Advances in Colloid and Interface Science (v.141, #1-2)

The spin labelling method has been used in a large variety of situations, in the broad field of polymers at solid interfaces. The relevance of the method is confirmed on linear neutral chains of poly (ethylene oxide) (PEO) in well defined situations and compared with the simple theoretical calculations of a mean field theory or some scaling arguments. Both theories have their own strengths and weaknesses. Then the fact, that polymers at solid liquid interfaces are three components systems, is considered and successively the effect of varying the polymer architecture, the solid surface and the solvent is studied. In all these cases specific results are obtained by Electron Paramagnetic Resonance (EPR) showing the usefulness and the versatility of the method.
Keywords: Solid fluid interface processes; Amorphous and polymeric materials; Magnetic resonance and relaxation;

This review covers the effects of hydrophobic counterions on the phase behavior of ionic surfactants and the properties of the phases. Mixing hydrophobic counterions with ionic surfactant micellar solutions may initiate the micellar growth and transform the micellar microstructure into different morphologies. This behavior may also be achieved by mixing ionic surfactants with hydrophilic counterions, although higher counterionic concentrations are then required. First, the role of hydrophilic and hydrophobic counterions in regards to micelle growth is discussed. Second, the effect of the hydrophobic counterion on the self-assembly of cationic and anionic surfactants and their viscoelastic behavior are presented. Third, the relationships between geometry, hydrophobicity and their consequences on micellar growth for different hydrophobic counterions are reviewed. Forth, the influence of hydrophobic counterion substituents (substitution pattern) on the phase behavior is discussed. Some results we previously obtained for different isomers of hydroxy naphthaoic acids and the cationic surfactant cetyltrimethylammonium hydroxide are included. With these systems the effect that the hydrophobic counterion microenvironment has on the phase behavior, rheological behavior and the micellar microstructure is discussed. The results from other research groups are also discussed.
Keywords: Hydrophobic counterions; Ionic surfactant; Micelle growth; Viscoelastic;

Self-assembly is a ubiquitous physicochemical phenomenon. It is inherent to molecular recognition effects in the biological domain, and thus presents a basis for understanding the constitution and dynamic organization of living beings. However, it is argued in this paper that the very notion of self-assembly presents an incorrect and misleading one for the physical effects that it stands for. Self-assembly presents a misnomer as each self-assembly process not only depends on, but also includes a certain degree of ordering in the immediate surrounding of the ‘self-assembling’ entities. Claims are provided to support the idea that every self-assembly process is, in fact, a co-assembly event, as it implies mutual changes and structuring of both the ‘self-assembled’ system and its nearest surrounding. This point of view is related to the systemic observation that there could be no physical qualities independent on the context of their existence. In order to illustrate that the concept of co-assembly presents only an instance of a more profound and systemic philosophy of life, the examples of the interplay between internal and external factors of development are provided from the fields of quantum and classical physics, biology, evolutionary theory and psychology.
Keywords: Self-assembly; Co-assembly; Colloids; Interfacial phenomena; Thermodynamics;

Materials cohesion and interaction forces by Jarl B. Rosenholm; Kai-Erik Peiponen; Evgeny Gornov (48-65).
The most important methods to determine the cohesive interactions of materials and adhesive interactions between different substances are reviewed. The term cohesion is generalized as representing the unifying interaction forces of a single material and adhesion forces between different substances due to attraction. The aim is to interlink a number of frequently used interaction parameters in order to promote the understanding of materials research executed within different scientific (Material, Colloid, Sol–Gel and Nano) communities. The modern interdisciplinary research requires a removal of the historical obstacles represented by widely differing nomenclature used for the same material properties.The interaction parameters of different models are reviewed and representative numerical values computed from tabulated thermodynamic and spectroscopic material constants. The results are compared with published values. The models are grouped to represent single and two component systems, respectively. The latter group includes models for films on substrates and work of adhesion between liquids and solids. In most cases rather rough approximations have been employed, mostly relating to van der Waals substances for which the gas state is common reference state. In order to improve the predictability of the key Hamaker constant, a novel model for interpreting the dielectric spectrum is presented.The interrelation between thermodynamic, electronic, spectroscopic and dielectric parameters is illustrated by model calculations on typical inorganic materials of current interest as model compounds. The ionic solids are represented by NaCl and KCl, while ZnO, FeO, Fe2O3, Fe3O4, Al2O3, SiO2, TiO2, ZrO2, SnO, SnO2 represent ceramic oxides and semiconductors. The model compounds thus illustrate the effect of bond type (covalent or ionic) and valence (charge number and sign) of the constituent elements. However, since the focus is placed on a phenomenological analysis, the number of examples remains self-evidently incomplete.
Keywords: Materials; Cohesion; Adhesion; Interaction; Thermodynamics; Spectroscopy; Hamaker;

Smectites are swelling clay materials with pronounced colloidal properties that are widely used in industry. These properties originate in the electrokinetic properties of the smectite layers and their linkage capacities. Thin layers may be dispersed or aggregated according to many parameters, such as concentration, particle size and morphology, exchangeable cation nature and chemical environment (pH, ionic strength). The literature usually provides general rules, like the sodium dispersion contains a lot of small units whereas the calcium dispersion contains a few large units. A volume of water molecules bound to the clay surface is considered as the immobile water phase that behaves like the solid phase obstructing the flow. The water immobilized around layers and trapped inside aggregates cannot participate to the flow.In this study, we evaluated the volume occupied by calcium and sodium units inside the dispersion containing the immobile water phase. First, the smectite was cautiously extracted from a raw bentonite and its physicochemical properties were determined. A large quantity of extracted and saturated smectite (Na-smectite and Ca-smectite) was obtained. Second, the unit size and a shape factor for each sample were evaluated using granulometry and scanning transmission electron microscopy on wet samples (Wet STEM) and some flow curves. Na-smectite dispersions contain 0.13 µm2 surface units with a shape factor of 50. Ca-smectite dispersions contain 0.32 µm2 surface units with a shape factor of 3.3. Finally, rheometry allowed us to evaluate the unit occupancy using an adaptation of the Krieger–Dougherty law. We used shape factors and evaluated the concentration from which the entire immobile volume was connected (6.4% for Na-smectite and 11.9% for Ca-smectite).This study explains the evolution of flow properties with increasing concentrations by the evolution of layer interactions at the microscopic scale for homoionic smectite particles in diluted dispersions.