Membranes glass transition

The porous electrodes in PEFCs are bonded to the surface of the ion-exchange membranes which are 0.12- to 0.25-mm thick by pressure and at a temperature usually between the glass-transition temperature and the thermal degradation temperature of the membrane. These conditions provide the necessary environment to produce an intimate contact between the electrocatalyst and the membrane surface. The early PEFCs contained Nafton membranes and about 4 mg/cm of Pt black in both the cathode and anode. Such electrode/membrane combinations, using the appropriate current coUectors and supporting stmcture in PEFCs and water electrolysis ceUs, are capable of operating at pressures up to 20.7 MPa (3000 psi), differential pressures up to 3.5 MPa (500 psi), and current densities of 2000 m A/cm. ... 

Polymer Processing. Polymer films were cast in trimethylsilyl coated glass molds from membrane filtered 15% (w/v) methylene chloride or chloroform solutions. Transparent films were obtained which were dried to constant weight in high vacuum. Rectangular strips or round disks were cut from the films. For compression molding a Carver laboratory press equipped with thermostated, heated platens was used. Polymers were placed in a stainless steel mold and heated to 40 °C above their glass transition temperature. Then a load of 1-2 tons was applied for 5 min. 

ISFETs), 3 799 9 585 74 24. See also Field effect transistors (FETs) Ion-selective membranes, cavities in, 9 584 Ion size, cluster glass transition and, 74 469, 470... 

The polycarbonate membranes are stretch-oriented during fabrication in order to improve their mechanical properties. If the membrane is subsequently heated above its glass-transition temperature ( 150°C), the polymer chains relax to their unstretched conformation and the membrane shrinks. This shrinking of the membrane around the Au nanowires in the pores causes the junction between the nanowire and the pore wall to be sealed. This is illustrated in Fig. 5, which shows voltammograms for tri-methylaminomethylferrocene (TMAFc+) before (Fig. 5A) and after (Fig. 

For instance, the Dow experimental membrane and the recently introduced Hyflon Ion E83 membrane by Solvay-Solexis are "short side chain" (SSC) fluoropolymers, which exhibit increased water uptake, significantly enhanced proton conductivity, and better stability at T > 100°C due to higher glass transition temperatures in comparison to Nafion. The membrane morphology and the basic mechanisms of proton transport are, however, similar for all PFSA ionomers mentioned. The base polymer of Nation, depicted schematically in Figure 6.3, consists of a copolymer of tetrafluoro-ethylene, forming the backbone, and randomly attached pendant side chains of perfluorinated vinyl ethers, terminated by sulfonic acid head groups. °... 

Glassy polymers with much higher glass transition temperatures and more rigid polymer chains than rubbery polymers have been extensively used as the continuous polymer matrices in the zeolite/polymer mixed-matrix membranes. Typical glassy polymers in the mixed-matrix membranes include cellulose acetate, polysul-fone, polyethersulfone, polyimides, polyetherimides, polyvinyl alcohol, Nafion , poly(4-methyl-2-pentyne), etc. 

All of these polyperfluorosulfonic acid membranes are expensive and suffer from the same shortcomings as Nation, namely low conductivity at low water contents, relatively low mechanical strength at higher temperature, and moderate glass transition temperatures. 

The inorganic poly(phosphazene) backbone has received attention as a PEM candidate. This is an attractive system for study due to its ease of synthesis and subsequent modification by many functional groups. However, these membranes generally show low glass transition temperatures and somewhat poor mechanical properties, and they require cross-linking to enhance their performance in hydrated environments. 

Because of the angled structure of poly(arylene ether sulfone)s, they generally do not crystallize. They are thus amorphous and optically transparent with glass transition temperatures between 150-200 °C. They are soluble in some polar solvents, hydrolysis resistant, and inherently flame resistant. Fields of application for these materials are found particularly in the area of electronics and membrane technology. 

Permeation is dependent on the segmental motion of the polymer chains and the free volume of chain segments. The free volume decreases, whereas the chain stiffness increases, as the temperature of the polymeric membrane is lowered toward the glass transition temperature Tf. The free volume is similar for all polymers at the Tf. 

Much attention has been paid to the synthesis of fluorine-containing condensation polymers because of their unique properties (43) and different classes of polymers including polyethers, polyesters, polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, and epoxy prepolymers containing pendent or backbone-incorporated bis-trifluoromethyl groups have been developed. These polymers exhibit promise as film formers, gas separation membranes, seals, soluble polymers, coatings, adhesives, and in other high temperature applications (103,104). Such polymers show increased solubility, glass-transition temperature, flame resistance, thermal stability, oxidation and environmental stability, decreased color, crystallinity, dielectric constant, and water absorption. 

A new class of hydrophilic polyamides, poly(tetrahydropyran-2,6-diylimino-carbonyl) 1 was prepared by the anionic polymerization of a bicyclic oxalactam (abbreviated as BOL, 2) 38-42). The resulting polyamide / has glass transition, fusion, and decomposition points at 130,260-285, and 315 °C, respectively, and its membrane can be obtained by casting from a polyBOL solution. The solubility parameter... 

Membrane design and fabrication requires more optimization than the synthesis of the right type of polymer. For example, those phosphazene polymers that contained the highest ratios of methylamino groups were too brittle to be used as membranes (because of the high glass-transition temperatures) and too soluble in aqueous media. However, the polymers could be made insoluble in water by radiation cross-linking as shown in reaction (54). 

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