Permeability fluorinated polymers

Soft contact lenses incorporating fluorinated polymers (F-polyether dimethacrylates, fluorosiloxanes) and showing increased permeability to oxygen and... 

Abstract Pressure-sensitive paint (PSP) is applied to the areodynamics measurement. PSP is optical sensor based on the luminescence of dye probe molecules quenching by oxygen gas. Many PSPs are composed of probe dye molecules, such as polycyclic aromatic hydrocarbons (pyrene, pyrene derivative etc.), transition metal complexes (ruthenium(II), osumium(II), iridium(III) etc.), and metalloporphyrins (platinum (II), palladium(II), etc.) immobilized in oxygen permeable polymer (silicone, polystyrene, fluorinated polymer, cellulose derivative, etc.) film. Dye probe molecules adsorbed layer based PSPs such as pyrene derivative and porphyrins directly adsorbed onto anodic oxidised aluminium plat substrate also developed. In this section the properties of various oxygen permeable polymer for matrix and various dye probes for PSP are described. 

Many PSPs are composed of probe dyes, such as polycyclic aromatic hydrocarbons (e.g., pyrene) and coordination compounds (e.g., platinum por-phryins and ruthenium(II) polypyridyl complexes) immobilized in various gas permeable polymer films such as silicon polymer, organic glassy polymers (e.g., poly(methylmethacrylate), polystyrene), fluorinated polymers, or cellulose derivatives such as ethyl cellulose [9,10]. As probe molecules interact with polymer matrices directly, the properties of PSPs strongly depend on the properties of polymer matrices. The oxygen permeability of polymer matrix is an especially important factor for highly sensitive PSP. 

The second key factor determining permeability in polymers is the sorption coefficient. The data in Figure 2.18 show that sorption coefficients for a particular gas are relatively constant within a single family of related materials. In fact, sorption coefficients of gases in polymers are relatively constant for a wide range of chemically different polymers. Figure 2.25 plots sorption and diffusion coefficients of methane in Tanaka s fluorinated polyimides [23], carboxylated polyvinyl trimethylsiloxane [37] and substituted polyacetylenes [38], all amorphous glassy polymers, and a variety of substituted siloxanes [39], all rubbers. The diffusion... 

In the diaphragm (and in the membrane) process, the anode and cathode compartments are separated by a permeable -> diaphragm. The latter generally consist of asbestos, reinforced with fibers of fluorinated polymers, or more recently, they consist of asbestos-free diaphragms, that are instead... 

Among the proton-conducting membranes, Nafion or Nafion-like sulfonated perfluorinated polymers should also be mentioned. These materials are used for polymer electrolyte membrane (PEM) FCs, and in addition to being chemically very stable, they exhibit high proton conductivity at temperatures lower than 100°C. It is believed that permeability and thermal stability may be increased if tailor-made lamellar nanoparticles are added to a proton-conducting polymer. The sulfonated poly(ether ether ketone) (S-PEEK) type of polymers is also widely reported as an alternative to fluorinated polymers such as Nafion or Hyflon [51]. 

PEM fuel cells use a solid polymer membrane (a thin plastic film) as the electrolyte. The standard electrolyte material currently used in PEM fuel cells is a fully fluorinated Teflon-based material produced by DuPont for space applications in the 1960s. The DuPont electrolytes have the generic brand name Nafion, and the types used most frequently are 113, 115, and 117 [13, 57-62,68]. The Nafion membranes are fully fluorinated polymers that have very high chemical and thermal stability. This polymer is permeable to protons when it is saturated with water, but it does not conduct electrons. 

Methods of preparation of various functional fluoropolymers suitable for fuel cell applications have been discussed by Ameduri and coworkers [ 120]. They claimed that in spite of the high cost of Nafion and its permeability to methanol, it still remains the fluorinated polymer of choice for the preparation of the proton exchange membranes for PCs. 

Many fluorine containing polymers are being evaluated for possible use as permeable selective membranes. The fluorine containing polymers have been shown to increase permeation rates without decreasing in the selec-... 

Fluorinated poly(arylene edier)s are of special interest because of their low surface energy, remarkably low water absorption, and low dielectric constants. The bulk—CF3 group also serves to increase the free volume of the polymer, thereby improving various properties of polymers, including gas permeabilities and electrical insulating properties. The 6F group in the polymer backbone enhances polymer solubility (commonly referred to as the fluorine effect ) without forfeiture of die thermal stability. It also increases die glass transition temperature with concomitant decrease of crystallinity. 

Fluorine-containing polymers exhibit unique chemical and physical properties and high performance that are not observed with other organic polymers. They possess high thermal stability, high chemical stability, a low coefficient of friction, low adhesion, water and oil repellency, low refractive index, and outstanding electric insulation. In addition, there have recently been new expectations of selective permeability, piezoelectricity, and biocompatibility. 

Direct fluorination of polymer or polymer membrane surfaces creates a thin layer of partially fluorinated material on the polymer surface. This procedure dramatically changes the permeation rate of gas molecules through polymers. Several publications in collaboration with Professor D. R. Paul62-66 have investigated the gas permeabilities of surface fluorination of low-density polyethylene, polysulfone, poly(4-methyl-1 -pentene), and poly(phenylene oxide) membranes. 

Another interesting and possibly useful result of fluorination of XeF2-treated polymer surfaces is decreased gas permeability. For example, fluorinated poly-... 

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. 

Oxidation is also dependent on the permeability of the polymer to oxygen. Table 10.1 lists the permeabilities of selected polymers to oxygen. Because bulk oxidations are dependent on the permeability to oxygen, crystalline polymer forms are more resistant to oxidation than amorphous forms. Also, the very nature of the molecules present in the chains affects the tendencies toward oxidation. Thus the fluorine atom in polytetrafluoroethylene (ptfe)... 

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