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.     

Langmuir--Schaefer films of Nafion with incorporated TiO(2) nanoparticles

An easy method of incorporating TiO(2) nanoparticles into Nafion perfluorinated ionomer is proposed. Ultrathin films of Nafion were prepared by employing the Langmuir-Schaefer (LS) technique. The pressure-area isotherm study of a Langmuir monolayer of Nafion at the air-water interface on different concentrations of NaCl as the subphase allowed us to find the best experimental conditions for the deposition of stable Langmuir-Schaefer films. Incorporation of TiO(2) nanoparticles was performed by dipping Nafion LS films in a solution of TiO(2) nanoparticles. The uniformity of the TiO(2) incorporation was detected by UV-visible spectroscopy. The morphology of the Nafion, Nafion/TiO(2) nanoparticles thin films, and the changes due to the annealing procedure were investigated by atomic force microscopy. Interestingly, the AFM investigation showed that Nafion and Nafion/TiO(2) LS films have thermal stability up to 600 degrees C.     

Thermal Behavior of Nafion Membranes

The thermal behavior of Nafion-117 membranes was investigated by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). TG measurements revealed that the mechanism of thermal degradation of a Nafion membrane in the acid form is different from that of Nafion in the sodium form. The DSC curves for the first heating, for both acid and salt forms, display two endothermic peaks, near 120 and 230°C. The high-temperature peak was assigned to the crystalline domains melting in Nafion, and the low-temperature peak was attributed to a transition into ionic clusters, since this transition exhibits significant changes depending on the nature of the counterion and the degree of hydration.This revised version was published online in November 2005 with corrections to the Cover Date.     

Vibrational and thermal characterization of Nafion membranes substituted by alkaline earth cations

The vibrational spectra of Nafion^® membranes with alkaline earth cations as counterions have been obtained by photoacoustic infrared spectroscopy (PAS-IR) and Fourier transform Raman spectroscopy (FT-Raman). The symmetrical stretching band of the sulfonate group (∼1060 cm⁻¹) decreases with increasing atomic mass of the countercation, excepting for Mg²⁺, in both techniques. The thermal behavior of Nafion membranes by means of differential scanning calorimetry (DSC) curves showed a dependence on the water content and a similar profile between Nafion-Mg²⁺ and -Ca²⁺, and between Nafion-Sr²⁺ and -Ba²⁺, for the first scanning curve. An ageing effect was also observed on Nafion by DSC curves. High-resolution thermogravimetry (TG) curves under nitrogen atmosphere showed similar decomposition profiles. It was determined from TG curves that there is a decreasing water content with increasing ionic radius of cation, and the thermal stability increasing from Nafion-Mg²⁺ to -Ba²⁺.     

Probing interfacial interactions of nafion ionomer: Thermal expansion of nafion thin films on substrates of different hydrophilicity/hydrophobicity

Interfacial interactions of Nafion ionomer with superhydrophilic (Pt, Au), hydrophilic (SiO₂), and hydrophobic (graphene, octyltrichlorosilane [OTS]‐modified SiO₂) is investigated, using in situ thermal ellipsometry, by quantification of substrate‐ and thickness‐dependent thermal properties of the ultrathin Nafion films of nominal thickness ranging 25–135 nm. For sub‐50 nm thin Nafion films, the thermal expansion coefficient of films decreased in the order of most hydrophobic to most hydrophilic substrate: OTS > graphene > SiO₂ > Au > Pt, implying weaker interpolymer and polymer–substrate interactions for films on hydrophobic substrates. Expansion coefficient of films on SiO₂, graphene, and OTS‐modified SiO₂ decreased with thickness whereas that of films on Au and Pt substrates increased with thickness. Above ~100 nm of thickness, films on all substrates converged toward a common value representative of bulk Nafion. Thermal transition temperature was found to be higher for films on hydrophilic SiO₂ than that for films on hydrophobic graphene and OTS‐modified SiO₂ but was not discernible for films on Au and Pt substrates. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 343–352     

The role of thermal analysis in optimization of the electrochromic effect of nickel oxide thin films, prepared by the sol–gel method: Part II

Thin films and the corresponding xerogels were prepared from nickel acetate precursor using the sol–gel dip-coating technique. The differences in thermal stability of the two forms of samples were studied by dynamic and isothermal thermogravimetry. For thin films, the onset decomposition temperature of acetate groups was 230 °C and for the xerogel 250 °C. During thermal decomposition, the formation of nanosized nickel oxide took place. Carbonate ions, which were formed during thermal decompostion of acetate groups, remained either free or bidentately coordinated to nickel. In situ monochromatic optical transmittance changes showed that an optical stability up to the 100th cycle was already achieved for films heated for 15 min at the isothermal temperature (thermal decompositon 25%). Comparison of the results obtained for nickel sulfate (Part I) and nickel acetate precursors shows that at least two parameters, the precursor used and the degree of thermal treatment, have considerable influence on the thermal stability of the thin film and also on its electrochromic response during the cycling process.     

Potential shifts at electrodes coated with ion-exchange polymeric films

Voltammetry at electrodes modified with ion-exchange polymers, named "ion exchange voltammetry", has been recently developed for characterizing and determining quantitatively ionic electroactive analytes preconcentrated at the electrode surface. Like for other voltammetric techniques, characterization is based on the position of the response on the potential scale, but an appreciable difference is frequently observed between the formal half-wave potential for redox couples incorporated within ion-exchange polymeric films and those for the same redox couples in solution as measured at bare electrodes. Such a difference has been rationalized here by a generalized equation, inferred from a suitable elaboration of the Nernst equation, whose validity has been tested by a thorough investigation performed at glassy carbon electrodes modified with either cationic (Nafion) or anionic (Tosflex) polymeric films. With this purpose, the effect of both charge and concentration of the analyte and of the loading counterion, this last introduced as the cation or anion of the supporting electrolyte, of the ion-exchange selectivity coefficients of the redox partners and of their stoichiometric coefficients, as well as of the number of electrons involved in the charge transfer has been evaluated. The results obtained agree quite well with theoretical expectations and indicate that the potential shifts found are mainly conditioned by both charge and concentration of the counterion from the supporting electrolyte and by the ratio of the ion-exchange equilibrium constants for the two redox partners involved. Other parameters considered have no influence on the potential shift or lead to negligible effects, provided that the quantities of the redox partners incorporated within the ion-exchange coating represents less than 5% of the film capacity. Again in agreement with theoretical expectations, positive shifts are found for increasing supporting electrolyte concentrations when cationic redox species incorporated within cationic films are involved, while the opposite effect is found for anionic redox species incorporated within anionic films.     

Preparation of highly porous heat-resistant polybenzoxazole network films and their electrical conductivities

Highly porous rigid polybenzoxazole (PBO) network films were prepared using a precursor-mediated fabrication method. The obtained PBO network films possessed high porosities of ~40%, as calculated from their apparent densities. In addition, the 5%-weight-loss temperatures of the films were ≥570°C under nitrogen atmosphere, demonstrating an excellent thermal stability. The electrical conductivities of the obtained PBO network films and phosphoric-acid-doped PBO network films were also evaluated. In addition, PBO network films containing pyridine rings were prepared and subjected to phosphoric acid doping. The resultant films were found to exhibit the highest conductivities of the films considered in this study owing to proton conduction both between phosphate groups and between the pyridine rings. The highest conductivity was found for a film prepared from a phosphoric-acid-doped PBO network containing pyridine rings, that is, 2.09 × 10^?1 S/cm at 150°C, which was higher than that of Nafion ? . Therefore, these films can be used at higher temperatures than that of Nafion ? .     

Thermal stability and decomposition of nafion® membranes with different cations

The thermal decomposition of Nafion has been studied by means of high-resolution and constant heating rate thermogravimetry (TG), under nitrogen and synthetic air atmospheres. Nafion membranes have been studied in acid and salt (alkali chlorides) forms. The TG curves of Nafion with alkali countercations show similar profiles, whichever the atmosphere employed. The kinetics of thermal decomposition of the Nafion-Cs⁺ has also been studied. The method employed to calculate the kinetic parameters and to estimate the polymer lifetime from the data was based on Kissinger's method. This revised version was published online in August 2006 with corrections to the Cover Date.     

Excess proton solvation and delocalization in a hydrophilic pocket of the proton conducting polymer membrane nafion

Solvation properties of the hydrated excess proton are studied in a hydrophilic pocket of Nafion 117 through a series of molecular dynamics simulations. The multistate empirical valence bond (MS-EVB) methodology, which enables the delocalization of the excess proton through the Grotthuss hopping mechanism, was employed for one of the excess protons in the simulation cell. Simulations were performed such that "classical" nondissociable hydronium cations and a single excess proton treated with the MS-EVB methodology were at a concentration ratio of 39:1. Two degrees of hydration of the Nafion polymer electrolyte membrane were simulated, each displaying the same marked difference between the solvation structures of the classical versus MS-EVB treated (Grotthuss shuttling) excess proton species. These differences are attributed to the solvent dynamics needed to transfer the cation between the solvent separated and contact pair positions about the sulfonic acid counterion. The results demonstrate that it is generally impossible to describe the low pH conditions in the hydrophilic domains of Nafion without the explicit treatment of Grotthuss delocalization in the underlying molecular dynamics model for the excess protons.     

Thermally Expanded Graphite as Functional Material in the Technology of Electrode Material with Mixed Conductivity

Methods of differential thermal analysis and cyclic voltammetry were used to examine the functional properties of thermally expanded graphite in an electrode material for electrochemical systems. This material contains platinum, carbon black, and proton-conducting polymer Nafion. It was shown that addition of thermally expanded graphite to the electrode material makes higher the thermal stability of Nafion. Under an electrochemical treatment, thermally expanded graphite compares well in stability against this treatment with the commonly used carbon black of the Vulcan XC-72 type. A mechanism is suggested for stabilizing the proton-conducting polymer Nafion in the presence of thermally expanded graphite. It was shown that thermally expanded graphite is promising for being used in the technology of electrode materials with mixed conductivity, which contain a proton-conducting polymer of the Nafion type, as a functional additive serving to improve the thermal stability.     

Effect of the composition of Nafion deposition solutions on the ion-exchange properties of the Nafion films by quartz crystal microbalance sensor (QCM)

A quartz crystal microbalance (QCM) sensor system was employed to investigate the properties of Nafion films on a gold surface supported on a quartz-crystal as a function of the water content in the deposition solutions (0.5% Nafion in mixed ethanol/water). The rates of loading and unloading of the complex ion Ru(bpy)(3)(2+) through Nafion films were measured. A linear dependence of the frequency changes on the percentage of water in the deposition solution was observed for both loading and unloading. The ion-exchange distribution coefficients for Nafion films from various deposition solutions were calculated. We concluded that films cast from solutions of higher water content had more ;open' structures which allowed faster diffusion of ions. This conclusion was further supported by the results of SEM experiments.     

Measurement of apparent diffusion coefficients within ultrathin nafion Langmuir-Schaefer films: comparison of a novel scanning electrochemical microscopy approach with cyclic voltammetry

The use of scanning electrochemical microscopy (SECM) to evaluate the apparent diffusion coefficient, Dapp, of redox-active species in ultrathin Nafion films is described. In this technique, an ultramicroelectrode (UME) tip, positioned close to a film on a macroscopic electrode, is used to oxidize (or reduce) a species in bulk solution, causing the tip-generated oxidant (reductant) to diffuse to the film/solution interface. The oxidation (reduction) of film-confined species regenerates the reductant (oxidant) in solution, leading to feedback to the UME. A numerical model is developed that allows Dapp to be determined. For these studies, ultrathin films of Nafion were prepared using the Langmuir-Schaefer (LS) technique and loaded with an electroactive species, either the ferrocene derivative ferrocenyltrimethylammonium cation, FA+, or tris(2,2'-bipyridyl)ruthenium(II), Ru(bpy)32+. The morphology and the thickness of the Nafion LS films (1.5 +/- 0.2 nm per layer deposited) were evaluated using atomic force microscopy (AFM). For comparison with the SECM measurements, cyclic voltammetry (CV) was employed to evaluate the concentration of electroactive species within the Nafion LS films and to determine Dapp. The latter was found to be essentially invariant with film thickness, but the value for Ru(bpy)32+ was 1 order of magnitude larger than for FA+. CV and SECM measurements yield different values of Dapp, and the underlying reasons are discussed. In general, the Dapp values for these films are considerably smaller than for recast Nafion films, which can be attributed to the compactness of Nafion LS films. Nonetheless, the ultrathin nature of the films leads to fast response times, and we thus expect that these modified electrodes could find applications in sensing, electroanalysis, and electrocatalysis.     

Excited‐State Proton Transfer and Conformational Relaxation of 2‐(4′‐Pyridyl)benzimidazole in Nafion Films

The effect of annealing on the acidity and water uptake of Nafion films has been studied by using the acidity sensing fluorophore 2‐(4′‐pyridyl)benzimidazole (4PBI). The difference in acidity and the microenvironment of the fluorophore in annealed and nonannealed films is brought out in this study. The annealed film is found to have less water uptake than nonannealed films. The amount of water uptake increases upon acid treatment of the films, as all the steady‐state and time‐resolved behaviour of the molecule in nonannealed films is restored. These observations are rationalised by the formation of anhydrides upon annealing and their hydrolysis to sulfonic acid groups upon acid treatment. Interestingly, the acidity of annealed films is found to be even less than that of Na⁺exchanged films, indicating that annealing removes more protons from the Nafion films than cation exchange can.     

Application of Thermal Lens Spectrometry to the Study of Chemical Adsorption in a Layer of a Nafion Solid Electrolyte

Thermal lens spectrometry was used to study Langmuir–Blodgett films of a weakly absorbing Nafion polyelectrolyte membrane on the surface of inert polyethylene terephthalate (PET) and glass substrates and to estimate the amount of Nafion (number of layers) using a change in the thermal characteristics of the sample. The sensitivity of thermal lens measurements at the wavelength of the exciting radiation 532.0 nm is comparable to that of solid-state spectrophotometry in the region of the maximum absorbance of Nafion (275 nm). However, the high locality of thermal lens spectrometry (the area of the signal generation zone is 100 μm²) ensures the estimation of the uniformity of the deposition of the polyelectrolyte layer. To increase the absorbance of the layer of the applied polyelectrolyte, the latter is saturated with a colored compound (ferroin). The adsorption of ferroin into the Nafion layer on the PET surface was confirmed; the absorbance of ferroin in the Nafion layer is in the range of 1 × 10–5^–5 × 10^–4 units of absorbance, which corresponds to the surface concentration of ferroin 1 × 10^–11–4 × 10^–10 mol/cm².     

Utilization of prompt‐γ neutron activation analysis in the evaluation of Nafion membranes

Researchers have performed evaluations on Nafion membranes for many years. An important aspect of the membranes is their chemical composition and uniformity. One technique that could provide accurate and fast quantitative measurements of the chemical composition and water within the membranes is prompt‐γ neutron activation analysis (PGAA). In this work, PGAA was applied to the chemical characterization of Nafion membranes in various forms. The evaluation confirmed the necessity of pretreatment of the membranes for the elimination of contamination. A series of counterion‐exchanged membranes were examined so that we could determine the degree of conversion achieved under different conditions and residual water levels. The results indicated that the type of counterion was an important factor determining conversion levels, that partial conversion could be achieved, and that counterion displacement could be forced to occur in certain environments. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1485–1492, 2003     

Nonideal mixing of dodecyltrimethylammonium halides and nonionic surfactant in adsorbed films and micelles

The ion–dipole interaction between dodecyltrimethylammonium cations and nonionic surfactant molecules in adsorbed films and micelles was investigated by concentrating on the difference in the degree of counterion binding by employing dodecyltrimethylammonium chloride (DTAC)–octyl methyl sulfoxide (OMS) and dodecyltrimethylammonium bromide (DTAB)–OMS mixtures. The phase diagrams of adsorption and micelle formation were constructed and then the nonideal mixing of different species of surfactants was demonstrated in terms of the excess Gibbs free energies of adsorption and micelle formation, and the surface excess areas. Furthermore the dependence of them on the counterion was clearly shown. All these results were found to support our previous view that the direct interaction between surfactant cation and the dipole of the hydrophilic part of a nonionic surfactant is essential in cationic-nonionic surfactant mixtures, i.e., the DTAC system with a lower counterion biding has more negative excess thermodynamic quantities than the DTAB system with a higher one.     

不同结构二苯胺重氮盐及重氮树脂的光,热分解

对二苯胺-4-重氮盐(DS)、邻-甲氧基二苯胺-4-重氮盐(MDS)和N-甲基-间硝基二苯胺-4-重氮盐(NDS)及它们的重氮树脂(DR,MDR,NDR)在水溶液中的光,热分解研究表明,这些重氮盐和树脂的光分解性质,即感光灵敏性差别不大,而热分解性质,即热稳定性差别很大.MDS的热稳定性最好.固相膜中3种树脂的光分解亦差别不大,但N-甲基-间硝基二苯胺-4-重氮树脂(NDR)固相膜的热稳定性出乎预料地好.从疏水性的角度对NDR固相膜突出的热稳定性作了初步解释.     

Blend membranes of Nafion/sulfonated poly(aryl ether ketone) for direct methanol fuel cell

Sulfonated poly(aryl ether ketone) (sPAEK) synthesized by LG Chem. was confirmed by FT-IR. To estimate the thermal stability, glass transition temperature and decomposition temperature were investigated. They showed that sPAEK had good thermal properties. The proton conductivity, methanol permeability and water uptake of sPAEK were also measured. Nafion/sulfonated poly(aryl ether ketone) composite membranes were prepared by blending two materials. The blend ratios of sPAEK and Nafion were 2:1, 3:1, 5:1, and 7:1. The blend membranes showed phase separated morphology since they became immiscible during the solvent evaporation process. Due to the differences in specific gravity and solvent concentration profile during the solvent evaporation process, the upper region had lower Nafion volume fraction with smaller domains and the lower region had higher Nafion volume fraction with larger domains. Mechanical properties such as the stress at break, yield stress, Young's modulus, and elongation at break were measured. The sPAEK had better mechanical properties than Nafion. The mechanical properties increased with increasing sPAEK content. Proton conductivity and methanol permeability of the blend membranes were lower than those of Nafion. Both decreased with decreasing Nafion content. Since the methanol permeability of sPAEK was lower than that of Nafion, sPAEK acted as the methanol barrier. Water uptake of sPAEK was higher than that of Nafion.     

Nafion膜在直接甲醇燃料电池中的应用及改进

Nafion质子交换膜性能优越,广泛应用于固体聚合物燃料电池中,但因存在甲醇渗透问题,使其在直接甲醇燃料电池中的应用受限制。本文讨论了Nafion质子交换膜的物质传输机理,侧重介绍甲醇分子的渗透机理,综述了基于降低甲醇渗透率而对Nafion膜所做的改进性研究和几种具有应用前景的替代膜。