Surface-liquid interactions

According to the Young s equation the contact angle can be calculated using the surface tension of the solid (/s), the liquid phase (yO, and the solid-liquid interfacial energy (y i) [43]  

The majority of chemical PU modification approaches are aimed at establishing hydrophilic surfaces repelling nonspecific protein adsorption [6,44,45]. The 

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Molecular mechanics methods have been used particularly for simulating surface-liquid interactions. Molecular mechanics calculations are called effective potential function calculations in the solid-state literature. Monte Carlo methods are useful for determining what orientation the solvent will take near a surface. Molecular dynamics can be used to model surface reactions and adsorption if the force held is parameterized correctly. 

Up until this point, we have been considering only surface-liquid interactions where the solid is purely rigid and is perfectly secured to some lower surface upon which it rests. This is usually a good approximation however, in some... 

Besides the capillary length, another key figure of merit is the work of adhesion (W a)-It describes the amount of work necessary to lift a droplet off the surface, hence it is associated with overcoming the surface-liquid interactions. values can be calculated using Dupre s equation [24] ... 

The following sections focus on both the chemical and the physical modification of PUs, summarize the different approaches, and highlight similarities as well as differences. Therefore, a short overview regarding blood-material interactions and the impact on medical devices is given first, followed by an explanation of surface-liquid interactions. 

The principal effect of the presence of a smooth wall, compared to a free surface, is the occurrence of a maximum in the density near the interface due to packing effects. The height of the first maximum in the density profile and the existence of additional maxima depend on the strength of the surface-water interactions. The thermodynamic state of the liquid in a slit pore, which has usually not been controlled in the simulations, also plays a role. If the two surfaces are too close to each other, the liquid responds by producing pronounced density oscillations. 

The first MC (16) and MD (17) studies were used to simulate the properties of single particle fluids. Although the basic MC (11,12) and MD (12,13) methods have changed little since the earliest simulations, the systems simulated have continually increased in complexity. The ability to simulate complex interfacial systems has resulted partly from improvements in simulation algorithms (15,18) or in the interaction potentials used to model solid surfaces (19). The major reason, however, for this ability has resulted from the increasing sophistication of the interaction potentials used to model liquid-liquid interactions. These advances have involved the use of the following potentials Lennard-Jones 12-6 (20), Rowlinson (21), BNS... 

Inner slip, between the solid wall and an adsorbed film, will also influence the surface-liquid boundary conditions and have important effects on stress propagation from the liquid to the solid substrate. Linked to this concept, especially on a biomolecular level, is the concept of stochastic coupling. At the molecular level, small fluctuations about the ensemble average could affect the interfacial dynamics and lead to large shifts in the detectable boundary condition. One of our main interests in this area is to study the relaxation time of interfacial bonds using slip models. Stochastic boundary conditions could also prove to be all but necessary in modeling the behavior and interactions of biomolecules at surfaces, especially with the proliferation of microfluidic chemical devices and the importance of studying small scales. 

Fruitful interplay between experiment and theory has led to an increasingly detailed understanding of equilibrium and dynamic solvation properties in bulk solution. However, applying these ideas to solvent-solute and surface-solute interactions at interfaces is not straightforward due to the inherent anisotropic, short-range forces found in these environments. Our research will examine how different solvents and substrates conspire to alter solution-phase surface chemistry from the bulk solution limit. In particular, we intend to determine systematically and quantitatively the origins of interfacial polarity at solid-liquid interfaces as well as identify how surface-induced polar ordering... 

The ultimate aim of scientists has always been to be able to see molecules while active. In order to achieve this goal, the microscope should be able to operate under ambient conditions. Further, all kinds of molecular interactions between a solid and its environment (gas or liquid or solid), initially, can take place only via the surface molecules of the interface. It is obvious that, when a solid or liquid interacts with another phase, knowledge of the molecular structures at these interfaces is of interest. The term surface is generally used in the context of gas-liquid or gas-solid phase boundaries, while the term interface is used for liquid-liquid or liquid-solid phases. Furthermore, many fundamental properties of surfaces are characterized by morphology scales of the order of 1 to 20 nm (1 nm = 10-9 m = 10 A (Angstrom = 10-8 cm). 

The heat values are markedly higher for the polar solid immersed in polar liquids they also vary considerably with the functional group of the liquid. For Graphon, however, the heats are almost unaffected by the structural features of the wetting liquid. This nonpolar solid, despite the presence of a small amount of hydrophilic sites on its surface 0), interacts with the liquids primarily through London dispersion forces. Because of the additive nature of these forces, each adsorbed molecule tends to lie flat on such a surface 40). In the case of a polar molecule the functional group is oriented somewhat away from the nonpolar surface toward the liquid. 

Some components in a gas or liquid interact with sites, termed adsorption sites, on a solid surface by virtue of van der Waals forces, electrostatic interactions, or chemical binding forces. The interaction may be selective to specific components in the fluids, depending on the characteristics of both the solid and the components, and thus the specific components are concentrated on the solid surface. It is assumed that adsorbates are reversibly adsorbed at adsorption sites with homogeneous adsorption energy, and that adsorption is under equilibrium at the fluid- adsorbent interface. Let (m" ) be the number of adsorption sites and (m 2) the number of molecules of A adsorbed at equilibrium, both per unit surface area of the adsorbent. Then, the rate of adsorption r (kmol m s ) should be proportional to the concentration of adsorbate A in the fluid phase and the number of unoccupied adsorption sites. Moreover, the rate of desorption should be proportional to the number of occupied sites per unit surface area. Here, we need not consider the effects of mass transfer, as we are discussing equilibrium conditions at the interface. At equilibrium, these two rates should balance. Thus,... 

Fowkes, F. M., F. L. Riddle Jr., W. E. Pastore, and A. E. Weber, Interfacial interactions between self-associated polar liquids and squalane used to test equations for solid-liquid interactions , Colloids and Surfaces, 43, 367-387 (1990). 

The third factor, ZR, in Eq. (5.1) is called the residual contribution in the chemical engineering notation and it arises from all kinds of non-steric interactions between molecules, i.e., usually from vdW, electrostatic, and hydrogen bond interactions. Despite its name, it is the most important contribution in most liquids. The basic assumption of surface-pair interaction models is that residual—i.e., non-steric—interactions can be described as local pairwise interactions of surface segments. The residual contribution is just the partition sum of an ensemble of pairwise interacting surface segments. 

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