Surface properties adhesion thermodynamics

It should be noted that for an adhesive which is behaving primarily as an elastic solid, the detachment failure criterion used by Derail et al. is equivalent to a stored elastic energy density criterion but under conditions where the deformation is primarily viscous, the two criteria are quite different. None of these authors has been able to successfully link the values of these failure criteria to fundamental interfacial properties or the thermodynamic work of adhesion. Clearly, much remains to be done to complete our understanding of the relationships among surface properties, adhesive rheology, and peel force. 

A surface is that part of an object which is in direct contact with its environment and hence, is most affected by it. The surface properties of solid organic polymers have a strong impact on many, if not most, of their apphcations. The properties and structure of these surfaces are, therefore, of utmost importance. The chemical stmcture and thermodynamic state of polymer surfaces are important factors that determine many of their practical characteristics. Examples of properties affected by polymer surface stmcture include adhesion, wettability, friction, coatability, permeability, dyeabil-ity, gloss, corrosion, surface electrostatic charging, cellular recognition, and biocompatibility. Interfacial characteristics of polymer systems control the domain size and the stability of polymer-polymer dispersions, adhesive strength of laminates and composites, cohesive strength of polymer blends, mechanical properties of adhesive joints, etc. 

Colloidal dispersions and other related systems are present in many applications, e.g., in paints and coatings and detergents. Here, phase equilibrium and surface phenomena are equally important. A unified representation of such phenomena, e.g., of adhesion phenomena and liquid-liquid equilibria with the same model/concepts is of interest. Thermodynamic models can be used to calculate certain surface properties such as surface tension. hi addition, properties such as the solubility parameters can be equally well employed for bulk and surface thermodynamic properties. ... 

The adhesion properties of all types of polyolefins are not easy to explain because these properties are affected by different phenomena. Using of a single theory or mechanisms based on the physical and chemical adhesion manifestations is difiicult for the description of interdisciplinary nature and diversity. There is considerable information to discuss each of the adhesion mechanisms. Therefore, it is not possible to select only the thermodynamic theory of adhesion that is the best to describe the surface free energy of the polyolefin. All mechanisms and adhesion theories are implied by the diversity of polymer systems, which are embraced in combination with research for the analyses of adhesion properties. The physical and chemical composition in the first atomic layers dictates the adhesion and some other properties of the polymer materials. This layer represents underneath layer and this subsurface partially controls the outer layers. The double bonds and cross-linked stmctures limit the mobility macromolecules of polyolefins in the subsurface layers, which results in the functional group stabilization on the surface. Other basic research is necessary for an examination of the polymer subsurface layer and explanation of its effect changes of the surface properties. Moreover, for the improvement of quantitative measurements of adhesion, additional investigation is required. 

Since changes on the enviroimient can significantly affect the thermodynamics at the surface level structural reorganization may occur. Hence, reversible changes on the surface properties of these materials can be easily accomplished, thus, creating switchable materials with controlled surface wettability, charge, adhesion, and chemical functionality. 

The right-hand member is a viscous drag proportional to the thermodynamic work of adhesion that means that losses only arise if the interface itself is capable of withstanding stresses. Reducing the work of adhesion increases the crack speed. Surface properties are thus completely de-coupled from elastic properties, geometry and loadingconditions included inG, and from viscoelastic properties described by ( )(a,pv). ... 

In all of them the acid-base interactions are fundamental. Their evaluations can be based on thermodynamic surface properties such as the work of adhesion/pH diagrams and inverse gas chromatography. 

For polymer surface properties controlled by the chemical composition, thermodynamic (equihbrium), non-equihbrium, and technical terms and definitions play an important role. These are not always used in a consistent way, hence a short recapitulation seems appropriate. The thermodynamic work of adhesion (Wa) is defined as the reversible work (the free energy change) required to separate two phases with unit area of contact, from contact to infinity. The corresponding work of adhesion (and cohesion for similar bodies) can be easily expressed with surface tension values. In general, for surfaces of two intimately contacting solids ( l and 2 , respectively) each with a unit area, are separated in a medium ( 3 ), a work VT132 is required which can be expressed as ... 

The van der Waals and other non-covalent interactions are universally present in any adhesive bond, and the contribution of these forces is quantified in terms of two material properties, namely, the surface and interfacial energies. The surface and interfacial energies are macroscopic intrinsic material properties. The surface energy of a material, y, is the energy required to create a unit area of the surface of a material in a thermodynamically reversible manner. As per the definition of Dupre [14], the surface and interfacial properties determine the intrinsic or thermodynamic work of adhesion, W, of an interface. For two identical surfaces in contact ... 

PDMS based siloxane polymers wet and spread easily on most surfaces as their surface tensions are less than the critical surface tensions of most substrates. This thermodynamically driven property ensures that surface irregularities and pores are filled with adhesive, giving an interfacial phase that is continuous and without voids. The gas permeability of the silicone will allow any gases trapped at the interface to be displaced. Thus, maximum van der Waals and London dispersion intermolecular interactions are obtained at the silicone-substrate interface. It must be noted that suitable liquids reaching the adhesive-substrate interface would immediately interfere with these intermolecular interactions and displace the adhesive from the surface. For example, a study that involved curing a one-part alkoxy terminated silicone adhesive against a wafer of alumina, has shown that water will theoretically displace the cured silicone from the surface of the wafer if physisorption was the sole interaction between the surfaces [38]. Moreover, all these low energy bonds would be thermally sensitive and reversible. 

In a fundamental sense, the miscibility, adhesion, interfacial energies, and morphology developed are all thermodynamically interrelated in a complex way to the interaction forces between the polymers. Miscibility of a polymer blend containing two polymers depends on the mutual solubility of the polymeric components. The blend is termed compatible when the solubility parameter of the two components are close to each other and show a single-phase transition temperature. However, most polymer pairs tend to be immiscible due to differences in their viscoelastic properties, surface-tensions, and intermolecular interactions. According to the terminology, the polymer pairs are incompatible and show separate glass transitions. For many purposes, miscibility in polymer blends is neither required nor de-... 

The formation of ordered two- and three-dimensional microstructuies in dispersions and in liquid systems has an influence on a broad range of products and processes. For example, microcapsules, vesicles, and liposomes can be used for controlled drug dehvery, for the contaimnent of inks and adhesives, and for the isolation of toxic wastes. In addition, surfactants continue to be important for enhanced oil recovery, ore beneficiation, and lubrication. Ceramic processing and sol-gel techniques for the fabrication of amorphous or ordered materials with special properties involve a rich variety of colloidal phenomena, ranging from the production of monodispersed particles with controlled surface chemistry to the thermodynamics and dynamics of formation of aggregates and microciystallites. 

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