Oxygen-permeable polymer

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. 

The conventional PSP consists of sensor probe molecules contained in a transparent oxygen-permeable polymer film matrix (Fig. 3). The oxygen molecules permeate into the polymer film matrix by diffusion. In contrast, PSP consists of sensor molecules directly adsorbed onto a substrate such as an anodic oxidized aluminum plate (Fig. 4). Thus, polymers and probes are important factors for PSP application. 

Another application of particular note involving SS-RTP is the technology named phosphorescence barometry, which provides an inexpensive method for continuous pressure mapping of aerodynamic and automotive surfaces. The technology makes use of a luminescent paint (pressure-sensitive paint) that consists of an oxygen permeable polymer (e.g., silicone resins) in which a phosphorescent compound, a platinum porphyrin derivative, is dispersed. A temperature-sensitive paint would be similar except that an oxygen impermeable support should be used (e.g., an epoxy resin). 

Because the cornea lacks blood vessels, oxygen supply is provided by the eyes own moisture. If the amount of oxygen available is inadequate, eye damage results. Oxygen is supplied when contact lenses are worn by the use of a highly oxygen permeable polymer and the design of lenses to include an internal curvature which permits natural bodily fluid to bathe the cornea. 

Cross-linked versions of water-soluble polymers swollen in aqueous media are broadly referred to as hydrogels (52) and have a growing commercial utility in such apphcations as oxygen-permeable soft contact lenses (qv) (53) (Table 4) and controUed-release pharmaceutical dmg deflvery devices (54). Cross-linked PVP and selected copolymers fit this definition and are of interest because of the following stmcture/performance characteristics ... 

Table 11. Effect of Orientation on Oxygen Permeability for Certain Polymers...

Fig. 15. Oxygen permeability versus 1/specific free volume at 25 °C (30). 1. Polybutadiene 2. polyethylene (density 0.922) 3. polycarbonate 4. polystyrene 5. styrene-acrylonitrile 6. poly(ethylene terephthalate) 7. acrylonitrile barrier polymer 8. poly(methyl methacrylate) 9. poly(vinyl chloride) 10. acrylonitrile barrier polymer 11. vinyUdene chloride copolymer 12. polymethacrylonitrile and 13. polyacrylonitrile. See Table 1 for unit conversions.

Certain copolymers of this type have been found to have excellent gas barrier properties, with the dry polymer having an oxygen permeability only about 1/lOth that of polyvinylidene chloride. Unsurprisingly, the copolymer has a high moisture absorption and a high moisture vapour transmission rate. Where the material is swollen by water, gas permeability is also higher. 

The diffusion of oxygen through polymer films has been examined by a number of workers. Guruviah measured the permeability to oxygen of films cast from five paints (Tabic 14.4) and compared the results with the... 

In a series of papers, Kennedy and co-workers studied the amphiphilic networks and their membrane characteristics. The use of poly(pentamethyl)cyclopentasiloxane)32 as an oxyphilic cross-linker in the novel tricontinuous membranes, consisting of hydrophilic and lipophilic polymers, was reported.466 The presence of polysiloxane brought about high oxygen permeability, which was studied in the water-swollen membranes.467 The use of polysiloxanes as sorbents,468 and as carriers for the receptor molecules in the ion-exchange membranes,469 470 was reviewed. 

Dual lifetime referencing (DLR) is another powerful technique that enables referenced measurements in case of fluorescent indicators [23]. In this method, the analyte-dependent signal from an indicator is referenced against the signal from an inert luminophore. This can be realized in both the time domain [24] and in the frequency domain [25]. Often, a luminescent reference dye is embedded into gas blocking nanobeads to avoid oxygen quenching. Polymers with very low gas permeability such as poly(acrylonitrile) [24] or poly(vinylidene chloride-co-acry-lonitrile) [26] are the best choice here. 

Table 7.3. Relative Fluorescence Quantum Yield of Crystal Violet,

Permeability and solubility measurements Permeability of the free films for water vapour was measured by means of the wet cup method (15). Oxygen permeability was measured using the Polymer Permeation Analyser of Dohrmann Envlrotech (16,17). Results are summarized In Table I. 

No amount of sterilization wiU prevent or even slow autooxidation, and there are only two defenses removal of O2 and addition of inhibitors. Oxygen barriers in food packaging are a major topic in the engineering of polymer films. The barrier properties of various polymers are very important in food applications, and many of these are multilayer polymers that have a thin layer of an impermeable polymer (such as polyacrylonitrile and ionic polymers) on a cheaper but O2-permeable polymer such as a polyolefin, which gives mechanical strength to the fikn. 

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)... 

---