Liquid Polymers surface thermodynamics

Equation (645) shows that contact angle is a thermodynamic quantity, which can be related to the work of adhesion and interfacial free energy terms. When 6 values are small, the work of adhesion is high and considerable energy must be spent to separate the solid from the liquid. If 0 = 0°, then W L = 2yv if 0 = 90°, then W L = yLV, and if 0 = 180°, then W1L = 0, which means that no work needs to be done to separate a completely spherical mercury drop from a solid surface (or a water drop from a superhydrophobic polymer surface), and indeed these drops roll down very easily even with a 1° inclination angle of the flat substrate. 

The equilibrium wetting behavior of simple liquids (including low MW polymers) on low polarity polymer surfaces is well documented and consistent with Gibbsian thermodynamics within specific constraints. Empirical relationships have been established between observed contact angles and polymer surface chemical composition. Predictive relationships have been established between contact angles and polymer substrate surface chemistry based on the theory of fractional polarity surface energies can be factored into dispersion and polar components. These relationships seriously break down with increasing polarity of either the liquid or solid surface. 

For example, the solid can swell in contact with a certain liquid or even interact by chemical interfacial reactions it can also be partially dissolved. In the case of polymer surfaces, the molecular reorientation in the surface region under the influence of the liquid phase is assumed to be a major cause of hysteresis. This reorientation or restructuring is thermodynamically favoured at the polymer-air interface, the polar groups are buried away from the air phase, thus causing a lower solid-vapour interfacial tension. In contact with a sessile water drop, the polar groups turn over to achieve a lower solid-liquid interfacial tension. Time-dependent changes in contact angles can also be observed (33). 

Wall FT (1942) Statistical thermodynamics of mbber. J Chem Phys 10(2) 132-134 Wall FT (1943) Statistical thermodynamics of mbber. 111. J Chem Phys 11(11) 527-530 Wall FT (1951) Statistical thermodynamics of mbber elasticity. J Chem Phys 19(12) 1435-1439 Ward JH, Bashir R, Peppas NA (2001) Micropatteming of biomedical polymer surfaces by novel UV polymerization techniques. J Biomed Mater Res 56(3) 351-360 Winter HH, Mours M (1997) Rheology of polymers near liquid-solid transitions. Adv Polym Sci 134 165-234... 

The simulations described above were performed at constant density, i.e., a volume was imposed on the system irrespective of the resulting pressure or chemical potential. MD simulations performed at constant chemical potential, where the confined liquid is in equilibrium with a vapor or bulk liquid phase, have also been performed. Simulations with free surfaces, i.e., with vapor/polymer interfaces, allow for the study of the equilibrium liquid-vapor interface structure and the calculation of the surface tension, a thermodynamic property fundamental to the understanding of the behavior of a material at interfaces. An MD study of the equilibrium liquid-vapor interface structure and surface tension of thin films of n-decane and n-eicosane (C20H42) has been performed in Ref. 26. The system studied consisted of a box with periodic boundary conditions in all directions. The liquid polymer, however, while fully occupying the x and y dimensions, occupied only a fraction of the system in the z direction, resulting in two liquid-vapor interfaces. The liquid phase ranged from about 4.0 to 7.0 nm in thickness. Simulations were performed at 400 K for both decane and eicosane, with additional decane simulations at 300 K. A similar system of tridecane molecules, using a well calibrated EA force field, has been studied at 400 K and 300 K in Ref 32. 

Combining the results of wetting experiments with an arbitrary choice of test liquids on a small number of polymer surfaces, he considers the phenomenological relationships found for that data pool as generally applicable. The treatment ignores the fact that all wetting pairs represent independent thermodynamic systems. 

A generalized density gradient theory of interfaces has been combined with a compressible lattice theory of polymers. This yields a unified theory of bulk and surface thermodynamic properties. A unique feature of this theory is that it is parameterless. The only parameters required to calculate a surface tension are obtained from pure component thermodynamic properties. Since the theory is a mean field theory, it is only applicable to non-polar and slightly polar liquids. For such systems, surface tensions can be accurately calculated. 

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. 

Advanced adhesives are composite liquids that can be used, for example, to join aircraft parts, thus avoiding the use of some 30,000 rivets that are heavy, are labor-intensive to install, and pose quality-control problems. Adhesives research has not involved many chemical engineers, but the generic problems include surface science, polymer rheology and thermodynamics, and molecular modeling of materials... 

It is postulated that the main thermodynamic driving force for particle adsorption at the liquid-liquid interface is the osmotic repulsion between the colloidal particles and hydrophilic starch polymer molecules. This leads to an effective depletion flocculation of particles at the boundaries of the starch-rich regions. At the same time, the gelatin has a strong tendency to adsorb at the hydrophobic surface of the polystyrene particles, thereby conferring upon them some degree of thermodynamic... 

A number of chapters have been overhauled so thoroughly that they bear only minor resemblance to their counterparts in the first edition. The thermodynamics of polymer solutions is introduced in connection with osmometry and the drainage and spatial extension of polymer coils is discussed in connection with viscosity. The treatment of contact angle is expanded so that it is presented on a more equal footing with surface tension in the presentation of liquid surfaces. Steric stabilization as a protective mechanism against flocculation is discussed along with the classical DLVO theory. 

In another case, depending on the reaction conditions, thermodynamic phase separation of the active-site-containing phase might occur during the polymerization process. In this case, active sites would be separated from the polymer, would not be covered by the polymer produced, and would be directly accessible on the surface of polymer particles, see Fig. 5.4-4(d). In this case, the surface concentration of the monomer, instead of the monomer concentration in the swollen polymer, is to be considered as the driving force of the polymerization process. If such a separation process is combined with capillary condensation then a direct contact of active sites with, for example, liquid monomer is enabled yielding high polymerization rates. 

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