Contact Angle energies

In practice, 7s 7sv is negligible as is dys/dT for systems having large contact angles. Also, low energy surfaces have a relatively constant value of dyst/dT = 0.07 0.02 erg cm K , leaving... 

When a surface-active agent is present in a liquid droplet, it can adsorb to the surface, lower the surface energy, and cause the liquid contact angle to increase. This phenomenon, known as autophobicity, was postulated by Zisman many years ago [78, 79]. Autophobicity is quite striking in wetting films on clean... 

Ruch and Bartell [84], studying the aqueous decylamine-platinum system, combined direct estimates of the adsorption at the platinum-solution interface with contact angle data and the Young equation to determine a solid-vapor interfacial energy change of up to 40 ergs/cm due to decylamine adsorption. Healy (85) discusses an adsorption model for the contact angle in surfactant solutions and these aspects are discussed further in Ref. 86. 

Bikerman [182] criticized the derivation of Eq. X-18 out of concern for die ignored vertical component of On soft surfaces a circular ridge is raised at the periphery of a drop (see Ref. 67) on harder solids there is no visible effect, but the stress is there. It has been suggested that the contact angle is determined by the balance of surface stresses rather than one of surface free energies, the two not necessarily being the same for a... 

The integral A/, while expressible in terms of surface free energy differences, is defined independently of such individual quantities. A contact angle situation may thus be viewed as a consequence of the ability of two states to coexist bulk liquid and thin film. 

There is no reason why the distortion parameter should not contain an entropy as well as an energy component, and one may therefore write 0 = 0q-sT. The entropy of adsorption, relative to bulk liquid, becomes A5fi = sexp(-ca). A critical temperature is now implied, Tc = 0o/s, at which the contact angle goes to zero [151]. For example, Tc was calculated to be 174°C by fitting adsorption and contact angle data for the -octane-PTFE system. 

The interesting implication of Eq. XII-24 is that for a given solid, the work of adhesion goes through a maximum as 7b(a) is varied [69]. For the low-energy surfaces Zisman and co-workers studied, )3 is about 0.04, and Wmax is approximately equal to the critical surface tension yc itself the liquid for this optimum adhesion has a fairly high contact angle. 

Returning to more surface chemical considerations, most literature discussions that relate adhesion to work of adhesion or to contact angle deal with surface free energy quantities. It has been pointed out that structural distortions are generally present in adsorbed layers and must be present if bulk liquid adsorbate forms a finite contact angle with the substrate (see Ref. 115). Thus both the entropy and the energy of adsorption are important (relative to bulk liquid). The... 

The basic phenomenon involved is that particles of ore are carried upward and held in the froth by virtue of their being attached to an air bubble, as illustrated in the inset to Fig. XIII-4. Consider, for example, the gravity-free situation indicated in Fig. XIII-5 for the case of a spherical particle. The particle may be entirely in phase A or entirely in phase B. Alternatively, it may be located in the interface, in which case both 7sa nnd 7sb contribute to the total surface free energy of the system. Also, however, some liquid-liquid interface has been eliminated. It may be shown (see Problem XIII-12) that if there is a finite contact angle, 0sab> the stable position of the particle is at the interface, as shown in Fig. XIII-5Z>. Actual measured detachment forces are in the range of 5 to 20 dyn [60]. 

If the contact angle is zero, as in Fig. XIII-8e, there should be no tendency to adhere to a flat surface. Leja and Poling [63] point out, however, that, as shown in Fig. XIII-8/, if the surface is formed in a hemispherical cup of the same radius as the bubble, then for step la, the free energy change of attachment is... 

The cleaning process proceeds by one of three primary mechanisms solubilization, emulsification, and roll-up [229]. In solubilization the oily phase partitions into surfactant micelles that desorb from the solid surface and diffuse into the bulk. As mentioned above, there is a body of theoretical work on solubilization [146, 147] and numerous experimental studies by a variety of spectroscopic techniques [143-145,230]. Emulsification involves the formation and removal of an emulsion at the oil-water interface the removal step may involve hydrodynamic as well as surface chemical forces. Emulsion formation is covered in Chapter XIV. In roll-up the surfactant reduces the contact angle of the liquid soil or the surface free energy of a solid particle aiding its detachment and subsequent removal by hydrodynamic forces. Adam and Stevenson s beautiful photographs illustrate roll-up of lanoline on wood fibers [231]. In order to achieve roll-up, one requires the surface free energies for soil detachment illustrated in Fig. XIII-14 to obey... 

Surfa.ce Energy. The surface energies of Parylenes N, C, and D were measured by observing the contact angles for several standard probe hquids. AH three have surface energies of approximately 45 mj/m (= dyn/cm), ie, all test Hquids having less than 45 mj/m surface tension completely wet the as-deposited parylene surfaces (43). 

Fig. 1. Schematic of a Hquid drop on a soHd surface showing the contact angle, 9, as weU as the Hquid—soHd interfacial energy, y, the Hquid—vapor...

Roll-up. The principal means by which oily soil is removed is probably roU-up. The appHcable theory is simply the theory of wetting. In briefest outline, a droplet of oily soil attached to the substrate forms at equiUbrium a definite contact angle at the oil-sohd-air boundary line. This contact angle (Fig. 4) is the result of the interaction of interfacial forces in the three phase boundaries of the system. These interfacial forces, expressed in mN/m(= dyn/cm), or interfacial free energy values expressed in mj/m (erg/cm s) are conveniently designated 1SA iSlj subscripts relate to the Hquid-air,... 

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