Elastomers, wettability

Plasma processing technologies ate used for surface treatments and coatings for plastics, elastomers, glasses, metals, ceramics, etc. Such treatments provide better wear characteristics, thermal stability, color, controlled electrical properties, lubricity, abrasion resistance, barrier properties, adhesion promotion, wettability, blood compatibility, and controlled light transmissivity. 

Tackifying resins enhance the adhesion of non-polar elastomers by improving wettability, increasing polarity and altering the viscoelastic properties. Dahlquist [31 ] established the first evidence of the modification of the viscoelastic properties of an elastomer by adding resins, and demonstrated that the performance of pressure-sensitive adhesives was related to the creep compliance. Later, Aubrey and Sherriff [32] demonstrated that a relationship between peel strength and viscoelasticity in natural rubber-low molecular resins blends existed. Class and Chu [33] used the dynamic mechanical measurements to demonstrate that compatible resins with an elastomer produced a decrease in the elastic modulus at room temperature and an increase in the tan <5 peak (which indicated the glass transition temperature of the resin-elastomer blend). Resins which are incompatible with an elastomer caused an increase in the elastic modulus at room temperature and showed two distinct maxima in the tan <5 curve. 

We therefore have qualitative evidence for the dependence of the dewetting speed on the elastic properties of the substrate. Dependence of wetting on the elastic modulus was previously suggested in the case of thin substrates [31], It may be conjectured that cross-linking affects the surface properties of the elastomer and, therefore, wettability. However,... 

Today it is claimed that the surface fluorination of polymers using F2 gas mixtures enhances a wide range of properties, e.g., low permeability to nonpolar liquids4 improved permselectivity,5-6 excellent wettability and adhesion,7 low friction coefficient (especially for elastomers),8 and chemical inertness.9 Obviously, these properties depend on the chemical composition ofthe fluorinated layer, which in turn is determined by the chemical structure ofthe base polymer, the composition of the F2 gas mixture, and the fluorination parameters. 

Keywords aggregation, interfacial interaction, reversible work of adhesion, wettability, matrix-filler interaction, surface treatment, interphase, surfactant, coupling agent, elastomer interlayer... 

Prior to this discovery, in 1954 Silberberg and Kuhn (62) were first to study the polymer-in-polymer emulsion containing ethylcellulose and polystyrene in a nonaqueous solvent, benzene. The mechanisms of polymer emulsification, demixing, and phase reversal were studied. Wetzel and Hocks discovery would then equate the pressure-sensitive adhesive to a polymer-polymer emulsion instead of a polymer-polymer suspension. Since the interface is liquid-liquid, the adhesion then becomes one type of R-R adhesion (35, 36). According to our previous discussion, diffusion is not operative unless both resin and rubber have an identical solubility parameter. The major interfacial interaction is physical adsorption, which, in turn, determines adhesion. Our previous work on the wettability of elastomers (37, 38) can help predict adhesion results. Detailed studies on the function of tackifiers have been made by Wetzel and Alexander (69), and by Hock (20, 21), and therefore the subject requires no further elaboration. 

Wettability of Elastomers and Copolymers. The wettability of elastomers (37, 38) in terms of critical surface tension was reported previously. The elastomers commonly used for the reinforcement of brittle polymers are polybutadiene, styrene-butadiene random and block copolymers, and butadiene-acrylonitrile rubber. Critical surface tensions for several typical elastomers are 31 dyne/cm. for "Diene rubber, 33 dyne/cm. for both GR-S1006 rubber and styrene-butadiene block copolymer (25 75) and 37 dyne/cm. for butadiene-acrylonitrile rubber, ( Paracril BJLT nitrile rubber). The copolymerization of butadiene with a relatively polar monomer—e.g., styrene or acrylonitrile—generally results in an increase in critical surface tension. The increase in polarity is also reflected in the increase in the solubility parameter (34,39, 40) and in the increase of glass temperature (40). We also noted a similar increase in critical surface tensions of styrene-acrylonitrile copolymers with the... 

The surface of PDMS is hydrophobic which results in poor wettability with aqueous solvents and promotes non-specific protein adsorption. It is also relatively inert to chemical modification [25]. The liquid silicon rubber chosen for fabrication of the reaction plate contained pyrogenic silicic acid as a filler. Aside from its effect on elastomer properties the silicic acid can be expected to provide additional silanol... 

The characterization of surface activity of fillers is obtained by use of several analytical techniques [1]. Examples of them are inverse gas chromatography [1, 2], the adsorption of a low molecular weight analog of elastomers [3], the adsorption of elastomer chains fi om dilute solutions [4], the wettability, viscosity of PDMS fluids in the boundary layer at the surface of solids [5], the determination of the specific surface area, and the analysis of surface groups [1]. It should, however, be mentioned that the results obtained by these methods do not provide direct information on the elastomer behavior at the interface, due to the use of small probe molecules or the presence of a solvent in the systems studied. 

Elastomer Properties. Mechanical properties, wettability, and swelling characteristics of a typical elastomer are summarized In Table IV. 

Perz and coworkers [17] earlier published Si 2p and C Is specUa of untreated and various plasma-treated samples of PMTFPS gum and elastomer. PMTFPS is affected by RF plasma treatment in much the same way as PDMS. Significant improvements in wettability are possible but the treatments are temporary and hydrophobic recovery is mostly complete within 24 hours. A related topic to preformed fluoropolymers is the introduction of fluorocarbon gases into the plasma to create fluorinated surface layers. In the specific example of the use of a CF4 plasma to treat PDMS surfaces [30], a fluorine content as high as 47% can be achieved. Unlike, for example, an oxygen plasma that produces a brittle surface, the CF4 treatment is not brittle. However, contrary to expectations, the CF4 treatment resulted in a decreased water contact angle, from 119° to 101° at 100 W, 300 s. This was attributed to possible side effects such as surface oxidation, chemical heterogeneity, and surface reorganization. 

Changes in wettability are unlikely, since the base polymer of Elastomers A, B, C, CC, D, DD, and E has a contact angle of <1.5 to untreated aluminum. Scanning electron micrograph (18,000 x) shows no surface change resulting from acetic acid treatment. 

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