Structural and transport effects of doping perfluorosulfonic acid polymers with the heteropoly acids, H3PW12O40 or H4SiW12O40

A perfluorosulfonic acid (PFSA) polymer with pendant side chain -O(CF₂)₄SO₃H was doped with the heteropoly acids (HPAs), H₃PW₁₂O₄₀ and H₄SiW₁₂O₄₀. Infrared spectroscopy revealed a strong interaction between the HPA and the PFSA ionomer. Modes associated with the peripheral bonds of the HPA were shifted to lower wave numbers when doped into PFSA membranes. Small-angle X-ray scattering (SAXS) measurements showed the presence of large crystallites of HPA in the membrane with d spacings of ca. 10 Å, close to the lattice spacing observed in bulk HPA crystals. Under wet conditions the HPA was more dispersed and constrained the size of the sulfonic acid clusters to 20 Å at a 5 wt% HPA doping level, the same as in the vacuum treated ionomer samples. Under conditions of minimum hydration the HPA decreased the E_a for the self-diffusion of water from 27 to 15 kJ mol⁻¹. The reverse trend was seen under 100% RH conditions. Proton conductivity measurements showed improved proton conductivity of the HPA doped PFSAs at a constant dew point of 80 °C for all temperatures up to 120 °C and at all relative hummidities up to 80%. The activation energy for proton conduction generally was lower than for the undoped materials at RH ≤80%. Significantly the E_a was 1/2 that of the undoped material at RHs of 40 and 60%. A practical proton conductivity of 113 mS cm⁻¹ was observed at 100 °C and 80% RH.     

Dynamic mechanical properties of three different combinations taken from styrene-co-itaconate, styrene-co-methacrylate, and styrene-co-sulfonate ionomers

Dynamic mechanical properties of three different styrene-based ionomer blends containing ca. 5 mol% of ionic repeat units were investigated; the three ionic units were itaconate (ITANa), methacrylate (MANa), and styrenesulfonate (SNa). For SNa-MANa ionomers, it was observed that this ionomer system showed only two loss tangent peaks, implying that this ionomer system resembles a typical miscible system. When the ion content increased, however, the ionomer blend showed two cluster loss tangent peaks, indicating the presence of phase-separated cluster regions. This suggests that, with increasing ion content, the role of ionic units becomes more important than that of host non-ionic units to determine ionomer properties. In the case of ITANa-MANa and ITANa-SNa ionomers, however, it was suggested that the multiplets of the MANa and SNa ionomers might be disrupted upon the addition of the ITANa ionomers. In addition, the SEM images showed that the fracture surfaces of ionomers changed upon blending.     

Ionomer-silica hybrids via sol-gel reaction

Ionomer-silica hybrid materials were made from polyethylene-co-acrylic acid neutralized by a zinc salt (PI) and tetraethoxy silane (TEOS) via the sol-gel reaction. The effects of various experimental parameters such as solvents, H₂O/Si ratio and the amount of TEOS in the ionomer solution on the hybrid structure and properties were examined. The spectroscopic results show that solvents do not affect the structure of the hybrids, but influence the thermal properties. The hybrids made using highly polar solvent exhibit better thermal stability and dynamic mechanical properties at high TEOS contents. The amount of water used for hydrolysis and subsequent condensation play a significant role in the network formation. The varying amount of TEOS in solutions gives rise to different silica content of the hybrid. Above 50 wt%, the sample becomes opaque due to silica aggregation. The high ratio of H₂O/Si leads to phase separation during the reaction. Transparent hybrid materials can only be obtained when the ratio of H₂O/Si is below 5.     

Poly(styrene-b-isobutylene-b-styrene) block copolymer ionomers (BCPI) and BCPI/silicate nanocomposites. 2. NaBCPI sol-gel polymerization templates

Polystyrene (PS) blocks in poly(styrene-b-isobutylene-b-styrene) (PS-PIB-PS) block copolymers were partially sulfonated and the acid groups converted to Na⁺SO₃⁻ groups to create ionomers. Then, dimethylacetamide was used to selectively swell the ionic PS domains and the swollen films were exposed to sol-gel reactive tetraethylorthosilicate solutions. (EtO)_4−xSi(OH)_x monomers then permeated films so that sol-gel reactions occurred within/around the ionic PS domains. Environmental scanning electron microscopy/energy dispersive X-ray spectroscopy investigations showed that silicate structures can be incorporated within the interior of the ionomer films. Differential scanning calorimetry studies indicated that there is no variance in the PIB block T_g with respect to ionomer formation, or with respect to silicate loading of the ionomer at low levels, which suggests that the silicate component does not reside in the PIB phase. ²³Na solid state NMR spectroscopy detected isolated Na⁺SO₃⁻ groups as well as aggregated SO₃⁻Na⁺ ion pairs for ‘as cast’ and ‘dry’ non-silicate containing ionomer samples. In a hydrated sample, almost all Na⁺ ions were solvent-separated. AFM analysis showed that phase separation exists, but that the degree of order is significantly less than that for hybrids based on the corresponding benzyltrimethylammonium ionomer. This frustrated morphology was also seen in the results of small angle X-ray scattering experiments. Given the scale of organic/inorganic heterogeneity, these hybrids are properly classified as nanocomposites.     

Ionomer content effects on the electrocatalyst layer with in-situ grown Pt nanowires in PEMFCs

The effects of ionomer contents were investigated in composite electrodes with in-situ grown single crystal Pt nanowires (Pt-NWs) for PEMFCs, including the amount in the carbon matrix and impregnated on the surface of the electrocatalyst layer. The electrocatalyst layer was prepared by growing Pt-NWs directly on the carbon matrix with a simple one-step wet chemical approach at room temperature. Transmission electron microscopy (TEM), scanning electron microscopy (SEM), polarization curve tests, electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV) were employed to evaluate the ionomer effects. The experimental results showed that the ionomer in the carbon matrix had an influence on the ionic conductivity and aggregation and distribution of the Pt-NWs, and the ionomer impregnated on the surface of the electrocatalyst layer affected the mass transport and ionic conductivity. The performance of the MEA was improved by optimizing the ionomer contents.     

Sulfonated poly(ether ether ketone) as an ionomer for direct methanol fuel cell electrodes

Sulfonated poly(ether ether ketone) has been investigated as an ionomer in the catalyst layer for direct methanol fuel cells (DMFC). The performance in DMFC, electrochemical active area (by cyclic voltammetry), and limiting capacitance (by impedance spectroscopy) have been evaluated as a function of the ion exchange capacity (IEC) and content (wt.%) of the SPEEK ionomer in the catalyst layer. The optimum IEC value and SPEEK ionomer content in the electrodes are found to be, respectively, 1.33 meq. g⁻¹ and 20 wt.%. The membrane-electrode assemblies (MEA) fabricated with SPEEK membrane and SPEEK ionomer in the electrodes are found to exhibit superior performance in DMFC compared to that fabricated with Nafion ionomer due to lower interfacial resistance in the MEA as well as larger electrochemical active area. The MEAs with SPEEK membrane and SPEEK ionomer also exhibit better performance than that with Nafion 115 membrane and Nafion ionomer due to lower methanol crossover and better electrode kinetics.     

The effect of solvent and ionomer on agglomeration in fuel cell catalyst inks: Simulation by the Discrete Element Method

We simulate agglomeration in different fuel cell catalyst ink solutions using Discrete Element Method. Carbon support is modelled as particles in various inks with ionomer and various solvents. The particles interact with particle-pair forces resulting in agglomerate build-up. The classical colloidal theory with van der Waals and electric double layer forces underestimates the ink stability, which motivates the development of a new model of polymer force between particles. The force is activated when there is a bridging of polymer between the carbon black particles, and the strength is dependent on the ionomer interaction with the solvent by the dielectric constant. A critical dielectric constant was defined for which ionomer form a web-like polymer network that increases the ink stability. This modification can explain the trend of the ink stability, and the model can simulate the effect of different solvents on the agglomerate size distribution with good agreement with experimental results.     

Isobutylene-based ionomer composites: siliceous filler reinforcement

The morphology, mechanical, and barrier properties of composites derived from phosphonium bromide ionomer derivatives of an isobutylene-based elastomer (IIR-PPh₃Br) are compared with analogous non-ionic composites. Improved adhesion between the ionomer and onium ion-exchanged montmorillonite clay allowed standard polymer compounding techniques to yield highly reinforced elastomer nanocomposites. Similar increases in the strength of interactions between ionomer and precipitated silica resulted in reduced filler agglomeration, and higher degrees of composite reinforcement.     

Influence of ionomer content on the structure and performance of PEFC membrane electrode assemblies

Nafion^® ionomer content of the cathode catalyst-layer of a polymer electrolyte fuel cell (PEFC), made by the “decal” hot pressing method, has been investigated for its effect on performance and structure of the membrane electrode assembly (MEA). Varying Nafion^® content was shown to have an effect on performance within the entire range of polarization curves (i.e. kinetic, ohmic, and mass-transport regions) as well as on the structure. AFM analysis shows the effect of Nafion on the dispersion of carbon aggregates. Further analysis using TEM demonstrates the effect of Nafion on both the dispersion of carbon aggregates and the distribution and thickness of the Nafion ionomer films surrounding the catalyst/carbon aggregates. The MEA structure change correlates well with the MEA performance on both kinetics and mass-transport region. The determining factors on the performance of MEA are the interfacial zone (between the ionomer and catalyst particle), the dispersion of catalyst/carbon aggregates and the distribution/thickness of Nafion films. An optimized Nafion^® content in the range of 27 ± 6 wt.% for the cathode was determined for an E-TEK 20% Pt₃Cr/C catalyst at a loading of 0.20 mg Pt/cm².     

Nanocomposites from poly(ethylene-co-methacrylic acid) ionomers: effect of surfactant structure on morphology and properties

A detailed study of the structure-property relationships for nanocomposites prepared using melt processing techniques from a sodium ionomer of poly(ethylene-co-methacrylic acid) and a series of organoclays is reported. Transmission electron microscopy, X-ray scattering, stress-strain behavior, and Izod impact analysis were used to evaluate the nanocomposite morphology and physical properties. Four distinct surfactant structural effects lead to improved levels of exfoliation and higher stiffness for these nanocomposites: higher number of alkyl tails on the amine rather than one, longer alkyl tails instead of shorter ones, use of 2-hydroxy-ethyl groups as opposed to methyl groups on the ammonium ion, and an excess amount of the amine surfactant on the clay instead of an equivalent amount. These trends are opposite of what has been seen in nylon 6 based nanocomposites but are similar to those observed in nanocomposites formed from LDPE and LLDPE. Although some organoclays were exfoliated better than others, none of the ionomer-based nanocomposites exhibited exfoliation levels as great as those seen in nylon 6 nanocomposites; nevertheless, these nanocomposites offer promising improvements in performance and may be particularly interesting for barrier applications.