Proton conducting polymer blends from poly(2,5‐benzimidazole) and poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid)

Proton conducting polymer electrolyte membranes were produced by blending of poly(2,5‐benzimidazole) (ABPBI) and poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid) (PAMPS) at several stoichiometric ratios with respect to polymer repeating units. The membranes were characterized by using Fourier transform infrared spectroscopy for interpolymer interactions and scanning electron microscope for surface morphology. Thermal stability of the materials was investigated by thermogravimetric analysis. Glass transition temperatures of the samples were measured via differential scanning calorimetry. The spectroscopic measurements and water uptake studies indicate a complexation between ABPBI and PAMPS that inhibited polymer exclusion up on swelling in excess water. Proton conductivities of the anhydrous and humidified samples were measured using impedance spectroscopy. The proton conductivity of the humidified ABPBI:PAMPS (1 : 2) blend showed a proton conductivity of 0.1 S/cm, which is very close to Nafion 117, at 20°C at 50% relative humidity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Recent advances in polybenzimidazole/phosphoric acid membranes for high‐temperature fuel cells

Proton exchange membrane fuel cells are one of the most promising technologies for sustainable power generation in the future. In particular, high‐temperature proton exchange membrane fuel cells (HT‐PEMFCs) offer several advantages such as increased kinetics, reduced catalyst poisoning and better heat management. One of the essential components of a HT‐PEMFC is the proton exchange membrane, which has to possess good proton conductivity as well as stability and durability at the required operating temperatures. Amongst the various membrane candidates, phosphoric acid‐impregnated polybenzimidazole‐type polymer membranes (PBI/PA) are considered the most mature and some of the most promising, providing the necessary characteristics for good performance in HT‐PEMFCs. This review aims to examine the recent advances made in the understanding and fabrication of PBI/PA membranes, and offers a perspective on the future and prospects of deployment of this technology in the fuel cell market. © 2014 Society of Chemical Industry     

Dielectric relaxations in phosphoric acid‐doped poly(2,5‐benzimidazole) and its composite membranes

Poly(2,5‐benzimidazole) (ABPBI)—a promising high‐temperature polymer electrolyte membrane—is characterized over a wide range of temperature (?50 to 220 °C) using broadband dielectric spectroscopy (BDS) to understand the various relaxation processes. The undoped ABPBI membrane shows two major secondary relaxations and a primary α relaxation. The effect of phosphoric acid (PA) and phosphotungstic acid grafted zirconium dioxide (PWA/ZrO₂) nanoparticles on the chain relaxation and the proton conductivity is investigated. The phosphoric acid alters the relaxation trends, increases the number of free ions in the polymer matrix, and therefore the conductivity. The shift in the peak frequencies of different chain relaxation processes in the presence of PA and PWA/ZrO₂ is attributed to the increase in free volume and the consequent easy motion of the polymer chains. The Fourier transform infra‐red (FTIR) spectroscopy of ABPBI and the acid‐doped composites show all the relevant peaks corresponding to C?C, C?N stretching, and phosphoric acid/phosphates, confirming the formation of ABPBI and doping with PA. The proton conductivity of the membranes is estimated from electrochemical impedance spectroscopy (EIS). To establish the effect of change in crystallinity on relaxations and proton conductivity, the undoped and PA‐doped membranes are characterized using thermogravimetric analysis and in situ XRD at high temperatures. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44867.     

Proton exchange composite membranes from blends of brominated and sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide)

New composite proton exchange membrane was prepared by mixing a 1‐methyl‐2‐pyrrolidone (NMP) solution of sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (SPPO) in sodium form and brominated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (BPPO) for hydrophilic‐hydrophobic balance, then casting the solution as a thin film, evaporating the solvent, and treating the membrane with aqueous hydrochloric acid. The resulting membranes were subsequently characterized using FTIR‐ATR, SEM‐EDXA, and TGA instrumentation as well as measurements of basic properties such as ion exchange capacity (IEC), water uptake, proton conductivity, methanol permeability, and single cell performance. Water uptake, IEC, proton conductivity, and methanol permeability all increased with a corresponding increase of SPPO content. By properly compromising the conductivity and methanol permeability, membranes with 60–80 wt % SPPO content exhibited comparable proton conductivity to that of Nafion^® 117, with only half the methanol permeability, thereby demonstrating higher single cell performance. The membranes developed in this study could thus be a suitable candidate electrolyte for proton exchange membrane fuel cells (PEMFCs). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A Three‐Dimensional Non‐isothermal Model of High Temperature Proton Exchange Membrane Fuel Cells with Phosphoric Acid Doped Polybenzimidazole Membranes

High temperature proton exchange membrane fuel cells (HT‐PEMFCs) with phosphoric acid doped polybenzimidazole (PBI) membranes have gained tremendous attentions due to its attractive advantages over conventional PEMFCs such as faster electrochemical kinetics, simpler water management, higher carbon monoxide (CO) tolerance and easier cell cooling and waste heat recovery. In this study, a three‐dimensional non‐isothermal model is developed for HT‐PEMFCs with phosphoric acid doped PBI membranes. A good agreement is obtained by comparing the numerical results with the published experimental data. Numerical simulations have been carried out to investigate the effects of operating temperature, phosphoric acid doping level of the PBI membrane, inlet relative humidity (RH), stoichiometry ratios of the feed gases, operating pressure and air/oxygen on the cell performance. Numerical results indicate that increasing both the operating temperature and phosphoric acid doping level are favourable for improving the cell performance. Humidifying the feed gases at room temperature has negligible improvement on the cell performance, and further humidification is needed for a meaningful performance enhancement. Pressurising the cell and using oxygen instead of air all have significant improvements on the cell performance, and increasing the stoichiometry ratios only helps prevent the concentration loss at high current densities.     

Phosphoric acid doped poly(2,5‐benzimidazole)‐based proton exchange membrane for high temperature fuel cell application

Undoped and doped poly(2,5‐benzimidazole) (ABPBI) membrane was prepared by solvent casting method using methane sulfonic acid as a solvent and phosphoric acid (H₃PO₄) as a doping agent. The concentration of H₃PO₄ was varied from 0 to 60 vol% to enhance the proton conductivity of the ABPBI membrane at higher temperature. Wide angle X‐ray diffraction analysis showed a decrease in crystallinity in ABPBI membrane with increase in H₃PO₄ doping concentration. The molecular signature and the presence of H₃PO₄ was observed in 1000–1500 cm^?1 in the Fourier transform infrared spectra, which was also supported by a corresponding weight loss at 180°C–200°C in the thermogravimetric analysis. Undoped ABPBI membrane registered the Young's modulus (E) and hardness (H) values of 2.46 and 0.92 GPa, respectively, and the corresponding E and H values for 1.65 doping level of 60 vol% H₃PO₄ doped ABPBI membrane were 0.14 and 0.067 GPa, respectively. The 60 vol% H₃PO₄ doped ABPBI membrane with doping level of 1.65 showed highest proton conductivity value of 2.2 × 10^?2 S/cm. The impedance spectroscopic analysis and the equivalent circuit model were discussed to understand the nature of proton conduction in H₃PO₄ doped ABPBI membrane. POLYM. ENG. SCI., 56:1366–1374, 2016. © 2016 Society of Plastics Engineers     

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     

Recent developments in fuel‐processing and proton‐exchange membranes for fuel cells

In recent years, great progress has been made in the development of proton‐exchange membrane fuel cells (PEMFCs) for both mobile and stationary applications. This review covers two types of new membranes: (1) carbon dioxide‐selective membranes for hydrogen purification and (2) proton‐exchange membranes; both of these are crucial to the widespread application of PEMFCs. On hydrogen purification for fuel cells, the new facilitated transport membranes synthesized from incorporating amino groups in polymer networks have shown high CO₂ permeability and selectivity versus H₂. The membranes can be used in fuel processing to produce high‐purity hydrogen (with less than 10 ppm CO and 10 ppb H₂S) for fuel cells. On proton‐exchange membranes, the new sulfonated polybenzimidazole copolymer‐based membranes can outperform Nafion^® under various conditions, particularly at high temperatures and low relative humidities. Copyright © 2010 Society of Chemical Industry     

Sulphonated Poly(ether ether ketone) Proton Exchange Membranes for Fuel Cell Applications

Polymer electrolyte membrane fuel cells (PEMFCs) are promising new power sources for automotive and portable devices. Nafion® is the currently used membrane in PEMFCs. Although these membranes show high proton conductivity and excellent chemical stability, their high cost makes them unpractical for commercial purposes. Sulphonated poly(ether ether ketone) (SPEEK) ionomers were synthesized using chlorosulphonic acid as the sulphonating agent in dichloromethane medium. Homogeneous proton-conducting membranes were developed from the obtained SPEEK by solvent casting method. Membranes were assessed for their suitability in fuel cell applications. The extent of sulphonation was controlled by varying the reaction time, concentration of polymer, and concentration of sulphonating agent. The SPEEK membranes exhibit degree of sulphonation from 10 to 66%, ion exchange capacity from 0.29 to 1.92 meq/g and maximum water and methanol uptake up to 54 and 22%, respectively, at 25°C. The membranes were characterized by FTIR to confirm sulphonation, and DSC and TGA to investigate the thermal stability. The proton conductivities of such membranes were found to be excellent in the order of 10^?2 S/cm in the fully hydrated condition at room temperature as measured by impedance spectroscopy. The durability of the membranes was also tested. The study revealed the possibility of a cheaper alternative membrane for use in PEMFC.     

Preparation and characterization of 2‐hydroxyethyl methacrylate‐based porous copolymeric particles

2‐Hydroxyethyl methacrylate was copolymerized with three different comonomers, methyl methacrylate (MMA), styrene (St), and N‐vinyl‐2‐pyrrolidone (NVP), respectively, to prepare porous particles crosslinked using ethylene glycol dimethacrylate (EGDMA) in the presence of an organic solvent, 1‐octanol (porogen), by means of suspension copolymerization in an aqueous phase initiated by 2,2‐azobisisobutyronitrile. Nano‐pores were observed in the particles. The pore size and the swelling properties of these particles can be controlled by changing comonomers or adjusting the crosslinker or porogen concentration. A lower crosslinker or porogen concentration favors generating smaller pores, whereas a higher concentration of a hydrophilic comonomer, higher concentration of crosslinker, and higher porogen volume ratio promote the generation of larger pores. In addition, the effects of the porous characteristics on the swelling properties were explored. The swelling capacity of the porous particles is reduced with the increase in the crosslinker concentration; however, there is a critical porogen volume ratio, in which the maximal swelling capacity is reached. Higher porosity in the particles and higher amount of hydrophilic comonomer favor a higher swelling capacity of the particles. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and characterization of sulfonated poly(arylene‐co‐naphthalimide)s for use as proton exchange membranes

In this study, conductive porous composites were fabricated using the host substrate with an interconnected porous network, followed by the penetration and deposition of polypyrrole (PPy) to create a continuous conductive network. The open‐porous host substrate was processed using polylactide (PLA) with compression molding and salt leaching techniques. Three different salt contents were varied from 75 wt %, 85 wt %, and 90 wt %, which were referred to by their salt‐to‐polymer mass ratios of 3, 6, and 9, respectively. The porous network was made conductive by coating its interior surfaces through in situ polymerization of PPy using iron (III) chloride as the oxidant species. These porous composites were then characterized to analyze the relationships between their morphology and their physical, conductive, and mechanical properties. The mechanical properties were then fitted with numerically simulated results from finite element modeling (FEM). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of interconnected poly(ε-caprolactone) porous scaffolds by a combination of polymer and salt particulate leaching

This paper examines a new technique for the preparation of porous scaffolds by combining selective polymer leaching in a co-continuous blend and salt particulate leaching. In the first step of this technique, a co-continuous blend of two biodegradable polymers, poly(ε-caprolactone) (PCL) and polyethylene oxide (PEO), and a certain amount of sodium chloride salt particles are melt blended using a twin screw extruder. Subsequently, extraction of the continuous PEO and mineral salts using water as a selective solvent yields a highly porous PCL scaffold with fully interconnected pores. Since, the salt particles and the co-continuous polymer blend morphology lead to very different pore sizes, a particular feature of this technique is the creation of a bimodal pore size distribution. Scanning electron microscopy, mercury intrusion porosimetry and laser diffraction particle size analysis were carried out to characterize the pore morphology. The prepared scaffolds have relatively homogeneous pore structure throughout the matrix and the porosity can be controlled between 75% and about 88% by altering the initial volume fraction of salt particles and to a lesser extent by changing the PCL/PEO composition ratio. Compared to the conventional salt leaching technique and to its different variants, the proposed process allows a better interconnection between the large pores left by the salt leaching and a fully interconnected porous structure resulting from the selective polymer leaching. The average compressive modulus of the different porous scaffolds was found to decrease from 5.2 MPa to about 1 MPa with increasing porosity, according to a power-law relationship. Since, the blending and molding of the scaffold (prior to leaching) can be made using conventional polymer processing equipment, this process seems very promising for a large scale production of porous scaffold of many sizes and in an economic way.     

Microstructure and mechanical properties of poly(L‐lactide) scaffolds fabricated by gelatin particle leaching method

Biodegradable poly(L ‐lactide) (PLLA) scaffolds with well‐controlled interconnected irregular pores were fabricated by a porogen leaching technique using gelatin particles as the porogen. The gelatin particles (280–450 μm) were bonded together through a treatment in a saturated water vapor condition at 70°C to form a 3‐dimensional assembly in a mold. PLLA was dissolved in dioxane and was cast onto the gelatin assembly. The mixtures were then freeze‐dried or dried at room temperature, followed by removal of the gelatin particles to yield the porous scaffolds. The microstructure of the scaffolds was characterized by scanning electron microscopy with respect to the pore shape, interpore connectivity, and pore wall morphology. Compression measurements revealed that scaffolds fabricated by freeze‐drying exhibited better mechanical performance than those by room temperature dying. Along with the increase of the polymer concentration, the porosity of the scaffolds decreased whereas the compressive modulus increased. When the scaffolds were in a hydrated state, the compressive modulus decreased dramatically. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1373–1379, 2005     

Durability of ABPBI‐based MEAs for High Temperature PEMFCs at Different Operating Conditions

High temperature PEMFCs based on phosphoric acid‐doped ABPBI membranes have been prepared and characterised. At 160 °C and ambient pressure fuel cell power densities of 300 mW cm^–2 (with hydrogen and air as reactants) and 180 mW cm^–2 (with simulated diesel reformate/air) have been achieved. The durability of these membrane electrode assemblies (MEAs) in the hydrogen/air mode of operation at different working conditions has been measured electrochemically and has been correlated to the cell resistivity, the phosphoric acid loss rate and the catalyst particle size. Under stationary conditions, a voltage loss of only –25 μV h^–1 at a current density of 200 mA cm^–2 has been deduced from a 1,000 h test. Under dynamic load changes or during start–stop cycling the degradation rate was significantly higher. Leaching of phosphoric acid from the cell was found to be very small and is not the main reason for the performance loss. Instead an important increase in the catalyst particle size was observed to occur during two long‐term experiments. At high gas flows of hydrogen and air ABPBI‐based MEAs can be operated at temperatures below 100 °C for several hours without a significant irreversible loss of cell performance and with only very little acid leaching.     

Development of polyethersulfone phase‐inversion membranes for membrane distillation using oleophobic coatings

Highly porous macrovoid‐free polyethersulfone membranes have been prepared using the phase‐inversion process with water as the non‐solvent. These membranes are of great interest for membrane distillation (MD) after application of a hydrophobic/oleophobic coating. The membrane structure was controlled by optimizing the process conditions and dope composition. Counter intuitively, increasing the polymer concentration favors the formation of larger surface pores under similar process conditions. A symmetric membrane is obtained when a sufficient amount of high‐molecular‐weight polyvinylpyrrolidone was added to the dope solution, which appears to play an important role in the structure formation process. The final membrane shows similar performance compared to commercial MD membranes. However, the membranes developed in this study show an oleophobic character, broadening the applications of MD. Moreover, the compressibility of these membranes is severely reduced compared to stretched membranes, which is expected to result in an improved MD performance at full scale. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45516.     

Preparation and morphology study of microporous poly(HEMA–MMA) particles

Porous poly(2‐hydroxyethyl methacrylate‐methyl methacrylate) particles crosslinked with ethylene glycol dimethacrylate were synthesized by free‐radical suspension copolymerization in an aqueous phase initiated by an oil‐soluble initiator, 2,2‐azobisisobutyronitrile. 1‐octanol was used as a pore forming agent (porogen). The porous structures, the particle morphology, and the swelling capacity of the resultant polymer in water at room temperature were studied at different crosslink densities and under various porogen concentrations. The analysis via Scanning Electronic Microscopy (SEM) indicated that permanent pores remained in the dried polymeric particles prepared in the presence of the porogen at certain crosslink densities. According to the studies via the SEM pictures and the pore size distributions, higher porogen concentration promotes the formation of more pores, and higher crosslink density results in narrower pore size distribution. The swelling capacity of the particles in water at room temperature decreases with an increase in the crosslink density, and the existence of the highly porous structures enhances the swelling capacity of the porous particles of poly(2‐hydroxyethyl methacrylate‐methyl methacrylate). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 707–715, 2007     

One‐Step Fabrication of Uniform Biodegradable Microbeads with Unimodal and Bimodal Porous Structures Using Spontaneous Microphase Separation

Uniform poly(l ‐lactic acid) (PLLA) microbeads with unimodal or bimodal porous structures are fabricated using a simple fluidic device based on a single oil‐in‐water emulsion method, where an alkane (octane, undecane, tridecane, and pentadecane) serves as the porogen. During the solvent evaporation, the alkanes spontaneously undergo a microphase separation, resulting in a highly porous structure. The size and size distribution of the pores in the PLLA microbeads can be easily controlled by changing the alkane type and concentration. When the undecane, tridecane, and pentadecane are used as the porogen at 6 wt%, the PLLA microbeads have the bimodal porous structure with a large hollow pore in the center and many small pores. In vitro and in vivo studies reveal that those PLLA microbeads with the bimodal porous structure readily facilitate the penetration and proliferation of cells and host tissues compared with the other PLLA microbeads. These results indicate that the superior properties of PLLA porous microbeads with a bimodal porous structure are suitable for diverse biomedical applications such as tissue engineering, cell delivery, and plastic surgery.     

A synthesis study of phosphonated PSEBS for high temperature proton exchange membrane fuel cells

A series of novel phosphonated proton exchange membranes has been prepared using poly(styrene‐ethylene/butylene‐styrene) block copolymer (PSEBS) as base material. Phosphonic acid functionalization of the polymer was performed by a simple two‐step process, via chloromethylation of PSEBS followed by phosphonation utilizing the Michaels–Arbuzov reaction. The successful phosphonation of the polymers were characterized by NMR and Fourier transform infrared. The phosphonated ester form of the membranes were obtained by solvent evaporation method and hydrolyzed to get a proton conducting membrane. The membrane properties such as ion exchange capacity, water uptake and proton conductivity at various temperatures were examined for their suitability to be utilized as a high temperature polymer electrolyte. Additionally, the morphology, thermal, and mechanical properties of the synthesized membranes were investigated, using scanning electron microscope, thermogravimetric analysis, and tensile test, respectively. The effective (anhydrous) proton conductivity was studied with respect to various degrees of functionalization. From the studies, the membranes were found to have a comparatively good conductivity and one of the membranes reached the maximum value of 5.81 mS/cm² at 140 °C as measured by impedance analyzer. It was found that the synthesized membranes were mechanically durable, chemically, and thermally stable. Hence, the synthesized phosphonated membranes could be a promising candidate for high temperature polymer electrolyte fuel cell applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45954.     

pH‐responsive permeability of PE‐g‐PMAA membranes

Poly(methacrylic acid) (PMAA) grafted porous PE membranes (PE‐g‐PMAA) were studied. It was found that (1) a wide range of graft yields can be achieved by varying irradiation time (20–240 min) and monomer concentration (0.22M–0.66M), (2) the grafted membrane exhibits reversible permeability response, (3) the membrane shows a maximum permeability response at an intermediate permeant molecular weight due to size exclusion effect, and (4) depending on the graft yield, two types of permeability response can be obtained. These observations are consistent with our earlier study on poly(N‐isopropylacrylamide) (PNIPAAm)–grafted porous polyethylene membranes. In addition, it was observed that the solvent used during grafting may influence the graft location—presumably due to variations in pore wetting. Specifically, compared to water solvent, methanol can increase grafting inside membrane pores, an observation inferred from membrane swelling, thickness measurement, and SEM characterization. Moreover, preferential grafting inside the membrane pores, as affected by increasing methanol content in the grafting solvent, results in lower membrane permeability and a greater pore graft‐controlled type of permeability response. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 778–786, 2000     

Processing of Porous SiC by Aluminum‐Derived Binders and Sacrificial Porogen Leaching Method

Porous SiC was successfully fabricated by a facile and energy efficient sacrificial porogen leaching method using in situ synthesized aluminum‐based binders by reaction bonding at low sintering temperatures of 600–1000°C. Porous SiC ceramics with porosity in the range of 30–58% and compressive strength of 1–33 MPa were obtained. Interconnected bimodal pores were produced by both stacking of SiC particles and leach out of salt. During sintering, the aluminum binder experienced metal to ceramic transformations forming various alumina polymorphs (γ, δ, θ and α‐Al₂O₃). The porogen content and sintering temperatures significantly influence the properties of porous SiC.