevant conditions. To overcome this limitation, an unified approach to the theory of electrophoresis for spherical particles with grafted PL was elaborated taking into account the existence of two different electrokinetic models for soft surfaces. While one model is focused on hydrodynamic permeability of soft surface and disregards surface current, another model considers the surface current and disregards electrokinetic water transport within the soft surface layer. Unification became possible through generalization of the capillary osmosis theory over soft surfaces.
Keywords: Electrokinetic fingerprinting; Soft surfaces; Electrokinetics; Grafted polyelectrolyte layers; Zeta potential; Donnan potential; Surface potential; Surface conductivity
Metallosurfactants: Interfaces and micelles by P.C. Griffiths; I.A. Fallis; T. Chuenpratoom; R. Watanesk (pp. 107-117).
Incorporating a metal cation as an integral component of the headgroup of a surfactant – a metallosurfactant – offers a route to concentrate these ions and their associated functionality at interfaces. To reduce the lability of the metal, various chelating or macrocyclic ligands may be employed leading to a family of homologous series of related metallosurfactants with a structural diversity that is arguably broader than is inherently possible with conventional surfactants. This review discusses the small number of key papers that are quantifying the physico–chemical properties of metallosurfactants and highlights their “classical� as well as “non-classical� surfactant behaviour, providing an insight into the structure of micelles and films formed from these novel materials.
Keywords: Aggregation; Adsorption; Surface layers; Metal ion; Self-association
Effects of organic ligands, electrostatic and magnetic interactions in formation of colloidal and interfacial inorganic nanostructures by G.B. Khomutov; Yu.A. Koksharov (pp. 119-147).
This paper discusses effects of organic ligands, electrostatic and magnetic interactions involved in morphological control of chemically synthesized inorganic nanostructures including colloid and planar systems. The special attention was concentrated on noble metal (gold and palladium) nanoparticles and nanostructures formed at the gas–liquid interface. The analysis of experimental data showed that electrostatic and ligand-related interactions influence very strongly on the metal nanostructure morphology. The hydrophobicity of ligand, charge and binding affinity to inorganic phase are important factors influencing the morphology of inorganic nanostructures formed in a layer at the gas/liquid interface by the interfacial synthesis method. The important point of this method is the quasi two-dimensional character of reaction area and possibilities to realize ultimately thin and anisotropic dynamic monomolecular reaction system with two-dimensional diffusion and interactions of precursors, intermediates and ligands resulting in planar growth and organization of inorganic nanoparticles and nanostructures in the plain of Langmuir monolayer. The morphology of resulting inorganic nanostructures can be controlled efficiently by variations of growth conditions via changes in state and composition of interfacial planar reaction media with the same precursor, and by variations of composition of adjacent bulk phases. The extreme anisotropy and heterogeneity of two-dimensional interfacial reaction system allows creating conditions when growing inorganic particles floating on the aqueous phase surface interact selectively with hydrophobic water-insoluble ligands in interfacial monolayer or with hydrophilic bulk-phase ligands, or at the same time with ligands of different nature present in monolayer and in aqueous phase. The spatial anisotropy of interfacial reaction system and non-homogeneity of ligand binding to inorganic phase gives possibilities for growth of integrated anisotropic nanostructures with unique morphologies, in particularly those characterized by very high surface/volume ratio, high effective perimeter, and labyrinth-like structure.In a case of magnetic nanoparticles dispersed in colloids specific magnetic dipolar interactions can result in formation of chains, rings and more complex nanoparticulate structures or separated highly anisotropic nanoparticles.Theoretical considerations indicate to the importance of system dimensionality in relation to the energy balance which determines specific features of structure organization in planar charged metallic and magnetic nanostructures. For example, a requirement of Coulomb energy minimum, the possibility of free electron redistribution and strengthened attractive interactions between particles in metallic nanostructures can explain formation of very branchy systems with extremely high “effective perimeter�. The obtained experimental and literature data show that system dimensionality, organic ligand nature along with electrostatic and magnetic interactions are most important factors of morphological control of chemically synthesized inorganic nanomaterials. The understanding and appropriate exploitation of these factors can be useful for further developments of efficient nanofabrication techniques based on colloidal and interfacial synthetic methods.
Keywords: Gas–liquid interface; Synthesis; Monolayer; Nanoparticles; Nanostructures; Ligands; Colloids; Electrostatic interactions; Magnetic interactions
XPS at solid–aqueous solution interface by A. Shchukarev (pp. 149-157).
Application of X-ray Photoelectron Spectroscopy (XPS) to study the solid–aqueous solution interface is reviewed. XPS provides complementary physicochemical information about electrical double layer from the perspective of the solid surface. Experimental techniques, such as differential pumping, controlled adsorption/co-adsorption, freeze-drying, and fast-freezing, are discussed for both electrochemical and dielectric solid-solution interfaces.The use of fast-freezing, as applied to wet pastes centrifuged from aqueous suspensions, makes it possible to approach a real solid-solution interface in UHV conditions. XPS data allow estimation of the surface density of counter-ions, surface point of zero charge, and in some cases the measurement of surface potential. Interfacial chemical reactions such as ion pair formation, specific adsorption and ligand exchange can be directly observed. The technique is easy to apply to any suspension including colloids and gels of inorganic or organic nature, and can be adapted for electrochemistry as complementary to traditional “emersed electrode� studies.