Polymer surface tension

Many aspects of the formation of symmetric or asymmetric membranes can be rationalized by applying the basic thermodynamic and kinetic relations of phase separation. There are, however, other parameters-such as surface tension, polymer relaxation, sol and gel structures-which are not directly related to the thermodynamics of phase separation but which will have a strong effect on membrane structures and properties. A mathematical treatment of the formation of porous structures is difficult. But many aspects of membrane structures and the effect of various preparation parameters Can be qualitatively interpreted. 

For comprehensive listings of experimental surface tension values for a wide variety of polymers, the reader is referred to several excellent references 3,4-5. The surface tension of even the most polar polymers generally fall well below that of water (as shown in Figure 4) so that in terms of surface tension, polymers should be considered at best only mildly hydrophilic. Poljnners are low surface energy materials in comparison with other classes of materials by virtue of their low mass density and consequently a low interaction density, as is demonstrated in Table 1, which shows typical values for a range of different types of materials. 

A recent design of the maximum bubble pressure instrument for measurement of dynamic surface tension allows resolution in the millisecond time frame [119, 120]. This was accomplished by increasing the system volume relative to that of the bubble and by using electric and acoustic sensors to track the bubble formation frequency. Miller and co-workers also assessed the hydrodynamic effects arising at short bubble formation times with experiments on very viscous liquids [121]. They proposed a correction procedure to improve reliability at short times. This technique is applicable to the study of surfactant and polymer adsorption from solution [101, 120]. 

In polymer solutions and blends, it becomes of interest to understand how the surface tension depends on the molecular weight (or number of repeat units, IV) of the macromolecule and on the polymer-solvent interactions through the interaction parameter, x- In terms of a Hory lattice model, x is given by the polymer and solvent interactions through... 

Finally, similar effects can be seen in miscible polymer blends where the surface tension correlates with the enrichment of the lower-energy component at the surface as monitored by x-ray photoelectron spectroscopy [104],... 

Smith [113] studied the adsorption of n-pentane on mercury, determining both the surface tension change and the ellipsometric film thickness as a function of the equilibrium pentane pressure. F could then be calculated from the Gibbs equation in the form of Eq. ni-106, and from t. The agreement was excellent. Ellipsometry has also been used to determine the surface compositions of solutions [114,115], as well polymer adsorption at the solution-air interface [116]. 

Plot the scaling behavior for the surface tension of polystyrene solutions using Eq. III-64, for N = 1,000 and T from zero to Tc- Now plot the behavior for T = 0.87 for N = 100-1000. Comment on the influence of polymers on surface tension. 

The extensive use of the Young equation (Eq. X-18) reflects its general acceptance. Curiously, however, the equation has never been verified experimentally since surface tensions of solids are rather difficult to measure. While Fowkes and Sawyer [140] claimed verification for liquids on a fluorocarbon polymer, it is not clear that their assumptions are valid. Nucleation studies indicate that the interfacial tension between a solid and its liquid is appreciable (see Section K-3) and may not be ignored. Indirect experimental tests involve comparing the variation of the contact angle with solute concentration with separate adsorption studies [173]. 

The lubricating properties of tears are an important feature in normal blinking. Kalachandra and Shah measured the coefficient of friction of ophthalmic solutions (artificial tears) on polymer surfaces and found no correlation with viscosity, surface tension or contact angle [58]. The coefficient of friction appears to depend on the structure of the polymer surfaces and decreases with increasing load and sliding speed. 

The circular cross section of the polymer blobs does not prove that the polymer existed in solution as a tangled coil (although this is the case). The shape displayed by the particles in the photograph is probably due in part to surface tension occurring during the drying of the sample. 

The surface of PTFE articles is sHppery and smooth. Liquids with surface tensions below 18 mN/m(=dyn/cm) are spread completely on the PTFE surface hence, solutions of various perfluorocarbon acids in water wet the polymer (78). Treatment with alkafl metals promotes the adhesion between PTFE and other substances (79) but increases the coefficient of friction (80). 

Surface Protection. The surface properties of fluorosihcones have been studied over a number of years. The CF group has the lowest known intermolecular force of polymer substituents. A study (6) of liquid and solid forms of fluorosihcones has included a comparison to fluorocarbon polymers. The low surface tensions for poly(3,3,3-trifluoropropyl)methylsiloxane and poly(3,3,4,4,5,5,6,6,6-nonafluorohexyl)methylsiloxane both resemble some of the lowest tensions for fluorocarbon polymers, eg, polytetrafluoroethylene. 

Foam Inhibitors. Methyl sihcone polymers of 300-1000 mm /s(= cSt)) at 40°C are effective additives at only 3—150 ppm for defoaming oils in internal combustion engines, turbines, gears, and aircraft appHcations. Without these additives, severe churning and mixing of oil with air may sometimes cause foam to overflow from the lubrication system or interfere with normal oil circulation. Because sihcone oil is not completely soluble in oil, it forms a dispersion of minute droplets of low surface tension that aid in breaking foam bubbles. 

Humectants and low vapor pressure cosolvents are added to inhibit drying of ink in the no22les. Surfactants or cosolvents that lower surface tension are added to promote absorption of ink vehicle by the paper and to prevent bleed. For improvements in durabiUty, additional materials such as film-forming polymers have been added. Ink developments are providing ink-jet prints with improved lightfastness, waterfastness, and durabiUty. As a result, such prints are beginning to rival the quaUty of electrophotographic prints. 

Release agents function by either lessening intermolecular interactions between the two surfaces in contact or preventing such close contact. Thus, they can be low surface-tension materials based on aUphatic hydrocarbon, fluorocarbon groups, or particulate soHds. The principal categories of material used are waxes, fatty acid metal soaps, other long-chain alkyl derivatives, polymers, and fluorinated compounds. 

Many of these features are interrelated. Finely divided soHds such as talc [14807-96-6] are excellent barriers to mechanical interlocking and interdiffusion. They also reduce the area of contact over which short-range intermolecular forces can interact. Because compatibiUty of different polymers is the exception rather than the rule, preformed sheets of a different polymer usually prevent interdiffusion and are an effective way of controlling adhesion, provided no new strong interfacial interactions are thereby introduced. Surface tension and thermodynamic work of adhesion are interrelated, as shown in equations 1, 2, and 3, and are a direct consequence of the intermolecular forces that also control adsorption and chemical reactivity. 

The excellent chemical resistance and physical properties of PVA resins have resulted in broad industrial use. The polymer is an excellent adhesive and possesses solvent-, oil-, and grease-resistant properties matched by few other polymers. Poly(vinyl alcohol) films exhibit high tensile strength, abrasion resistance, and oxygen barrier properties which, under dry conditions, are superior to those of any other known polymer. The polymer s low surface tension provides for excellent emulsification and protective coUoid properties. 

Surface Tension. The surface tension of aqueous solutions of PVA varies with concentration (Fig. 10), temperature, degree of hydrolysis, and acetate distribution on the PVA backbone. Random distribution of acetyl groups in the polymer results in solutions having higher surface tension compared to those of polymers in which blocks of acetyl groups are present (74—77). Surface tension decreases slightly as the molecular weight is reduced (Fig. 11). 

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