Ionic domains Ionomers

McLean, R. S., Doyle, M. and Sauer, B. B. 2000. High-resolution imaging of ionic domains and crystal morphology in ionomers using AFM techniques. 

The Rh, Ru, and Pt ionomers of perfluoro- carbonsulfonic acid polymers have been formed and reduced to investigate the formation of metal particles within the ionic domains of these materials 88). The particle size distributions peak in the 2.5 to 4.0 nm range. The reduced ionomers catalyze the CO oxidation with the activity sequence Ru > Rh > Pt. Diffusion limitations occur in the cases of the Rh and Ru, but not the Pt, ionomer catalysts. 

Furthermore, in 2001, Ballard entered an alliance with Victrex to produce two new membrane alternatives. One membrane is based on sulfonated poly(arylether) ketone (a variant of PEEK) supplied by Victrex, which may be better suited to PEMFC fabrication applications. In March 2002, U.S. Patent 6,359,019 was issued to Ballard Power for a graft-polymeric membrane in which one or more trifluorovinylaromatic monomers are radiation graft polymerized to a preformed polymeric base. The strucmres of BAM membranes have been studied by way of small-angle neutron scattering (SANS) [97]. The study of the ionomer peak position suggests the existence of relatively small ionic domains compared to Nalion, despite large water content. Phase separation in the polymer matrix is possibly crucial for the membrane s mechanical and transport properties. 

Sauer, B.B. McLean, R.S. AFM and x-ray studies of crystal and ionic domain morphology in poly(ethylene-co-methacrylic acid) ionomers. Macromolecules 2000, 33, 7939. 

It should be acknowledged that Risen utilized the concept of the ionic domains in ionomers (Nafion sulfonates, sulfonated linear polystyrene) as microreactors within which transition metal partides can be grown and utilized as catalysts (23-25). Transition metal (e.g. Rh, Ru, Pt, Ag) cations were sorbed by these ionomers from aqueous solutions and preferentially aggregated within the pre-existing clusters of fixed anions. Then, the ionomers were dehydrated, heated and reduced to the metallic state with Hg. Risen discussed the idea of utilizing ionomeric heterophasic morphology to tailor the size and size distributions of the incorporated metal particles. The affected particle sizes in Nafion were observed, by electron microscopy, to be in the range of 25-40 A, which indeed is of the established order of cluster sizes in the pre-modified ionomer. 

Small domains of high electronic density have been imaged in halato-telechelic ionomers by Scanning Transmission Electron Microscopy (STEM) using the technique of atomic number or Z-contrast. The possibility that these are ionic domains is evaluated and the morphology compared with that derived from recent SAXS experiments. 

Even less is known about ionomer/plasticizer interactions on a molecular level. A variety of scattering and spectroscopic techniques that can probe this level have been mentioned, but they have been applied primarily to the specific case of water in ionomers, and in particular to hjdrated perfluorinated ionomers. At the least, these studies demonstrate the powerful potential of the techniques to contribute to a more complete understanding of structure-property relationships in plasticizer/ionomer systems. For e.xample, to return to the question of the effect of nonpolar plasticizers on the ionic domains how can the decrease in the ionic transition temperature be reconciled with the apparently minimal effect on the SAXS ionomer peaks and with the ESR studies that indicate (not surprisingly) tiiat these plasticizers have essentially no influence on the local structure of the ions Is it due to their association with the hydrocai bon component of the large aggregates or clusters Or if these entities do not exist, as some researchers postulate, what is the interaction between the nonpolar plasticizer, the hydrocarbon component and the ionic domains These questions are, of course, intimately related to the understanding of ionomer microstructure even in the absence of plasticizer. The interpretation of SAXS data in particular is subject to the choice of model used. 

Ionomers are polymers that are functionalized with ionic groups (usually anionic sites) attached at various points along polymeric backbones that are not extensively crosslinked (1-2). Such materials have a tendency to form ionic domains in which the anionic groups and their associated cations are microphase separated from the typically hydrophobic portions of the polymer. Thus, the ionic domains formed are isolated by a medium of low dielectric constant (i.e. the polymeric backbone) although, in some cases, hydrophilic channels have been reported to connect adjacent ionic domains (3). The size and structures of these domains vary with the nature of the cation, the stoichiometry of the polymer, the degree of solvation of the system and the method of preparation. They can be as small as ion-pairscor small multiplets, but in some cases they have been reported to be in the 20-100 A" diameter range. 

The characteristics discussed above are mainly related to clustering in the ionic phase, but the role of the hydrophobic phase also is quite important. In some cases it controls the gas transport properties of the material (e.g. 02 through PFSA) (4). And, it makes it possible to keep hydrophobic reactions in the neighborhood of the ionic domain species (5). Moreover, metal complexes with bulky hydrophobic ligands can be supported in the ionomers because of synergystic interaction of both polymer phases (6). Interesting electrocatalytic or photocatalytic systems take advantage of these unique properties of ionomers (7-8). Moreover, support of the reactants in ionomers may be useful for reactant/product separations. 

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