Atomistic simulation of nafion membrane: I. Effect of hydration on membrane nanostructure

We used classical molecular dynamics simulation with the DREIDING force field to characterize the changes in the nanostructure of Nafion membrane brought about by systematically changing the hydration level. We calculated the relative percentages of free, weakly bound, and bound water in hydrated Nafion membranes. At low hydration levels, coordination of hydronium ions by multiple sulfonate groups prevents vehicular transport and impedes structural transport of protons through steric hindrance to hydration of the hydronium ions. Our results provide insights into the nanostructure of hydrated Nafion membrane and are in excellent agreement with experimental observations by neutron scattering of changes in the percentage of non diffusing hydrogen atoms.     

Atomistic simulations of hydrated nafion and temperature effects on hydronium ion mobility

The effects of hydration level and temperature on the nanostructure of an atomistic model of a Nafion (DuPont) membrane and the vehicular transport of hydronium ions and water molecules were examined using classical molecular dynamics simulations. Through the determination and analysis of structural and dynamical parameters such as density, radial distribution functions, coordination numbers, mean square deviations, and diffusion coefficients, we identify that hydronium ions play an important role in modifying the hydration structure near the sulfonate groups. In the regime of low level of hydration, short hydrogen bonded linkages made of water molecules and sometimes hydronium ions alone give a more constrained structure among the sulfonate side chains. The diffusion coefficient for water was found to be in good accord with experimental data. The diffusion coefficient for the hydronium ions was determined to be much smaller (6-10 times) than that for water. Temperature was found to have a significant effect on the absolute value of the diffusion coefficients for both water and hydronium ions.     

Comparative studies on performance of radiation-induced and thermal cross-linked ion-exchange membrane for water electrolysis

Radiation-induced and thermal cross-linked sulfonated poly(ether sulfone) (SPS)–sulfonated poly(ether ether ketone) (SPK) composite ion-exchange membranes (SPS/SPK(γ) and SPS/SPK(T), respectively) were prepared. Their performances for water electrolysis were comparatively assessed. Thermal cross-linked membrane (SPS/SPK(T)) showed cross-linking of part functional groups (–SO₃H) and thus deterioration in membrane conductivity. While, radiation-induced cross-linked membrane (SPS/SPK(γ)) avoided any cross-linking between functional groups and thus conductivity. Electrolysis performances of these membranes were evaluated in comparison with Nafion117 membrane. Relatively low current efficiency (CE) for SPS/SPK and SPS/SPK(T) membranes was due to their high mass transfer (water) via electro-osmotic drag, which was negligible for SPS/SPK(γ) membrane. SPS/SPK(γ) membrane exhibited comparable stabilities and water splitting performance with Nafion117 membrane, which revealed its suitability as substitute for electrochemical applications.     

Molecular modeling of proton transport in the short-side-chain perfluorosulfonic acid ionomer

An explanation for the superior proton conductivity of low equivalent weight (EW) short-side-chain (SSC) perfluorosulfonic acid membranes is pursued through the determination of hydrated morphology and hydronium ion diffusion coefficients using classical molecular dynamics (MD) simulations. A unique force field set for the SSC ionomer was derived from torsion profiles determined from ab initio electronic structure calculations of an oligomeric fragment consisting of two side chains. MD simulations were performed on a system consisting of a single macromolecule of the polymer (EW of 580) with the general formula F3C-[CF(OCF2CF2SO3H)-(CF2)7]40-CF3 at hydration levels corresponding to 3, 6, and 13 water molecules per sulfonic acid group. Examination of the hydrated morphology indicates the formation of hydrogen bond "bridges" between distant sulfonate groups without significant bending of the polytetrafluoroethylene backbone. Pair correlation functions of the system identify the presence of ion cages consisting of hydronium ions hydrogen-bonded to three sulfonate groups at the lowest water content. Such structures exhibit very low S-OH3+ separations, well below 4 A and severely inhibit vehicular diffusion of the protons. The number of sulfonate groups in the first solvation shell of a given hydronium ion correlates well with the differences between Nafion and the SSC polymer (Hyflon). The calculated hydronium ion diffusion coefficients of 2.84 x 10-7, 1.36 x 10-6, and 3.47 x 10-6 cm2/s for water contents of 3, 6, and 13, respectively, show only good agreement to experimentally measured values at the lowest water content, underscoring the increasing contribution of proton shuttling or hopping at the higher hydration levels. At the highest water content, the vehicular diffusion accounts for only about 1/5 of the total proton transport similar to that observed in Nafion.     

耗散粒子动力学模拟Nafion膜和PVA/Nafion共混膜的介观结构

采用耗散粒子动力学模拟方法研究了水化Nafion膜和水化聚乙烯醇(PVA)/Nafion共混膜的微结构.模拟结果表明水化Nafion膜和水化PVA/Nafion共混膜均能形成相分离的微结构.在水化Nafion膜中,水与磺酸根混合形成管状的水团簇.随着膜内水含量增多,管状水团簇的尺寸逐渐变大并在膜内形成连续的水通道.在水化PVA/Nafion共混膜中,PVA、水、磺酸根混合形成亲水性区域.共混膜中PVA的质量分数和水含量共同影响膜的微结构.当膜中PVA质量分数较低时,PVA主要分布在Nafion的磺酸根基团周围;PVA质量分数升高后,PVA会在膜内单独成一相.当膜中的水含量相对较低时,水分子会溶解于PVA中,此时膜内不存在单独的水团簇;膜中的水含量增多后,膜内会形成接近于球形的水团簇.本文工作可为直接甲醇燃料电池用的PVA改性Nafion膜的开发提供参考.     

Molecular dynamics simulations of triflic acid and triflate ion/water mixtures: a proton conducting electrolytic component in fuel cells

Triflic acid is a functional group of perflourosulfonated polymer electrolyte membranes where the sulfonate group is responsible for proton conduction. However, even at extremely low hydration, triflic acid exists as a triflate ion. In this work, we have developed a force-field for triflic acid and triflate ion by deriving force-field parameters using ab initio calculations and incorporated these parameters with the Optimized Potentials for Liquid Simulations - All Atom (OPLS-AA) force-field. We have employed classical molecular dynamics (MD) simulations with the developed force field to characterize structural and dynamical properties of triflic acid (270-450 K) and triflate ion/water mixtures (300 K). The radial distribution functions (RDFs) show the hydrophobic nature of CF(3) group and presence of strong hydrogen bonding in triflic acid and temperature has an insignificant effect. Results from our MD simulations show that the diffusion of triflic acid increases with temperature. The RDFs from triflate ion/water mixtures shows that increasing hydration causes water molecules to orient around the SO(3)(-) group of triflate ions, solvate the hydronium ions, and other water molecules. The diffusion of triflate ions, hydronium ion, and water molecules shows an increase with hydration. At λ = 1, the diffusion of triflate ion is 30 times lower than the diffusion of triflic acid due to the formation of stable triflate ion-hydronium ion complex. With increasing hydration, water molecules break the stability of triflate ion-hydronium ion complex leading to enhanced diffusion. The RDFs and diffusion coefficients of triflate ions, hydronium ions and water molecules resemble qualitatively the previous findings using per-fluorosulfonated membranes.     

Thermal stability of ion-exchange Nafion N117CS membranes

The effect of exchanged ions on the thermal stability of Nafion N117CS membranes was investigated by X-ray photoelectron spectra (XPS), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), thermomechanical analysis (TMA), and ion exchange capacity determinations. The ion exchange of alkaline metal ions was effective in improving the thermal stability of the Nafion N117CS membrane. Findings reveal that when Nafion was exchanged for cations with a larger ionic radius, the membrane attained superior thermal stability. On the other hand, we confirmed that the Na-exchange Nafion N117CS membrane possessed a distinctive degree of thermal stability among the alkaline ion-exchange Nafions, although the order of ionic radii is K > Na > Li. Thermal stability improved the most when the Nafion membrane was exchanged for alkaline ions, followed by divalent ions, then trivalent ions. As for the Nafion membrane when it was exchanged for divalent ions or trivalent ions, Nafion following the ion exchange had a thermal stability proportional to an increase in the ionic radius of the cation. This stability may be explained by the reduction of water content and a greater interaction between the sulfonate groups and the cations with larger ionic radii. Since the Al cations acted as a Lewis acid center, the decomposition of the ether bonds of the perfluoroalkylether pendant-chains of the Nafion membrane was observed for the Nafion N117CS membrane that had been exchanged for Al ions. The activation of molecular mobility in Nafion was observed between the decomposition stages of the loss of water and the loss of sulfonic groups. The temperature of activation of cation-exchange Nafion became much higher than that of Nafion in an acid form.     

Electric mass transport through homogeneous and surface-modified heterogeneous ion-exchange membranes at a rotating membrane disk

Polarization characteristics of the homogeneous MF-4SK perfluorinated sulfonated cation-exchange membrane and the heterogeneous MK-40 sulfonic acid membrane with its surface modified by a homogeneous film of Nafion are studied at a rotating membrane disk in 0.1 and 0.001 M sodium chloride solutions. Partial current-voltage curves (CVC) are obtained for sodium and hydrogen ions, and limiting current densities in the electromembrane systems (EMS) under study are calculated as a function of the rotation rate of the membrane disk. Contribution from different mechanisms (electrodiffusion, electroconvection, dissociation of water, and the effect of the limiting-current exaltation) to the total ion flow is estimated experimentally and theoretically under conditions that the diffusion layer in the EMS has stabilized in thickness. It is established that surface modification of the heterogeneous MK-40 membrane with a 7 μm layer of a modifying agent almost completely eliminates the dissociation of water molecules, and the properties of the heterogeneous MK-40 membrane approximate those of the homogeneous Nafion membrane. From IR spectra and potentiometric titration curves of the MK-40 and MF-4SK membranes, it is shown that the acidity of the sulfonate groups in these membranes is nearly identical, but a difference in the dissociation rate of water at these membranes is determined by a different character of charge-density distribution and potential near the membrane-solution interphase boundary. By means of the theory of the overlimiting state in EMS, the internal parameters of the systems under investigation are calculated: distribution of space-charge density and electric-field potential in the diffusion layer and in the membrane. Partial CVC are calculated for H⁺ ions for the space-charge region in the phase of the MF-4SK and MK-40/Nafion ion-exchange membranes. Partial CVC with similar characteristics are compared for the heterogeneous monopolar MK-40 and the bipolar MB-2 membranes, which contain sulfonate groups. It is concluded that the membrane surface layer, where the space charge is localized, plays a dominant role in speeding up the dissociation of water in EMS.     

Insight from molecular modelling: does the polymer side chain length matter for transport properties of perfluorosulfonic acid membranes?

We present a detailed analysis of the nanostructure of the short side chain (SSC) perfluorosulfonic acid membrane and its effect on H(2)O clustering, H(3)O(+) and H(2)O diffusion, and mean residence times of H(2)O near SO(3)(-) groups based on molecular dynamics simulations. We studied a range of hydration levels (λ) at temperatures of 300 and 360 K, and compare the results to our findings in the benchmark Nafion? membrane. The water cluster diameter is nearly the same in the two membranes, while the extent of SO(3)(-) clustering is more in the SSC membrane. The calculated cluster diameter of about 2.4 nm is in excellent agreement with the recently proposed cylindrical water channel model of these membranes. The diffusion coefficients of H(2)O and H(3)O(+) are similar in SSC and Nafion membranes. Raising the temperature of the SSC membrane from 300 to 360 K provides a much bigger increase in proton vehicular diffusion coefficient (by a factor of about 4) than changing the side chain length. H(3)O(+) ions are found to exchange more frequently with SO(3)(-) partners at the higher temperature. Our key findings are that (a) the hydrophobic-hydrophilic separation in the two membranes is surprisingly similar; (b) at all hydration levels studied, the long side chain of Nafion is bent and is effectively equivalent to a short side chain in terms of extension into the water domain; (c) vehicular proton transport occurs mainly between SO(3)(-) groups; and (d) changing the size of the simulation cell does not change the results significantly. The simulations are validated in good agreement with the corresponding experimental values for the simulated membrane density and diffusion coefficients of H(2)O.     

Effects of dielectric saturation and ionic screening on the proton self-diffusion coefficients in perfluorosulfonic acid membranes

Proton transport in perfluorosulfonic acid (PFSA) membranes is investigated through a statistical mechanical model that includes the effects of the interaction of the tethered sulfonate groups with both the water and solvated protons. We first derive a potential that describes the electrostatic field due to the dissociated sulfonic acid groups by extending the work of Gronbech-Jensen et al. [ Mol. Phys. 92, 941 (1997)] to a finite array of point charges. A highly convergent series is obtained which includes the effects of screening due to the protons. We then investigate the effects of both dielectric saturation and two distinct formulations of ionic screening on the proton self-diffusion coefficient in Nafion membranes over a range of water contents. Our computations show that the two phenomena (i.e., dielectric saturation and ionic screening) under constant temperature conditions result in canceling affects. Our calculations provide a radial dependence of the proton mobility suggesting that the dominant self-diffusion occurs in the central region of the pores, well separated from the sulfonate groups. Through comparison of our calculated diffusion coefficients with the experimental values we derived a slightly smaller average separation distance of the hydronium ion from the sulfonate ions than suggested by either electronic structure calculations or multistate empirical valence bond molecular-dynamics simulations.     

Transport properties of Nafion membranes modified with tetrapropylammonium ions for direct methanol fuel cell application

This work presents a study of transport properties (proton conductivity, methanol permeability, and water uptake) and acid-base properties of commercial Nafion-112, -115, and -117 membranes modified with tetrapropylammonium (TPA) cations. In the interaction between TPA hydroxide and protons of sulfonate groups in the Nafion matrix, some of the protons are shown to be bound to sulfonate groups and do not participate in transport processes. These findings are confirmed by IR spectroscopy, acid-base titration, and data on proton conductivity of the modified membranes. Proton conductivity of the modified membranes is shown to be effectively described by a percolation model with parameters that agree with published data for commercial Nafion membranes. Based on these results, a model is proposed for the interaction of TPA cations with the sulfonate groups in Nafion membranes. According to this model, TPA cations form hydrophobic clusters in hydrophilic regions of the polymer matrix, thus preventing some of the protonated sulfonate groups from participating in transport processes.     

Atomistic simulation of nafion membrane. 2. Dynamics of water molecules and hydronium ions

We have performed a detailed and comprehensive analysis of the dynamics of water molecules and hydronium ions in hydrated Nafion using classical molecular dynamics simulations with the DREIDING force field. In addition to calculating diffusion coefficients as a function of hydration level, we have also determined mean residence time of H(2)O molecules and H(3)O(+) ions in the first solvation shell of SO(3)(-) groups. The diffusion coefficient of H(2)O molecules increases with increasing hydration level and is in good agreement with experiment. The mean residence time of H(2)O molecules decreases with increasing membrane hydration from 1 ns at a low hydration level to 75 ps at the highest hydration level studied. These dynamical changes are related to the changes in membrane nanostructure reported in the first part of this work. Our results provide insights into slow proton dynamics observed in neutron scattering experiments and are consistent with the Gebel model of Nafion structure.     

A molecular dynamics study of a nafion polyelectrolyte membrane and the aqueous phase structure for proton transport

A molecular dynamics simulation study of hydrated Nafion at water contents ranging from 5 to 20 wt % was performed to examine the structure and dynamics of the hydrated polyelectrolyte system. The simulations show that the system forms segregated hydrophobic regions consisting primarily of the polymer backbone and hydrophilic regions with an inhomogeneous water distribution. We find that the water clustering strongly depends on the water content. At low water content, only isolated small water clusters are formed. As the water content increases, it becomes increasingly possible that a predominant majority of water molecules form a single cluster, suggesting that the hydrophilic regions become connected. We characterize the atomic structures formed within the system by various atomic pair correlation functions. The water structure factor shows a peak at q values corresponding to an intercluster distance about 2.5 nm and greater. With increasing water content, the distance moves to larger values, consistent with findings from scattering experiments. We find that the degree of solvation of hydronium ions by water molecules is a strong function of water content. At 5 wt %, a majority of the hydronium ions are hydrated by no more than two water molecules, prohibiting structural diffusion. As water content increases, the hydronium ions continue to become increasingly hydrated, resulting in structures capable of forming eigen ions, a necessary step in structural diffusion. Addressing the experimentally observed fact that conductivity in these membranes abruptly drops near 5 wt %, we find that both the local structure of the poorly hydrated hydronium ions and the disconnected nature of the global morphology of the water nanonetwork at low water content should contribute to poor conductivity.     

Specifics of solvation of sulfonated polyelectrolytes in water, dimethylmethylphosphonate, and their mixture: a molecular simulation study

Sulfonated polyelectrolyte membranes (PEMs), such as Nafion and styrene-olefin block copolymers, are explored as permselective membranes for fuel cells as well as suitable barrier materials against chemical agents. The permselective properties of PEM are determined by their microphase segregation into hydrophilic and hydrophobic domains. We performed classical molecular dynamics simulations of solvation of the hydrophilic fragments of PEM exemplified on sulfonated polystyrene (sPS) with potassium, calcium, and aluminum as counterions, in water, phosphor-organic nerve agent simulant dimethylmethylphosphonate (DMMP), and their binary mixture. The force field for the sulfonate group has been developed by optimizing the potential parameters to fit the benzenesulfonate conformations obtained from the density functional theory. For a comparison, we considered perfluorosulfonate oligomers representing fragments of Nafion polymer. We found a noticeable difference between the geometries of the polymer backbone in different solvents. The polymer backbone is stiffer in DMMP for both sPS and Nafion. An anisotropic structuring of the solvent around the phenylsulfonate group is substantially stronger than around the Nafion sidechain due to the rigidity and the anisotropy of the phenylsulfonate group. The counterion significantly affects the conformations of solvated sPS: the rigidity of the backbone increases when potassium or calcium ions are replaced by trivalent aluminum ions.     

Nanophase segregation and water dynamics in the dendrion diblock copolymer formed from the Fréchet polyaryl ethereal dendrimer and linear PTFE

We propose a new material consisting of a dendrion copolymer formed from (a) a water-soluble dendritic polymer and (b) a hydrophobic backbone. Using molecular dynamics simulations techniques, we determine the structure and dynamics of the dendrion formed by second-generation Fréchet polyaryl ethereal dendrimer as the hydrophilic component and linear polytetrafluoroethylene (PTFE) as the hydrophobic polymer, with 5 and 10 wt % of water. We find that this material produces a well-developed nanoscale structure in which water forms a continuous nanophase, making this new family of compounds promising candidates for applications in fuel cell membranes. We find that the water molecules are incorporated into the dendrimer block of the copolymer to form a nanophase-segregated structure. The well-developed nanophase-segregated structures rendered by this material have characteristic dimensions of segregation ( approximately 30 Angstrom) and dendrimer conformational properties that are independent of water content. Calculations of water dynamics and proton transport in these nanophase-segregated structures indicate that the dendrion copolymer membrane with 10 wt % of water content has a water structure and transport properties equivalent to that of the hydrated Nafion membrane with 20 wt % of water content.     

Effect of SiO2 on relaxation phenomena and mechanism of ion conductivity of [Nafion/(SiO2)x] composite membranes

This report describes a study of the effect of SiO2 nanopowders on the mechanism of ionic motion and interactions taking place in hybrid inorganic-organic membranes based on Nafion. Five nanocomposite membranes of the formula [Nafion/(SiO2)x] with SiO2 ranging from 0 to 15 wt % were prepared by a solvent casting procedure. TG measurements demonstrated that the membranes are thermally stable up to 170 degrees C but with the loss water it changes the cluster environments and changes the conductivity properties. MDSC investigations in the 90-300 degrees C temperature range revealed the presence of three intense overlapping endothermal peaks indicated as I, II, and III. Peak I measures the order-disorder molecular rearrangement in hydrophilic polar clusters, II corresponds to the endothermic decomposition of -SO3 groups, and III describes the melting process in microcrystalline regions of hydrophobic fluorocarbon domains of the Nafion moiety. ESEM with EDAX measurements revealed that the membranes are homogeneous materials with smooth surfaces. DMA studies allowed us to measure two relaxation modes. The mechanical relaxation detected at ca. 100 degrees C is attributed to the motion of cluster aggregates of side chains and is diagnostic for R-SO3H...SiO2 nanocluster interactions. DMA disclosed that at SiO2/-SO3H (psi) molar ratios lower than 1.9, the oxoclusters act to restrict chain mobility of hydrophobic domains of Nafion and the dynamics inside polar cages of [Nafion/(SiO2)x] systems; at psi higher than 1.9, the oxoclusters reduce the cohesiveness of hydrophilic polar domains owing to a reduction in the density of cross-links. FT-IR and FT-Raman studies of the [Nafion/(SiO2)x] membranes indicated that the fluorocarbon chains of Nafion hydrophobic domains assume the typical helical conformation structure with a D(14pi/15) symmetry. These analyses revealed four different species of water domains embedded inside polar cages and their interconnecting channels: (a) bulk water [(H2O)n]; (b) water solvating the oxonium ions directly interacting with sulfonic acid groups [H3O+...SO3(-)-].(H2O)n; (c) water aggregates associated with H3O+ ions [H3O+.(H2O)n]; and (d) low associated water species in dimer form [(H2O)2]. The conductivity mechanism and relaxation events were investigated by broadband dielectric spectroscopy (BDS). [Nafion/(SiO2)x] nanocomposite membranes were found to possess two different molecular relaxation phenomena which are associated with the alpha-relaxation mode of PTFE-like fluorocarbon domains and the beta-relaxation mode of acid side groups of the Nafion component. Owing to their strong coupling, both these relaxation modes are diagnostic for the interactions between the polar groups of the Nafion host polymer and the (SiO2)x oxoclusters and play a determining role in the conductivity mechanism of the membranes. The studies support the proposal that long-range proton charge transfer in [Nafion/(SiO2)x] composites takes place due to a mechanism involving exchange of the proton between the four water domains. This latter proton transfer occurs owing to a subsequent combination of domain intersections resulting from the water domain fluctuations induced by the molecular relaxation events of host Nafion polymer.     

Effects of water freezing on the mechanical properties of nafion membranes

Most of the research efforts on Nafion have been devoted to the study of the perfluorinated ionomer membranes at optimal conditions for the desired applications, such as high temperature and low relative humidity for polymer electrolyte membrane fuel cells (PEM FC). In view of the possible changes induced by the freezing of water in the structure of Nafion and considering that in cold start conditions of a PEM FC device, Nafion needs to work also below 273 K, we measured the Young's modulus (Y) and the elastic energy dissipation (tan δ) in the temperature range between 90 and 470 K and the stress–strain curves between 300 and 173 K. The measurements reported here indicate that the mechanical properties of wet Nafion membrane change dramatically with temperature, that is, from a rubber‐like behavior at room temperature to a brittle behavior below 180 K. Moreover, we observed that the freezing of the nanoconfined water is complete only below 180 K, as indicated by a large increase of the Young's modulus. Between 180 and 300 K, the large values of tan δ suggest the occurrence of friction between the liquid water bound to the walls of the hydrophilic domains and the solid ice residing in the center of channels. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Synthesis of highly sulfonated poly(arylene ether sulfone) random (statistical) copolymers via direct polymerization

Novel biphenol‐based wholly aromatic poly (arylene ether sulfones) containing pendant sulfonate groups were prepared by direct aromatic nucleophilic substitution polycondensation of disodium 3,3′‐disulfonate‐4,4′‐dichlorodiphenyl sulfone (SDCDPS), 4,4′‐dichlorodiphenylsulfone (DCDPS) and biphenol. Copolymerization proceeded quantitatively to high molecular weight in N‐methyl‐2‐pyrrolidinone at 190°C in the presence of anhydrous potassium carbonate. Tough membranes were successfully cast from the control and the copolymers, which had a SDCDPS/DCDPS mole ratio of either 40:60 or 60:40 using N,N‐dimethylactamide; the 100% SDCDPS homopolymer was water soluble. Short‐term aging (30 min) indicates that the desired acid form membranes are stable to 220°C in air and conductivity values at 25°C of 0.110 (40%) and 0.170 S/cm (60%) were measured, which are comparable to or higher than the state‐of‐the art fluorinated copolymer Nafion 1135 control. The new copolymers, which contain ion conductivity sites on deactivated rings, are candidates as new polymeric electrolyte materials for proton exchange membrane (PEM) fuel cells. Further research comparing their membrane behavior to post‐sulfonated systems is in progress.     

Structure of hydrated Na-Nafion polymer membranes

We use molecular dynamics simulations to investigate the structure of the hydrated Na-Nafion membranes. The membrane is "prepared" by starting with the Nafion chains placed on a cylinder having the water inside it. Minimizing the energy of the system leads to a filamentary hydrophilic domain whose structure depends on the degree of hydration. At 5 wt % water the system does not have enough water molecules to solvate all the ions that could be formed by the dissociation of the -SO3Na groups. As a result, the -SO3Na groups aggregate with the water to form very small droplets that do not join into a continuous phase. The size of the droplets is between 5 and 8 A. As the amount of water present in the membrane is increased, the membrane swells, and SO3Na has an increasing tendency to dissociate into ions. Furthermore, a transition to a percolating hydrophilic network is observed. In the percolating structure, the water forms irregular curvilinear channels branching in all directions. The typical dimension of the cross section of these channels is about 10-20 A. Calculated neutron scattering from the simulated system is in qualitative agreement with experiment. In all simulations, the pendant sulfonated perfluorovinyl side chains of the Nafion hug the walls of the hydrophilic channel, while the sulfonate groups point toward the center of the hydrophilic phase. The expulsion of the side chains from the hydrophilic domain is favored because it allows better interaction between the water molecules. We have also examined the probability of finding water molecules around the Na+ and the -SO3(-) ions as well as the probability of finding other water molecules next to a given water molecule. These probabilities are much broader than those found in bulk water or for one ion in bulk water (calculated with the potentials used in the present simulation). This is due to the highly inhomogeneous nature of the material contained in the small hydrophilic pores.     

Preparation and properties of weak acid ion-exchange membranes based on poly(vinylchloride)/poly(methylmethacrylate-co-divinylbenzene) system

Weak acid ion-exchange membranes were obtained on the basis of PVC/poly(MMA-co-DVB) interpolymer-type systems. Carboxylic groups were introduced by acid hydrolysis of ester groups in poly(MMA-co-DVB) copolymer. It was found that suitable conditions for preparation of carboxylic membranes were: temperature of 353 K, 3 h reaction time, and acetic acid used. The best ion-exchange and electrochemical properties had membrane prepared from hydrolyzed PVC/poly(MMA-co-DVB) system with 5 wt % DVB. © 1996 John Wiley & Sons, Inc.