Equivalent weight (EW) is the number of grams of dry Nafion per mole of sulfonic acid groups when the material is in the acid form. This is an average EW in the sense that the comonomer sequence distribution (that is usually unknown to the investigator and largely unreported) gives a distribution in m in this formula. EW can be ascertained by acid-base titration, by analysis of atomic sulfur, and by FT-IR spectroscopy. The relationship between EW and m is EW ) 100m + 446 so that, for example, the side chains are separated by around 14 CF2 units in a membrane of 1100 EW. Common at the time of this writing are Nafion 117 films. The designation “117” refers to a film having 1100 EW and a nominal thickness of 0.007 in., although 115 and 112 films have also been available. Early-reported studies involved 1200 EW samples as well as special experimental varieties, some being rather thin. The equivalent weight is related to the property more often seen in the field of conventional ion exchange resins, namely the ion exchange capacity (IEC), by the equation IEC ) 1000/EW. The mention of the molecular weight of high equivalent weight (EW > 1000 g‚mol-1) Nafion is almost absent in the literature, although the range 105-106 Da has been mentioned. As this polymer does not form true solutions, the common methods of light scattering and gel permeation chromatography cannot be used to determine molecular weight as well as the size and shape of isolated, truly dissolved molecules. Studies of the structure of this polymer in solvent (albeit not a true solution) will be mentioned in the scattering section of this review. It should be noted that Curtin et al. performed size exclusion chromatography determinations of the molecular weight distribution in Nafion aqueous dispersions after they were heated to high temperatures (230, 250, and 270 °C).1 Before heating, there was a high molecular weight shoulder on a bimodal distribution, due to molecular aggregates, but this shoulder disappeared upon heating, which indicated that the aggregates were disrupted. The peaks for the monomodal distribution for the heated samples were all located at molecular weights slightly higher than 105 g‚mol-1. Also, light scattering experiments revealed that the radius of gyration had a linear dependence on the molar mass of the aggregates, which suggests that the particles are in the form of rods or ribbons, or at least some elongated structure. Nafion ionomers are usually derived from the thermoplastic -SO2F precursor form that can be extruded into sheets of required thickness. Strong interactions between the ionic groups are an obstacle to melt processing. This precursor does not possess the clustered morphology that will be of great concern in this article but does possess Teflon-like crystallinity which persists when the sulfonyl fluoride form is converted to, for example, the K+ form by reacting it with KOH in water and DMSO. Thereafter, the -SO3H form is achieved by soaking the film in a sufficiently concentrated aqueous acid solution. Extrusion of the sulfonyl fluoride precursor can cause microstructural orientation in the machine direction, * Address correspondence to either author. Phone: 601-266-5595/ 4480. Fax: 601-266-5635. E-mail: Kenneth.Mauritz@usm.edu; RBMoore@usm.edu. 4535 Chem. Rev. 2004, 104, 4535−4585

State of Understanding of Nafion

Block copolymers are all around us, found in such products as upholstery foam, adhesive tape and asphalt additives. This class of macromolecules is produced by joining two or more chemically distinct polymer blocks, each a linear series of identical monomers, that may be thermodynamically incompatible (like oil and vinegar). Segregation of these blocks on the molecular scale (5–100 nm) can produce astonishingly complex nanostructures, such as the “knitting pattern” shown on the cover of this issue of PHYSICS TODAY. This striking pattern, discovered by Reimund Stadler and his coworkers, reflects a delicate free‐energy minimization that is common to all block copolymer materials.

Block Copolymers—Designer Soft Materials

DLS and zeta potential - What they are and what they are not?

The structure of the Nafion ionomer used in proton-exchange membranes of H(2)/O(2) fuel cells has long been contentious. Using a recently introduced algorithm, we have quantitatively simulated previously published small-angle scattering data of hydrated Nafion. The characteristic 'ionomer peak' arises from long parallel but otherwise randomly packed water channels surrounded by partially hydrophilic side branches, forming inverted-micelle cylinders. At 20 vol% water, the water channels have diameters of between 1.8 and 3.5 nm, with an average of 2.4 nm. Nafion crystallites (approximately 10 vol%), which form physical crosslinks that are crucial for the mechanical properties of Nafion films, are elongated and parallel to the water channels, with cross-sections of approximately (5 nm)(2). Simulations for various other models of Nafion, including Gierke's cluster and the polymer-bundle model, do not match the scattering data. The new model can explain important features of Nafion, including fast diffusion of water and protons through Nafion and its persistence at low temperatures.

Parallel cylindrical water nanochannels in Nafion fuel-cell membranes.

In this comprehensive review, recent progress and developments on perfluorinated sulfonic-acid (PFSA) membranes have been summarized on many key topics. Although quite well investigated for decades, PFSA ionomers’ complex behavior, along with their key role in many emerging technologies, have presented significant scientific challenges but also helped create a unique cross-disciplinary research field to overcome such challenges. Research and progress on PFSAs, especially when considered with their applications, are at the forefront of bridging electrochemistry and polymer (physics), which have also opened up development of state-of-the-art in situ characterization techniques as well as multiphysics computation models. Topics reviewed stem from correlating the various physical (e.g., mechanical) and transport properties with morphology and structure across time and length scales. In addition, topics of recent interest such as structure/transport correlations and modeling, composite PFSA membranes, degradat...

New Insights into Perfluorinated Sulfonic-Acid Ionomers

Small-angle x-ray scattering study of perfluorinated ionomer membranes. 1. Origin of two scattering maxima

Domain-Boundary Structure of Styrene-Isoprene Block Copolymer Films Cast from Solutions. 5. Molecular-Weight Dependence of Spherical Microdomains

Small-angle x-ray scattering study of perfluorinated ionomer membranes. 2. Models for ionic scattering maximum

Ordered structure in dilute solutions of ionic biopolymers. 2. Small-angle x-ray scattering study of sodium polyacrylate solution

It was shown that some block copolymers and their blends with corresponding homopolymers exhibit stress softening. When the specimens are stretched beyond the yield point, they become rubbery and exhibit high elasticity and large recoverable deformation, as a result of a breakup of their original rigid structure. Moreover, the deformed specimens heal, in that the properties of the original undeformed specimens are recovered upon removal of applied stress. This effect was attributed to the reformation of the original microdomain structure. In this work, we investigated an SBS block copolymer and a blend of the copolymer with homopolystyrene in regard to the structural change accompaning the plastic-to-rubber transition and the healing process. Electron microscopy and small angle X-ray scattering (SAXS) were used.

Mineo Fujimura

Papers

Small-angle x-ray scattering study of perfluorinated ionomer membranes. 1. Origin of two scattering maxima

Domain-Boundary Structure of Styrene-Isoprene Block Copolymer Films Cast from Solutions. 5. Molecular-Weight Dependence of Spherical Microdomains

Small-angle x-ray scattering study of perfluorinated ionomer membranes. 2. Models for ionic scattering maximum

Ordered structure in dilute solutions of ionic biopolymers. 2. Small-angle x-ray scattering study of sodium polyacrylate solution

Structural Change Accompanied by Plastic-to-Rubber Transition of SBS Block Copolymers