Advances in Colloid and Interface Science (v.93, #1-3)
Interface-mediated oscillatory phenomena by R.P Rastogi; R.C Srivastava (1-75).
Oscillatory transport processes which occur in the far from equilibrium region have assumed great significance from the viewpoint of science of complexity. Oscillatory phenomena in the chemical reaction systems have been subjected to intense investigations both from theoretical and experimental angles. In the present review an effort has been made to bring transport processes other than conventional chemical reactions into focus: transport processes mediated by solid–liquid and liquid–liquid interfaces have been discussed. Transport through membranes including liquid membranes, liquid–liquid interfaces and the recently reported hydrodynamic oscillator have been covered. Applications of these systems in areas such as fabrication of sensors, phase transfer catalysis and, of course, the obvious biological action, e.g. excitation of biomembranes and tissues, have been reviewed. Theoretical frameworks proposed to rationalize the phenomena have also been critically reviewed.
Keywords: Oscillatory phenomena; Membrane oscillator; Hydrodynamic oscillator; Oscillations – interface mediated;
Steady shear rate rheology of suspensions, as described by the giant floc model by H.N. Stein; J. Laven (77-90).
The break-down of a particle network by shear is described as the development of shear planes: a region able to withstand low shear stresses may break down under a larger stress; thus with increasing shear stress and shear rate, the mutual distance (A) between successive shear planes decreases until, at very high shear rates, A approaches the particle diameter. The shear planes are idealised as flat planes. Energy dissipation during shear is predominantly due to the energy dissipated through the movement of the particles; the energy dissipation due to breakage and renewed formation of bonds between particles is relatively small. A consideration of the energy dissipated during the encounters of particles during shear, including that dissipated by entrained particles, then leads to a relation between this energy dissipation and the average fraction L, over which a moving particle entrains a neighbour. L includes the effect of parts of the network which are rotating under the influence of the shear. In the limit of large shear rates, L is found to depend only to a small extent on whether the suspension is coagulated or not.
Keywords: Rheology; Concentrated suspensions; Particle network; Network destruction by shear;
At the solid/liquid interface: FTIR/ATR — the tool of choice by Andrew R Hind; Suresh K Bhargava; Anthony McKinnon (91-114).
For the last 7 years, we have been researching various aspects of the Bayer process. Predominant among these has been the surface chemistry of Bayer process solids. To this end, we have been using Fourier transform infrared (FTIR) attenuated total reflection (ATR) spectroscopy for in situ studies of the surfaces of the Bayer process solids sodium oxalate and aluminium trihydroxide under extreme (high ionic strength, high pH), Bayer-like conditions. FTIR/ATR is one of the few techniques currently available to scientists wishing to explore solid/liquid interfacial phenomena in situ. Using this investigative technique, information regarding the nature of adsorbed species can be readily acquired, with details concerning adsorbate orientation and adsorption/desorption equilibria, speciation, mechanisms and kinetics obtainable. Not surprisingly, FTIR/ATR has become one of the tools of choice for those wishing to explore the solid/liquid interface, and the body of literature available on the subject has been steadily growing over the last 10–15 years. This review addresses the current state of knowledge in the area of FTIR/ATR with respect to interfacial spectroscopy, as well as introducing some of the more fundamental theoretical and practical aspects of the technique. Particular emphasis is placed upon applied interfacial research. In writing this review, we draw on a considerable amount of expertise in the use of FTIR/ATR in interfacial studies (in particular, the practical considerations involved), as well as a large and comprehensive literature database focussing primarily on the investigation of interfacial processes using the FTIR/ATR technique.
Keywords: FTIR/ATR; Solid/liquid interface; Interfacial phenomena; Adsorption;
Properties of the amphiphilic films in mixed cationic/anionic vesicles: a comprehensive view from a literature analysis by Christian Tondre; Céline Caillet (115-134).
The so-called ‘catanionic’ vesicles are made from mixtures of cationic and anionic surfactants. They are attracting much interest because they form spontaneously and they can be obtained from a variety of surfactants, either commercially available or issued from original synthesis. A distinction can be made between the properties of simple surfactant mixtures and of ion pair amphiphiles (IPA), in which the counterions have been removed. We have drawn up in this paper, an inventory of the different vesicular systems which have been described in the literature, insisting on the specific features associated with these two categories of systems. We have collected here especially, information concerning the phase behaviors, the microscopic composition of the vesicular particles, their structural and size determinations, the dynamic aspects (including the micelle–vesicle transition), the theoretical predictions from thermodynamic models and the entrapment of probe molecules. We discuss the potential of catanionic vesicles as delivery systems and we show that a full understanding of their entrapment/release properties will call for much more experimental work with well defined protocols. We also point out some unsolved questions concerning the role of the excess surfactant in the stabilization of the particles and the conditions required to obtain a favourable curvature of the surfactant film.
Keywords: Vesicles; Encapsulation; Mixed surfactants; Catanionic amphiphiles; Ion pair amphiphiles;
Adsorption — from theory to practice by A Dąbrowski (135-224).
Adsorption at various interfaces has concerned scientists since the beginning of this century. This phenomenon underlies a number of extremely important processes of utilitarian significance. The technological, environmental and biological importance of adsorption can never be in doubt. Its practical applications in industry and environmental protection are of paramount importance. The adsorption of substrates is the first stage in many catalytic processes. The methods for separation of mixtures on a laboratory and on an industrial scale are increasingly based on utilising the change in concentration of components at the interface. Moreover, such vital problems as purification of water, sewages, air and soil are involved here too. On the other hand, many areas in which technological innovation has covered adsorption phenomena have been expanded more through art and craft than through science. A basic understanding of the scientific principles is far behind; in part because the study of interfaces requires extremely careful experimentation if meaningful and reproducible results are to be obtained. In recent years, however, considerable effort has been increasingly directed toward closing the gap between theory and practice. Crucial progress in theoretical description of the adsorption has been achieved, mainly through the development of new theoretical approaches formulated on a molecular level, by means of computer simulation methods and owing to new techniques which examine surface layers or interfacial regions. Moreover, during the last 15 years new classes of solid adsorbents have been developed, such as activated carbon fibres and carbon molecular sieves, fullerenes and heterofullerenes, microporous glasses and nanoporous — both carbonaceous and inorganic — materials. Nanostructured solids are very popular in science and technology and have gained extreme interest due to their sorption, catalytic, magnetic, optical and thermal properties. Although the development of adsorption up to the 1918s has been following rather a zig–zag path, this arm of surface science is now generally considered to have become a well-defined branch of physical science representing an intrinsically interdisciplinary area between chemistry, physics, biology and engineering. This review presents in brief the history of adsorption and highlights the progress in theoretical description of the phenomenon under consideration. The paper deals with the above problems critically, showing the development of adsorption, presenting some of the latest important results and giving a source of up-to-date literature on it. Moreover, in this paper the most important aspects are overviewed referring to today's trends and visions in application of adsorption science in industry, environmental protection and in environmental analysis. The relationship between development of adsorption theory and adsorption practice is pointed out. Current understanding and perspectives pertaining to applications of adsorption phenomena on laboratory and on industrial scale as well as environmental protection are discussed and illustrated by means of a few spectacular examples.