Polysiloxane surfaces

Three primary mechanisms have been suggested for enhanced adhesion via silane coupling agents.5 The classical explanation is that the functional group on the silane molecule reacts with the adhesive resin. Another possibility is that the polysiloxane surface layer has an open porous structure. The liquid adhesive penetrates the porosity and then hardens to form an interpenetrating interphase region. The third mechanism applies only to polymeric adherends. It is possible that the solvent used to dilute and apply the silane adhesion promoter opens the molecular structure on the substrate surface, allowing the silane to penetrate and diffuse into the adherend. 

Liquid Crystalline Polysiloxane Surfaces and Edges of a Smectic Layered Ferroelectric... 

In some cases, it is necessary to modify a polysiloxane surface to make it hydrophilic or hydrophobic. Hydrophobization is one aspect of the general topic of modifying and managing the properties of polymer sur-faces. An important example involves soft contact lenses that contain... 

Satriano, C. Carnazza, S. Guglielmino, S. Marietta, G., Differential Cultured Fibroblast Behavior on Plasma and lon-Beam-Modified Polysiloxane Surfaces. Langmuir 2002,18, 9469-9475. 

Plueddemann has recently published a book on the subject of silane coupling agents. According to Plueddemann and references cited in his book, the mechanism of action of silane coupling agents involves not just interfacial reactivity, but also the formation of an interpenetrating polymer network between a polysiloxane surface layer and the overlying polymer. 

Figure 21.7 shows a scanning electron microscopy (SEM) image of the capillary. SEM and energy-dispersive X-ray (EDX) pattering of Si and Pd (16 h measurement) show the fused-silica micro capillary with the Pd/polysiloxane surface coating. The Pd loading is extremely low, only 0.73 10" mol cm" capillary. 

High quahty SAMs of alkyltrichlorosilane derivatives are not simple to produce, mainly because of the need to carefully control the amount of water in solution (126,143,144). Whereas incomplete monolayers are formed in the absence of water (127,128), excess water results in facile polymerization in solution and polysiloxane deposition of the surface (133). Extraction of surface moisture, followed by OTS hydrolysis and subsequent surface adsorption, may be the mechanism of SAM formation (145). A moisture quantity of 0.15 mg/100 mL solvent has been suggested as the optimum condition for the formation of closely packed monolayers. X-ray photoelectron spectroscopy (xps) studies confirm the complete surface reaction of the —SiCl groups, upon the formation of a complete SAM (146). Infrared spectroscopy has been used to provide direct evidence for the hiU hydrolysis of methylchlorosilanes to methylsdanoles at the soHd/gas interface, by surface water on a hydrated siUca (147). 

Fig. 7. Schematic description of a polysiloxane at the monolayer—substrate surface (4). The arrow points to an equatorial Si—O bond that can be connected either to another polysiloxane chain or to the surface. The dashed line on the left is a bond in a possible precursor trimer where the alkyl chains can occupy...

Alkoxysilanes undergo hydrolysis, condensation (catalysts for alkoxysilane hydrolysis are usually catalysts for condensation), and a bond formation stage under base as well as under acid catalyzed mechanisms. In addition to this reaction of silanols with hydroxyls of the fiber surface, the formation of polysiloxane structures also can take place. 

Siloxane containing interpenetrating networks (IPN) have also been synthesized and some properties were reported 59,354 356>. However, they have not received much attention. Preparation and characterization of IPNs based on PDMS-polystyrene 354), PDMS-poly(methyl methacrylate) 354), polysiloxane-epoxy systems 355) and PDMS-polyurethane 356) were described. These materials all displayed two-phase morphologies, but only minor improvements were obtained over the physical and mechanical properties of the parent materials. This may be due to the difficulties encountered in controlling the structure and morphology of these IPN systems. Siloxane modified polyamide, polyester, polyolefin and various polyurethane based IPN materials are commercially available 59). Incorporation of siloxanes into these systems was reported to increase the hydrolytic stability, surface release, electrical properties of the base polymers and also to reduce the surface wear and friction due to the lubricating action of PDMS chains 59). 

Hybrid organosilicon-organophosphazene polymers have also been synthesized (15-18) (structure ) (the organosilicon groups were introduced via the chemistry shown in Scheme 11). These are elastomers with surface contact angles in the region of 106°. Although no biocompatibility tests have been conducted on these polymers, the molecular structure and material properties would be expected to be similar to or an improvement over those of polysiloxane (silicone) polymers. 

Figure 2.6 Reagents used for the deactivation of silanol groups on glass surfaces. A - disilazanes, B > cyclic siloxanes, and C -silicon hydride polysiloxanes in which R is usually methyl, phenyl, 3,3,3-trifluoropropyl, 3-cyanopropyl, or some combination of these groups. The lover portion of the figure provides a view of the surface of fused silica with adsorbed water (D), fused silica surface after deactivation with a trimethylsilylating reagent (E), and fused silica surface after treatment with a silicon hydride polysiloxane (F).

As mentioned earlier, siloxanes impart a number of beneficial properties to polymeric systems into which they are incorporated, including enhanced solubility, resistance to degradation in aggressive oxygen environments, impact resistance and modified surface properties. These particular advantages render polysiloxane-modified polyimides attractive for aerospace, microelectronic and other high performance applications (40-43). 

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