Microscopic Determination of the Local Hydration Number of Polymer Electrolyte Membranes Using SANS Partial Scattering Function Analysis.

The conventional hydration number, λ, of a polymer electrolyte membrane (PEM) is estimated by the gravimetric measurement of the total water uptake in the membrane. This is the overall water molecules divided by the number of ionic groups covering the water distribution from the macroscale to the molecular level. For a more precise evaluation of the local ion-water interactions and ion transport efficiency in hydrophilic channels, in contrast to λ, we here propose an index, local hydration number (λlocal), defined as the number of water molecules located adjacent to and interacting with ionic groups in a PEM, per ionic group in the hydrophilic channels. We introduce an experimental method using partial scattering function analysis through a contrast-variation small-angle neutron scattering technique to precisely determine λlocal at the micro- (nano-) scale to the molecular level for PEMs. When applied to the benchmark material Nafion and the well-studied radiation-grafted PEM, consisting of poly(styrene sulfonic acid) grafted onto poly(ethylene-co-tetrafluoroethylene) (ETFE-g-PSSA), the obtained λlocal was close to the conventional λ. This means all water molecules interacted with sulfonic acid groups, which is much different from the case of anion-type grafted PEMs. Comparing the λlocal value obtained in this study with the conventional λ value confirmed that water existed only in nanostructured hydrophilic channels in these PEMs. The result of this work provides a route to understand local molecular structures of high-performing PEMs for energy conversion applications.

Direct Observation and Semiquantitative Analysis of Hierarchical Structures in Graft-Type Polymer Electrolyte Membranes Using the AFM Technique.

The structural features of a polymer electrolyte membrane (PEM), consisting of polystyrene sulfonic acid (PSSA) grafted onto poly(ethylene-co-tetrafluoroethylene) (ETFE), can be characterized semiquantitatively by atomic force microscopy (AFM). The cross-sectional AFM phase images are converted to the binarized image by fitting two Gaussian functions. The domains correspond to hydrophilic PSSA domains and hydrophobic ETFE crystalline and amorphous regions, respectively, at lower and higher phase shift values. The area fraction of PSSA domains was consistent with the volume fraction determined by the grafting degree (GD). The dependence of the radius and interdomain distance of the PSSA domains on the GDs of PEMs shows discontinuous features at the threshold GD (39%). The former slightly increased from 10 to 12 nm and significantly increased to 17 nm at a GD greater than 39%; the latter decreased from 140 to 54 nm with increases in GDs up to 39% but inversely increased to 78 nm at a GD of 46%. This discontinuous change in radius and interdomain distance should be caused by the fusion of adjacent PSSA domains to form a larger size and spacing and thus less connectivity between each large domain, thereby lowering the conductivity at GD greater than 39%. We were able to demonstrate the existence of an ion-conducting hydrophilic path with a radius of approximately 10 nm. Even though it has received little attention in the past, it is expected to enable the design of electrolyte membrane functions in the future.

Radiation-Induced Asymmetric Grafting of Different Monomers into Base Films to Prepare Novel Bipolar Membranes.

We prepared novel bipolar membranes (BPMs) consisting of cation and anion exchange layers (CEL and AEL) using radiation-induced asymmetric graft polymerization (RIAGP). In this technique, graft polymers containing cation and anion exchange groups were introduced into a base film from each side. To create a clear CEL/AEL boundary, grafting reactions were performed from each surface side using two graft monomer solutions, which are immiscible in each other. Sodium p-styrenesulfonate (SSS) and acrylic acid (AA) in water were co-grafted from one side of the base ethylene-co-tetrafluoroethylene film, and chloromethyl styrene (CMS) in xylene was simultaneously grafted from the other side, and then the CMS units were quaternized to afford a BPM. The distinct SSS + AA- and CMS-grafted layers were formed owing to the immiscibility of hydrophilic SSS + AA and hydrophobic CMS monomer solutions. This is the first BPM with a clear CEL/AEL boundary prepared by RIAGP. However, in this BPM, the CEL was considerably thinner than the AEL, which may be a problem in practical applications. Then, by using different starting times of the first SSS+AA and second CMS grafting reactions, the CEL and AEL thicknesses was found to be controlled in RIAGP.

A long side chain imidazolium-based graft-type anion-exchange membrane: novel electrolyte and alkaline-durable properties and structural elucidation using SANS contrast variation.

Newly designed styrylimidazolium-based grafted anion-exchange membranes (StIm-AEMs), in which imidazolium ionic groups are attached to styrene at the far side from the graft chains, were prepared by radiation-induced graft polymerization of p-(2-imidazoliumyl) styrene onto poly(ethylene-co-tetrafluoloethylene) (ETFE) films, followed by N-alkylation and ion-exchange reactions. StIm-AEM having an ion exchange capacity (IEC) of 0.54 mmol g-1 with a grafting degree (GD) of ∼18%, possesses practical conductivity (>50 mS cm-1) even with a very low water uptake (∼10%) and high stability over 600 h in a 1 M KOH solution at 80 °C. There exists a critical IEC (IECc) in the range of 0.7-0.8 mmol g-1 over which the membrane showed high water uptake, which resulted in pronounced susceptibility to hydrolysis. Using small-angle neutron scattering technique with a contrast variation method, we found the hydrophilic phase in StIm-AEMs with IECs lower and higher than IECc shows "reverse-micelles" with water domains dispersed in the polymer matrix and "micelles" with graft polymer aggregates dispersed in the water matrix, respectively. The further analysis of micelle structures using the hard-sphere liquid model and Porod limit analysis reveals that the interfacial structures of ionic groups are essential for the electrochemical properties and durability of StIm-AEMs. In addition, StIm-AEM with an IEC of 0.95 mmol g-1 and the maximum power density of 80 mW cm-2 in the hydrazine hydrate fuel cell test, exhibited long-term durability under constant current (8.0 mA) up to 455 h, which, thus far, is the best durability at 80 °C for platinum-free alkaline-type liquid fuel cells.

Soft x-ray laser beamline for surface processing and damage studies.

We have developed a soft x-ray laser (SXRL) beamline equipped with an intensity monitor dedicated to ablation study such as surface processing and damage formation. The SXRL beam having a wavelength of 13.9 nm, pulse width of 7 ps, and pulse energy of around 200 nJ is generated from Ag plasma mediums using an oscillator-amplifier configuration. The SXRL beam is focused onto the sample surface by the Mo/Si multilayer coated spherical mirror. To get the correct irradiation energy/fluence, an intensity monitor composed of a Mo/Si multilayer beam splitter and an x-ray charge-coupled device camera has been installed in the beamline. The Mo/Si multilayer beam splitter has a large polarization dependence in the reflectivity around the incident angle of 45°. However, by evaluating the relationship between reflectivity and transmittance of the beam splitter appropriately, the irradiation energy onto the sample surface can be derived from the energy acquired by the intensity monitor. This SXRL beamline is available to not only the ablation phenomena but also the performance evaluation of soft x-ray optics and resists.

Development of a Simplified Radiation-Induced Emulsion Graft Polymerization Method and Its Application to the Fabrication of a Heavy Metal Adsorbent.

A simplified radiation-induced emulsion graft polymerization (SREG) method is proposed. This method involves a convenient and easy degassing process of a monomer solution using a commercially available sealed glass jar. A loaded weight on the lid of the jar was used to control the jar's internal pressure as the degassing of the monomer solution took place using a vacuum pump. The degassing method was highly reproducible, resulting from no bumping of the monomer solution. The initial grafting velocity was proportional to the absorbed doses of pre-irradiation between 5 and 20 kGy. This result indicates that dissolved oxygen was sufficiently eliminated from the monomer solution at such a level where the remaining oxygen had little effect on the grafting reaction at a dose of 5 kGy. The method was then applied to the fabrication of a heavy metal adsorbent that possessed a sufficient adsorption capacity of Co(II) ions. The SREG method is applicable to the fabrication of a wide variety of functional graft polymers because high-dose-rate gamma-ray radiation and expensive experimental equipment are not necessary.

Reverse relationships of water uptake and alkaline durability with hydrophilicity of imidazolium-based grafted anion-exchange membranes.

We found unprecedented reverse relationships in anion-exchange membranes (AEMs) for Pt-free alkaline fuel cell systems, i.e., the increase in hydrophobicity increased water uptake and susceptibility to hydrolysis. AEMs with graft copolymers that composed of anion-conducting 2-methyl-N-vinylimidazolium (Im) and hydrophobic styrene (St) units were employed. We characterized two new structures in these AEMs using a small-angle neutron scattering with a contrast variation method. (1) The distribution of graft polymers in conducting (ion channel) or non-conducting (hydrophobic amorphous poly(ethylene-co-tetrafluoroethylene) (ETFE)) phase was evaluated in a quantitative manner. High fraction in conducting layer for AEMs having high grafting degrees was found using the proposed structural model of "conducting/non-conducting two-phase system". (2) Assuming a hard-sphere fluid model, we found AEMs having high St contents and low alkaline durability possessed nanophase-separated water puddles with diameters of 3-4 nm. The AEM having a low St content and the best alkaline durability did not show evident nanophase separation. The above hierarchical structures elucidate the unexpected reverse relationships that the AEM having highly hydrophobic graft polymers was subjected to the morphological transition to give water puddles at nanoscale. The imidazolium groups that were located at the boundary between graft polymers and water puddles should be susceptible to hydrolysis.

Imidazolium-based anion exchange membranes for alkaline anion fuel cells: (2) elucidation of the ionic structure and its impact on conducting properties.

In our previous study (Soft Matter, 2016, 12, 1567), the relationship between the morphology and properties of graft-type imidazolium-based anion exchange membranes (AEMs) was revealed, in that the semi-crystalline features of the polymer matrix maintain its mechanical properties and the formation of interconnected hydrophilic domains promotes the membrane conductivity. Here, we report a novel ionic structure of the same graft-type AEMs with different grafting degrees, analyzed using a small-angle X-ray scattering method under different relative humidity (RH) conditions. The characteristic "ionomer peak" with a corresponding correlation distance of approximately 1.0 nm was observed at RH < 80%. This distance is much smaller than the literature-reported mean distance between two ionic clusters, but close to the Bjerrum length of water. Since the representative number of water molecules per cation, nw, was small, we proposed that dissociated ion-pairs are distributed in the hydrophilic domains (ion-channels). At RH < 80%, ion-channels are disconnected, however in liquid water, they are well-connected as evidenced by the sharp increase in nw. The disconnected ion-channels even under relatively high RH conditions should be a substantial factor for the low power generation efficiency of AEM-type fuel cells.

Imidazolium-based anion exchange membranes for alkaline anion fuel cells: elucidation of the morphology and the interplay between the morphology and properties.

We investigated the morphology and swelling behavior of a new graft-type of anion exchange membrane (AEM) containing 2-methylimidazolium groups by using a contrast variation small angle neutron scattering (SANS) technique. These AEMs were prepared by radiation-induced grafting of 2-methyl-1-vinylimidazole and styrene into poly(ethylene-co-tetrafluoroethylene) (ETFE) films and subsequent N-alkylation with methyliodide, and possessed both high alkaline durability and high conductivity. Our results showed that the crystalline lamellar and crystallite structures originating from the pristine ETFE films were more or less conserved in these AEMs, but the lamellar d-spacing in both dry and wet membranes was enlarged, indicating an expansion of the amorphous lamellae due to the graft chains introduced in the grafting process and the water incorporated in the swelling process. For the first time, the swelling behavior of the AEMs was studied quantitatively in various water mixtures of water and deuterated water with different volume ratios (contrast variation method), and the morphology of these membranes was elucidated by three phases: phase (1) crystalline ETFE domains, which offer good mechanical properties; phase (2) hydrophobic amorphous domains, which are made up of amorphous ETFE chains and offer a matrix to create conducting regions; phase (3) interconnected hydrated domains, which are composed of the entire graft chains and water and play a key role in promoting the conductivity.

Chemical modification of the internal surfaces of cylindrical pores of submicrometer size in poly(ethylene terephthalate).

Chemical modification of the internal surfaces of cylindrical pores with submicrometer pore diameter in a poly(ethylene terephthalate) (PET) film was examined. The modification involved the alkylation of the carboxylic acid on the surfaces with the alkylation reagent containing a fluorescent probe, and it was monitored by observing the change in fluorescent emission intensity. When the N,N-dimethylformamide solution of 4-(bromomethyl)-6,7-dimethoxycoumarin (BrCU), which bore a coumarin fluorophore, was introduced into the pores, the emission and excitation intensities of the membranes increased proportionally with increases of the pore surface areas. Fluorescent spots about 300 nm in diameter, which were located at the positions of the pores, can be observed in the fluorescence microscope image of the membranes, indicating that highly concentrated fluorescent probes are chemically incorporated on the internal surfaces of the cylindrical pores with 210 nm diameter in the membranes. In the reactions of the PET surfaces with BrCU, the fluorescent intensities increased with increases of the contact angles. This result indicates that the hydrophilicity of the internal pore surfaces can be qualitatively modified by controlling the change in the fluorescent intensities.

Regioselectivity control of radiation-induced reaction: electron beam-induced fries rearrangement of sulfonamide within a beta-cyclodextrin inclusion complex.

EB (electron beam) irradiation of sulfonamide within a beta-cyclodextrin (beta-CD) inclusion complex in the solid state induced the solvent-free Fries rearrangement, which proceeded at a shorter reaction time with reversed regioselectivity by inclusion into the beta-CD, compared with that of sulfonamide crystals; the beta-CD as a restricted nanospace had a large effect on the reactivity and regioselectivity of the solvent-free EB-Fries rearrangement.

Radiation-induced reactions via the lowest excited states in cinnamic acid crystals.

Radiation-induced reactions of cinnamic acid derivatives have been examined and compared with photoreactions in the crystalline state; all the reaction products were exactly the same as those of the photoreactions, indicating that the reactions proceed only via the lowest excited state to give [2 + 2] cycloadducts, E/Z isomerization products, or starting molecules.