The Ionic Conductivity of a Nafion® 1100 Series of Proton‐exchange Membranes Re‐cast from Butan‐1‐ol and Propan‐2‐ol

The ionic conductivity of Nafion® 1100 extruded membranes re‐cast from solutions of butan‐1‐ol and propan‐2‐ol is measured in 0.5 mol dm^–3 H₂SO₄ at 295 K, using an immersed, four‐electrode d.c. technique. The general trend is an increasing conductivity for the thicker membranes. Materials which were solution‐cast from butan‐1‐ol yielded the highest conductivity while a series of membranes with lower conductivities (similar to those of an extruded Nafion® 1100 series of membranes) was found using propan‐2‐ol. The conductivity results indicate that membranes manufactured by extrusion and casting from various solvents might have different structures. Differences in the water content and conductivity of the membranes are considered to arise from the impact of processing conditions on the surface and bulk structure of the membranes.     

Temperature Effects on the Molecular Dynamics of Modified Nafion® Membranes Incorporating Ionic Liquids' Cations: A 1H NMRD Study

Nafion® is the polymer electrolyte membrane most used in fuel cells (PEMFC), however Nafion® presents some limitations due to the water loss with increasing temperature. In this work is presented the study of the molecular dynamics in modified Nafion®/ionic liquids (IL) cations membranes with increasing temperature, by proton NMR relaxometry (¹H NMRD). Three Nafion® membranes modified with Phenyltrimethylammonium (TMPA⁺), 1‐n‐butyl‐3‐methylimidazolium (BMIM⁺) and n‐dodecyltrimethylammonium (DTA⁺) IL cations were considered. This study allowed the evaluation of the effect of the IL cations incorporation in Nafion® membranes and to assess the degree of confinement of the IL cations in the membranes matrix in relation with the water content. Thermogravimetry analysis was also performed to study the water loss with increasing temperature of the Nafion®/IL cations membranes. It was possible to establish a correlation between the water content and the IL cations self‐diffusion coefficients. The sequential order of the hydration level obtained for the studied systems was Nafion®/DTA⁺>Nafion®/BMIM⁺ ≳ Nafion®/H⁺>Nafion®/TMPA⁺, while the water loss follows the sequence Nafion®/H⁺>Nafion®/BMIM⁺∼Nafion®/DTA⁺>Nafion®/TMPA⁺. The Nafion®/BMIM⁺ presented the largest temperature variation of both the self‐diffusion coefficient and the hydration conditions. In terms of PEMFCs efficiency, the Nafion®/DTA⁺ modified membrane seems to offer the largest and stable hydration conditions with temperature.     

Sorption and transport properties of the semi‐interpenetrating network based on crosslinked poly(vinyl alcohol) and poly(styrene sulfonic acid‐co‐maleic anhydride) as proton‐conducting membranes

This study investigates the sorption and transport properties of hydrocarbon membranes based on poly(vinyl alcohol) network and poly(styrene sulfonic acid‐co‐maleic acid) (PSSA‐MA). The water and methanol self‐diffusion coefficients through an 80 wt % PSSA‐MA interpenetrating SIPN‐80 membrane measured 3.75 × 10^?6 and 5.47 × 10^?7 cm²/s, respectively. These results are lower than the corresponding values of Nafion® 115 (8.89 × 10^?6 cm²/s for water and 8.63 × 10^?6 cm²/s for methanol). The methanol permeability of SIPN‐80 membrane is 4.1 × 10^?7 cm²/s, or about one‐fourth that of Nafion® 115. The difference in self‐diffusion behaviors of Nafion® 115 and SIPN‐80 membranes is well correlated with their sorption characteristics. The solvent uptake of Nafion® 115 increased as the methanol concentration increased up to a methanol mole fraction of 0.63, and then decreased. However, the solvent uptake of the SIPN‐80 membranes decreased sluggishly as the methanol concentration increased. The λ values of water and methanol (i.e., λ and λ) in Nafion® 115 are quite close, indicating no sorption preference between water and methanol. In contrast, the λ value is only one‐third λ for a SIPN‐80 membrane. Accordingly, the SIPN membranes are regarded as candidates for direct methanol fuel cell applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of polybenzimidazole/α‐zirconium phosphate composites as proton exchange membrane

To improve the high‐temperature performance of proton exchange membranes, the polybenzimidazole (PBI)/α‐zirconium phosphate (α‐Zr(HPO₄)₂·nH₂O, α‐ZrP) proton exchange composite membranes were prepared in this study. PBI polymer containing a large amount of ether units has been synthesized from 3,3′‐ diaminobenzidine (DAB) and 4,4′‐oxybis (benzoic acid) by a direct polycondensation in polyphosphoric acid. The polymer exhibited a good solubility in most polar solvents. Inorganic proton conductor α‐ZrP nanoparticles have been obtained using a synthesis route involving separate nucleation and aging steps (SNAS). The effects of α‐ZrP doping content on the composite membrane performance were investigated. It was found that the introduction of ZrP improved the thermal stability of the composite membranes. The PBI/ZrP composite membranes exhibited excellent mechanical strength. The composite membrane with 10 wt% ZrP showed the highest proton conductivity of 0.192 S cm^?1 at 160°C under anhydrous condition. The proton conducting mechanism of the PBI/ZrP composite membranes was proposed to explain the proton transport phenomena. The experimental results suggested that the PBI/ZrP composite membranes may be a promising polymer electrolyte used in high temperature proton exchange membrane fuel cells (HT‐PEMFCs) under anhydrous condition. POLYM. ENG. SCI., 56:622–628, 2016. © 2016 Society of Plastics Engineers     

Evaluating the Effectiveness of Using Flexography Printing for Manufacturing Catalyst‐Coated Membranes for Fuel Cells

This study is an evaluation of the effectiveness of the flexography printing process for manufacturing catalyst‐coated membranes (CCMs) for use in proton exchange membrane fuel cells (PEMFCs). Flexography is a maskless and continuous process that is used in large‐scale production with water‐based inks to reduce the cost of production of PEMFC components. Unfortunately, water has undesirable effects on the Nafion® membrane: water wets the membrane surface poorly and causes the membrane to bulge outwards significantly. Membrane printability was improved by pre‐treating membrane samples by water immersion for short periods (<2 min). This pre‐treatment was used to control the membrane deformation before printing to limit the impact of the ink transfer. Water and ink drop deposition experiments were performed to estimate the liquid‐air‐Nafion® apparent contact angle and the locally induced membrane deformation. Despite the short immersion times used in the tests, the immersion pre‐treatment appeared to induce structural modifications that enhanced both the membrane wettability and the dimensional stability. Flexography printability tests were performed on these treated membranes and showed that the dimensional instability of the Nafion® membrane was the critical parameter for limiting the ink transfer. The immersion pre‐treatment improved the printability of the Nafion® membranes, which were used to fabricate cathodes that were tested in an operational fuel cell.     

Synthesis of poly(β‐pinene)‐g‐polystyrene from allylic brominated poly(β‐pinene)

Poly(β‐pinene) was brominated by N‐bromosuccinimide on the allylic carbons. Then the brominated product was activated by AlEt₂Cl to initiate the polymerization of styrene to give a β‐pinene/styrene graft copolymer. AlEt₂Cl was selected because it alone could not initiate the polymerization of styrene. The obtained graft copolymer was characterized by GPC, ¹H‐NMR, and DSC measurements, respectively. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 599–603, 2000     

Conventional and RAFT radical copolymerizations of β‐pinene with N‐substituted maleimides

The feasibility of the radical copolymerizations of β‐pinene with three N‐substituted maleimides, i.e. N‐phenylmaleimide (PhMI), N‐methylmaleimide (MeMI), and N‐ethylmaleimide (EtMI), was clarified for the first time. The copolymerization rates decreased in the order PhMI > MeMI > EtMI. A marked penultimate effect on the activity of the N‐substituted maleimide‐terminated radicals was found in these copolymerizations. The penultimate monomer reactivity ratios evaluated by the nonlinear method were r₁ = 0.10, r′₁ = 8.30, r₂ = r′₂ = 0 for PhMI–β‐pinene, r₁ = 0.20, r′₁ = 7.09, r₂ = r′₂ = 0 for MeMI–β‐pinene, and r₁ = 0.16, r′₁ = 6.50, r₂ = r′₂ = 0 for EtMI–β‐pinene. Furthermore, the possible controlled copolymerizations of β‐pinene and N‐substituted maleimides were then attempted via the reversible addition‐fragmentation chain transfer (RAFT) technique. In the presence of RAFT agent 1‐phenylethyl phenyldithioacetate, the copolymerization of β‐pinene with MeMI or EtMI was retarded severely. However, much smaller retardation was observed in the RAFT copolymerization of β‐pinene with PhMI, and, more importantly, the copolymerization exhibited typical features of a controlled system. The solvent effect on the RAFT copolymerization of β‐pinene and PhMI was also investigated using matrix‐assisted laser desorption ionization time‐of‐fight mass spectrometry (MALDI‐TOF‐MS) analysis. The results clearly indicated that copolymerization in tetrahydrofuran suffered from competitive transfer and termination side‐reactions arising from the solvent in spite of the presence of the RAFT agent. Copyright © 2007 Society of Chemical Industry     

Hydration of α-pinene over molybdophosphoric acid immobilized in hydrophobically modified PVA membranes

A polyvinylalcohol/molybdophosphoric acid (PVA/HPMo) membrane crosslinked with succinic acid was modified by treatment with acetic anhydride in order to improve its hydrophobic properties, and was used as catalyst in the hydration reaction of α-pinene. The increase of membrane hydrophobicity with acetylation is documented not only by the water droplet contact angle but also by the sorption coefficients of α-pinene and water. The introduction of acetyl groups improves the membrane transport properties, as reflected by pinene diffusivity calculated from permeation data.A kinetic-diffusion model was developed assuming that the reaction product α-terpineol affects the transport of water and α-pinene across the acetylated PVA membranes. When membrane acetylation increases, the model predicted kinetic constants for hydration and isomerization reactions decrease, although the initial water diffusivity increases. These results suggest that the increase of catalytic activity may be due to an improvement of water transport across the membrane.     

A Sulfophenylated Polysulfone as the DMFC Electrolyte Membrane – an Evaluation of Methanol Permeability and Cell Performance

A sulfophenylated polysulfone (PSU‐sph), carrying 0.8 sulfonic acid units per repeating unit of the polymer, is evaluated as a membrane electrolyte for DMFC applications. The liquid uptake, methanol transport characteristics, electrolyte conductivity, and fuel cell performance are investigated. The methanol transport and DMFC performance results are compared to those of Nafion® 117. The PSU‐sph membrane investigated shows superior qualities with regard to methanol crossover, with a methanol permeability of approximately 25% compared to that of Nafion®. The conductivity was measured to be 15% compared to that of Nafion®. However, this could not fully account for the internal resistance of the cell, implying that the contact resistance between the electrodes and electrolyte is higher when PSU‐sph is used, probably because the electrodes are developed for use with Nafion® membranes. The stability of the PSU‐sph membrane seems promising, with very low degradation observed over a period of 72 hours. It was concluded that although the mass transport properties of the PSU‐sph membrane sample investigated were superior, it could not match the performance of Nafion® 117 in a DMFC application. However, a higher degree of sulfonation may have a significant positive effect on cell performance. The results also showed that a fully intergrated MEA is needed to fully assess new menbrane materials.     

Durability enhancement of Nafion® fuel cell membranes via in situ sol‐gel‐derived titanium dioxide reinforcement

To improve durability of Nafion® membranes, samples were modified via an in situ sol‐gel polymerization of titanium isopropoxide to generate titania quasi‐networks in the polar domains. The incorporated titania reduced water uptake but equivalent weight was essentially unchanged. Fuel cell performance of the modified membrane was inferior to that of the unfilled membrane although these were considered as model studies with focus on mechanical durability. Mechanical analysis of contractile stress buildup during drying from a swollen state in samples clamped at constant length demonstrated considerable reinforcement of Nafion® by the titania structures. Tensile studies showed that at 80°C and 100% relative humidity the dimensional change of the composite membrane is one half and the initial modulus is three times higher than that of the unmodified membrane. During an open circuit voltage decay test the voltage decay rate for the modified membrane is 3.5 times lower than that of control Nafion®. Fluoride emission for the composite is at least an order of magnitude lower than that of the control Nafion® membrane indicating reduced chemical degradation. These model studies indicate that this in situ inorganic modification offers a way to enhance fuel cell membrane durability by reducing both physical and chemical degradation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of γ‐aminopropyltriethoxylsilane on morphological characteristics of hybrid nylon‐66‐based membranes before electron beam irradiation

Nylon‐66 is a typical semicrystalline polymer that can be crosslinked using crosslinking agents and electron beam irradiation. Hybrid nylon‐66‐based membranes are more porous but denser compared to the pure nylon‐66 membrane. Besides that, hybrid nylon‐66 membranes exhibit higher water uptake and severe swelling in water. Si/nylon‐66 membranes were prepared by adding γ‐aminopropyltriethoxylsilane (APTEOS). Crosslinked silica in nylon‐66 membranes is confirmed with high gel content and Fourier transform infrared peaks, but XRD results showed that there is a low crystalline degree in these membranes. The thermal stability of hybrid nylon‐66 membranes is also less affected by APTEOS. The crosslinking agent only improves storage modulus in hybrid nylon‐66 membranes. After irradiation, it is learned that APTEOS improves separation performance of nylon‐66 membranes. However, excessive APTEOS causes the ratio of effective thickness over porosity (Δx/A_k) reduces significantly resulting a lower permeability membrane. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Performance Study of Direct Borohydride Fuel Cells Employing Polyvinyl Alcohol Hydrogel Membrane and Nickel‐Based Anode

A direct borohydride fuel cell (DBFC) employing a polyvinyl alcohol (PVA) hydrogel membrane and a nickel‐based composite anode is reported. Carbon‐supported platinum and sputtered gold have been employed as cathode catalysts. Oxygen, air and acidified hydrogen peroxide have been used as oxidants in the DBFC. Performance of the PVA hydrogel membrane‐based DBFC was tested at different temperatures and compared with similar DBFCs employing Nafion® membrane electrolytes under identical conditions. The borohydride–oxygen fuel cell employing PVA hydrogel membrane yielded a maximum peak power density of 242 mW cm^–2 at 60 °C. The peak power densities of the PVA hydrogel membrane‐based DBFCs were comparable or a little higher than those using Nafion® 212 membranes at 60 °C. The fuel efficiency of borohydride–oxygen fuel cell based on PVA hydrogel membrane and Ni‐based composite anode was found to be between 32 and 41%. The cell was operated for more than 100 h and its performance stability was recorded.     

The preparation of α‐bis and α,ω‐tetrakis aromatic oxazolyl‐ and carboxyl‐functionalized polymers using 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene in atom transfer radical polymerization reactions

The preparation of new compounds, 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethanol and a new symmetrically disubstituted 1,1‐diphenylethylene derivative, 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene, is described. 1,1‐Bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene was utilized as a dioxazolyl initiator precursor for the polymerization of styrene by atom transfer radical polymerization (ATRP) methods to produce α‐bis(oxazolyl) polystyrene. The kinetic study of the polymerization process indicated that the free radical polymerization reaction for the preparation of α‐bis(oxazolyl) polystyrene follows first‐order rate kinetics with respect to monomer consumption. α,ω‐Tetrakis(oxazolyl) polystyrene was prepared by a new, in situ, controlled/living, post‐ATRP chain‐end‐functionalization reaction which involves the direct addition of 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene to the ω‐terminus of the α‐bis(oxazolyl) polystyrene derivative, without the isolation and purification of the polymeric precursor. α‐Bis(carboxyl) and α,ω‐tetrakis(carboxyl) polystyrene derivatives were obtained by the quantitative chemical transformation of the oxazoline groups of the respective aromatic oxazolyl chain‐end‐functionalized polystyrene derivatives to the aromatic carboxyl groups. The organic precursor compounds, the dioxazolyl‐functionalized 1,1‐diphenylethylene derivative and the functionalized polymers were characterized using ¹H NMR and ¹³C NMR spectrometry and Fourier transform infrared spectroscopy, size‐exclusion and thin‐layer chromatography and non‐aqueous titration measurements. © 2014 Society of Chemical Industry     

Separation of α‐Lactalbumin and β‐Lactoglobulin by a Convenient Liquid‐Solid Extraction System: Application to Milk Whey

A liquid‐solid extraction system based on Tween 80/phosphate was developed. Under the optimized conditions (9 wt % Tween 80, 1.6 : 1 (molar ratio) K₂HPO₄ : NaH₂PO₄, 1.25 mol/L total phosphate, pH = 7.4), α‐Lactalbumin (α‐La) and β‐Lactoglobulin (β‐Lg) were separated with recovery rates of 87.6 % (in the solid polymeric phase) and 98.2 % (in the salt aqueous phase), respectively. Under the effects of water and salt, the solid phase had the ability to form a new liquid‐solid extraction system, and 85.1 % of α‐La could be reversely extracted into the new salt aqueous phase. Following dialysis against water, proteins obtained through extraction and reverse extraction, were analyzed by polyacrylamide gel electrophoresis (PAGE) and thin‐layer scanning. The method was applied successfully to separate α‐La and β‐Lg from milk whey.     

Stereo‐Controlled Asymmetric Bioreduction of α,β‐Dehydroamino Acid Derivatives

α,β‐Dehydroamino acid derivatives proved to be a novel substrate class for ene‐reductases from the ‘old yellow enzyme’ (OYE) family. Whereas N‐acylamino substituents were tolerated in the α‐position, β‐analogues were generally unreactive. For aspartic acid derivatives, the stereochemical outcome of the bioreduction using OYE3 could be controlled by variation of the N‐acyl protective group to furnish the corresponding (S)‐ or (R)‐amino acid derivatives. This switch of stereopreference was explained by a change in the substrate binding, by exchange of the activating ester group, which was proven by ²H‐labelling experiments.     

Chiral recognition of enantiomeric isobornyl methacrylate‐containing hydrogels with α‐cyclodextrin

Two enantiomers of isobornyl methacrylate (iBMA) were prepared by reducing (1R,4R)‐(+)‐camphor and (1S,4S)‐(?)‐camphor followed by simple methacrylation reaction. The iBMA enantiomers were incorporated into hydrophilic polymer networks by free radical polymerization with N,N‐dimethylacrylamide and diethylene glycol dimethacrylate at different molar ratios. The influence of α‐cyclodextrin (α‐CD) and randomly methylated β‐cyclodextrin (rβ‐CD), and thereby enantioselectivity, on the swelling behaviour of the enantiomeric networks in water and alcoholic solutions was examined. An increase of swelling was observed on addition of α‐CD and rβ‐CD. While rβ‐CD showed a greater influence on the swelling itself, only α‐CD was able to achieve a minor differentiation between the polymer networks by their enantiomeric components and therefore a chiral recognition of the iBMA moieties. These results were validated using rheological measurements. © 2015 Society of Chemical Industry     

Mechanical and hydration properties of Nafion®/ceramic nanocomposite membranes produced by mechanical attrition

A solid state method of Nafion®/ceramic nanocomposite membrane preparation is described. A nanocomposite powder from Nafion pellets and a zirconium phosphate ceramic is formed by mechanical milling. The nanoparticles are then consolidated into membrane form by mechanical pressing. Cross‐sectional analysis by scanning electron microscopy indicates that the ceramic particles exist in agglomerates that are evenly dispersed across the membrane. Dynamic mechanical analysis and tensile testing found the membranes to be mechanically equivalent, and in some cases superior, to a commercial extruded membrane. Increasing ceramic content is accompanied by an increase in modulus and shift in the alpha peak to higher temperature. Maximum water uptake of the membranes, as measured by thermal gravimetric analysis, is double that of values reported for the commercial membrane, and complete dehydration is postponed to higher temperature. The proton conductivity of fully hydrated membranes, measured by the 4‐probe method at 60°C in water, is comparable with that of the extruded membrane. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Performance and Durability of Membrane Electrode Assemblies Based on Radiation‐Grafted FEP‐g‐Polystyrene Membranes

Membrane electrode assemblies (MEAs) based on radiation‐grafted proton exchange membranes developed at PSI have shown encouraging performance in the past in hydrogen and methanol fuelled polymer electrolyte fuel cells. In this study, the effect of the pre‐treatment of crosslinked radiation‐grafted FEP membranes prior to lamination with the electrodes on the performance of the MEAs was investigated. Two approaches were assessed separately and in combination: (1) the impregnation of the radiation‐grafted membranes with solubilised Nafion®, and (2) the use of a swollen vs. dry membrane. It is found that the combination of coating the membrane with Nafion® ionomer and hot‐pressing the MEA with the membrane in the wet state produce the best single cell performance. In the second part of the study, the durability of an MEA, based on a radiation‐grafted FEP membrane, was investigated. The performance was stable for 4,000 h at a cell temperature of 80 °C. Then, a notable degradation of the membrane, as well as the electrode material, started to occur as a consequence of either controlled or uncontrolled start‐stop cycles of the cell. It is assumed that particular conditions, to which the cell is subjected during such an event, strongly accelerate materials degradation, which leads to the premature failure of the MEA.     

Fuel Cell Membranes Based on Grafted and Post‐Sulfonated Glycidyl Methacrylate (GMA)

Glycidyl methacrylate (GMA) was pre‐irradiation grafted into ETFE base film of 25 μm thickness up to graft levels of 300%. The grafted films were sulfonated using a mixture of sulfite and bisulfite. FTIR and SEM–EDX analysis of the synthesized films and membranes was performed to confirm the grafting and the sulfonation. A pronounced front mechanism for grafting of GMA into ETFE was found. Regarding ex situ fuel cell relevant properties, conductivities of up to 0.25 S cm^–1 were attained. For the first time, fuel cell testing of this type of membrane is reported. These grafted membranes performed comparable to a commercial benchmark membrane (Nafion® 212) and better than a styrene‐based grafted membrane with similar conductivity. Post‐test FTIR analysis showed that a fraction of the grafted chains was lost during the test under constant current conditions, yet the membrane still exhibited superior durability compared to a styrene‐based grafted membrane. Hydrolysis of the methacrylate groups was shown not to be the principle cause of the loss of sulfonic acid groups.     

RuO4 staining and lamellar structure of α‐ and β‐PP

Monoclinic (α) and hexagonal (β) polypropylene (α‐ and β‐PP) were stained in the vapor of a ruthenium tetroxide solution prepared in situ. The effect of staining on the fusion behavior was investigated using a DSC. A staining duration between 10 and 24 h was found suitable for obtaining a good electron contrast between the crystalline and amorphous regions for TEM examination without causing severe damage to the crystals. The spherulites of the water‐quenched α‐PP were found to be composed of very fine cross‐hatched lamellae whose long period was about 10 nm. In comparison, the β‐PP spherulites crystallized isothermally at 130°C had a category 2 morphology and the lamellae have a long period of 20 nm. The morphology of the spherulite boundary varied depending on the contact angle between the lamellae of the neighboring spherulites. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1529–1538, 1999