Ionomer cluster

Microstructures of CLs vary depending on applicable solvenf, particle sizes of primary carbon powders, ionomer cluster size, temperafure, wetting properties of carbon materials, and composition of the CL ink. These factors determine the complex interactions between Pt/carbon particles, ionomer molecules, and solvent molecules, which control the catalyst layer formation process. The choice of a dispersion medium determines whefher fhe ionomer is to be found in solubilized, colloidal, or precipitated forms. This influences fhe microsfrucfure and fhe pore size disfribution of the CL. i It is vital to understand the conditions under which the ionomer is able to penetrate into primary pores inside agglomerates. Another challenge is to characterize the structure of the ionomer phase in the secondary void spaces between agglomerates and obtain the effective proton conductivity of the layer. 

X-ray diffraction work (11,15) shows that there is an ionomer peak at 4°C which is absent in the acid precursor. This low, broad peak is not affected by annealing or ion type and persists up to 300°C. Since the 4°C peak corresponds to a spacing of about 2.5 nm, it is reasonable to propose a stmctural feature of this dimension in the ionomer. The concept of ionic clusters was initially suggested to explain the large effects on properties of relatively sparse ionic species (1). The exact size of the clusters has been the subject of much debate and has been discussed in a substantial body of Hterature (3,4,18—20). A theoretical treatment has shown that various models can give rise to supramoleculat stmctures containing ionic multiplets which ate about 10 nm in diameter (19). 

Ethylene—Dicarboxylic Acid Copolymers. Partial neutralization of copolymers containing carboxyls in pairs on adjacent carbons, eg, ethylene—maleic acid, has been described (11). Surprisingly, there is no increase in stiffness related to neutralization. Salts with divalent metal cations are not melt processible. The close spacing of the paired carboxyl groups has resulted in ionic cluster morphology which is distinct from that of the commercial ionomer family. 

As the ion content of an ionomer increases, the proportion of the cluster phase to the multiplet-containing... 

Figure 1 (tan 5)max versus ion content for the multiplet phase and the cluster phase of Na-SPS ionomers. 

Thermal treatment and the nature of the casting solvent can also affect the deformation modes achieved in strained films of ionomers. For example, in films cast from polar dimethylformamide (DMF), the solvent interacts with ion-rich clusters and essentially destroys them, as is evident form absence of a second, higher temperature loss peak in such samples. As a result, even in a cast DMF sample of Na-SPS ionomer of high ion content (8.5 mol%), the only deformation mode observed in tensile straining is crazing. However, when these films are given an additional heat treatment (41 h at 210°C), shear... 

Studies of PMMA-based ionomers also demonstrate the influence of thermal treatment on deformation modes (16). For Na salts of PMMA-based ionomers of 6 and 12 mol% that were cast from DMF, only crazes were observed on straining. However, after an additional heat treatment (48 h at 160°C), which also removes any DMF solvent that is present, shear deformation zones are induced. Hence, the ionic cluster phase, which was destroyed by the polar solvent, has been restored by the heat treatment. 

The mechanical properties of ionomers are generally superior to those of the homopolymer or copolymer from which the ionomer has been synthesized. This is particularly so when the ion content is near to or above the critical value at which the ionic cluster phase becomes dominant over the multiplet-containing matrix phase. The greater strength and stability of such ionomers is a result of efficient ionic-type crosslinking and an enhanced entanglement strand density. 

FIGURE 5.10 (a) Scientific representation of the three-phase structure of a dry ionomer, consisting of cation clusters, lamellae, and disordered regions. (From Cowie, J.M.G., Polymer Chemistry and Physics of Modern Materials, Intertext, London, 1973.)... 

Ethylene ionomers consist of copolymers of ethylene and an organic add, such as methacrylic acid, the acid moieties of which have been neutralized to form a metal salt. The metal salts from neighboring chains tend to form clusters, such as the one shown schematically in Fig. 18.3. The net result is the overall structure shown in Fig. 18.2 g), in which the ionic clusters form weak crosslinks between adjacent chains. Ionomers also contain short and long chain branches, which are similar to those found in low density polyethylene. 

The crystallinity levels in ethylene ionomers are generally low due to their high levels of branching and the clustering of the metal salts. At high temperatures, the clusters dissociate and the individual chains can move independently in the molten state, permitting them to be molded. When the ionomer is cooled dusters reform, crosslinking the chains... 

Another approach has been developed to fabricate electrodes with loading as low as 0.1 mg Pt/cm (32). The electrode structure was improved by increasing the contact area between the electrolyte and the platinum clusters. The advantages of this approach are that a thinner catalyst layer of 2 to 3 microns and a uniform mix of catalyst and ionomer are produced. For example, a cell with a Pt loading of 0.17 to 0.13 mg/cm has been fabricated. The cell generated 3 A/cm at > 0.4V on pressurized O2 and 0.65 V at 1 A/cm on pressurized air (32,... 

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