Polymer surface wetting

Thermal welding can also be used to bond one polymeric substrate to another substrate that is not polymeric. In these cases, the molten polymer surface wets the other substrate and acts as a hot-melt type of adhesive. Internal stresses that occur on cooling the interface from the molten condition are the greatest detriment to this method of bonding. 

Nevertheless, surface tensions are related to wetting phenomena. Roughly, a hquid will wet a solid if its surface tension is lower than that of the sohd (Ti < Ys)- High energy surfaces like clean metals, glass, ceramics and metal oxides are much easier to wet than plastic (polymer) surfaces. Wetting becomes more difficult when there are adsorbed liquids or contaminations as the surface energy is reduced. Solid... 

An important newer use of fluorine is in the preparation of a polymer surface for adhesives (qv) or coatings (qv). In this apphcation the surfaces of a variety of polymers, eg, EPDM mbber, polyethylene—vinyl acetate foams, and mbber tine scrap, that are difficult or impossible to prepare by other methods are easily and quickly treated. Fluorine surface preparation, unlike wet-chemical surface treatment, does not generate large amounts of hazardous wastes and has been demonstrated to be much more effective than plasma or corona surface treatments. Figure 5 details the commercially available equipment for surface treating plastic components. Equipment to continuously treat fabrics, films, sheet foams, and other web materials is also available. 

Treatment of polymer surfaces to improve their wetting, water repulsion, and adhesive properties is now a standard procedure. The treatment is designed to change the chemistry of the outermost groups in the polymer chain without affecting bulk polymer properties. Any study of the effects of treatment therefore requires a technique that is specific mostly to the outer atomic layers this is why SSIMS is extensively used in this area. 

Another serious effect occurs with liquids which are not in themselves solvents but which may wet the polymer surfaces. These facilitate relief of frozen-in stresses by surface cracking which can be a severe problem in using many injection and blow mouldings with specific chemicals. Examples of this are white spirit with polystyrene, carbon tetrachloride with polycarbonates and soaps and silicone oils with low molecular weight polyethylenes. 

The chemical modification techniques refer to the treatments used to modify the chemical compositions of polymer surfaces. Those can also be divided into two categories modification by direct chemical reaction with a given solution (wet treatment) and modification by covalent bonding of suitable macromolecular chains to the polymer surface (grafting). Among these techniques, surface grafting has been widely used to modify the surface of PDMS. 

Fogging is formation of small water droplets (visible condensation) on the surface of a polymer film. Undesirable effects may result from fog formation, such as reduction of clarity and dripping. Incorporation of antifogging agents eliminates the reduction of transparency by migration to the surface and increases the polymer surface critical wetting tension. This results in... 

Wetting polymer surfaces with ethylene glycol (92) or isopropanol (93) has also been used as a means of promoting rapid polymer dispersion prior to the onset of hydration. 

Two major classes of hydrophobic chemical substances can be applied to glass in ultrathin layers to inhibit surface wetting. Siloxanes or polysiloxanes or silicones are polymers with a backbone of alternating silicon and oxygen atoms. These macromolecules are quite chemically inert, show resistance to water, and exhibit stability at high and low temperatures. The most common siloxane polymer, polydimethylsiloxane, is composed of the monomeric (i.e., repeating) unit illustrated in Fig. 7.5.1. 

Complete wetting of a solid is only possible if a drop of the liquid spreads spontaneously at the surface, i.e. for 9 = 0 or cos 9=1. The limiting value cos 6 = 1 is a constant for a solid and is named critical surface tension of a solid y... Therefore, only liquids with yl < Vc have the ability to spontaneously spread on surfaces and wet them completely. Tab. 4.2 gives an overview of critical surface tension values of different polymer surfaces [40]. From these data it can be concluded that polytetrafluoroethylene surfaces can only be wetted by specific surfactants with a very low surface tension, e.g. fluoro surfactants. 

Motomov M, Minko S, Eichhom KJ, Nitschke M, Simon F, Stamm M. Reversible tuning of wetting behavior of polymer surface with responsive polymer brushes. Langmuir 2003 19 8077-8085. 

In order to metallize a polymer surface, electroless plating can be applied. This process typically consists of a pretreatment process in order to improve the adhesion. In the second step a surface seeding of the electroless catalyst is done. Wet chemical methods of pretreatment are using strong acids such as chromic acid, sulfuric acid and acidified potassium permanganate in order to achieve a surface modification of the polymers (96). 

At the three-phase contact line the surface tension exerts strong forces on the surface. For instance, if we consider a water drop on a polymer surface, typical contact angles are 90°. The surface tension pulls upwards on the solid surface. If we estimate the wetting line to have a width of 6 = 10 nm, the force F per unit length l can be related to the effective pressure exerted on the solid surface ... 

With 7 = 0.072 Nm-1 and 5 = 10 nm the effective pressure is of the order of P = 72 x 10s Pa. Such a high pressure can change the surface structure, cause mechanical deformation at the moving wetting line [250], and can lead to contact angle hysteresis [251-253], especially on soft polymer surfaces. 

Ternary blends One way to overcome these limitations is the use of ternary polymer blends. This approach makes use of the principle described in section 1.1.2, in which one of the polymer components wets the interface of the other two. By providing a pre-pattemed substrate with surface regions, to which these two polymer segregate, it is possible to form structures in the intercalated polymer with dimensions that are not directly connected to the substrate pattern. 

Table 3.4 gives an overview of critical surface tension values of different polymer surfaces [10]. From these data it is obvious that polytetrafluoro ethylene surfaces can only be wetted by specific surfactants with a very low surface tension, e.g. fluoro surfactants. 

Even in polymer chemistry these species may be of interest since more and more attention is devoted to polymerization in confined volumes, such as micelles, whereby the graft copolymer could first help in the emulsion polymerization of a monomer compatible with the backbone and subsequently act as a surface modifier of the polymer formed (wetting agent, pigment binder, coating binder, antistatic compound, adhesion factor, etc.). 

There are many different methods for modifying polymer surfaces to improve their adhesion and wetting properties. They include chemical etching and oxidation, ion bombardment, plasma treatments, flame treatment, mechanical abrasion and corona-discharge treatments (1.2). Especially flame and corona treatments are widely used for the modification of polyolefin surfaces to enhance, for instance, their printabilify. Despite the widespread use of such processes in industry, the understanding of the fundamental processes which occur at the polymer surface is very limited. This is undoubtedly due to the shallow depth to which the polymer is modified, typically 5 nm or less. 

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