Characterization of cation-exchange membranes prepared from poly(vinyl alcohol) and poly(vinyl alcohol-b-styrene sulfonic acid)

Block-type cation-exchange membranes (CEMs) have been prepared by blending poly(vinyl alcohol) (PVA) and the polyanion poly(vinyl alcohol-b-styrene sulfonic acid) at various molar percentages of cation-exchange groups to vinyl alcohol groups, C_pa, and by cross-linking the PVA chains with glutaraldehyde (GA) solution at various GA concentrations, C_GA. The characteristics of the block-type CEMs were compared with random-type CEMs prepared in a previous study from the random copolymer, poly(vinyl alcohol-co-2-acrylamido-2-methylpropane sulfonic acid). At equal molar percentages of the cation-exchange groups, the water content of the block-type CEMs was less than that of the random-type CEMs. The charge density of the block-type CEMs increased with increasing C_pa and reached a maximum value. Further, the maximum value of the charge density increased with increasing C_GA. The maximum charge density value of 1.3 mol/dm³ was obtained for the block-type CEM with C_pa = 3.1 mol% and C_GA = 0.10 vol.%, which is almost two thirds of the value of a commercially available CEM [CMX: ASTOM Corp. Japan]. A comparison of the block-type and random-type CEMs with almost the same membrane resistance showed that the block-type CEMs had higher dynamic transport numbers than the random-type ones. The dynamic transport number and membrane resistance of the block-type CEM with C_pa = 4.0 mol% and C_GA = 0.10 vol.% were 0.96 and 4.9 Ω cm², respectively.     

Preparation and fuel cell performance of catalyst layers using sulfonated polyimide ionomers

Sulfonated polyimide (SPI-8) ionomers were used as binders in the catalyst layers, and their fuel cell performance was evaluated. SPI-8 ionomers functioned well in the anode with only minor overpotential even at low humidity (50% relative humidity (RH)). In contrast, the cathode performance was significantly dependent on the content and molecular weight of the ionomers and humidity of the supplied gases. Higher molecular weight of the ionomer caused larger potential drop at high current density at 80 and 100% RH since oxygen supply and/or water discharge became insufficient due to higher water uptake (swelling) of the ionomer. Similar results were obtained at higher ionomer content, because of the increase of thickness in the catalyst layer. The mass transport was improved with decreasing humidity, however, proton conductivity became lower. While the maximum values of j(@0.70?V) for all membrane electrode assemblies (MEAs) were ca. 0.35 A/cm(2), each electrode could have the different appropriate operating conditions. The results suggest that the parameters such as oxygen supply, proton conductivity, and water uptake and discharge need to be carefully optimized in the catalyst layers for achieving reasonable cathode performance with hydrocarbon ionomers.     

Argon Cluster Ion Beams for Organic Depth Profiling: Results from a VAMAS Interlaboratory Study

The depth profiling of organic materials with argon cluster ion sputtering has recently become widely available with several manufacturers of surface analytical instrumentation producing sources suitable for surface analysis. In this work, we assess the performance of argon cluster sources in an interlaboratory study under the auspices of VAMAS (Versailles Project on Advanced Materials and Standards). The results are compared to a previous study that focused on C(60)(q+) cluster sources using similar reference materials. Four laboratories participated using time-of-flight secondary-ion mass spectrometry for analysis, three of them using argon cluster sputtering sources and one using a C(60)(+) cluster source. The samples used for the study were organic multilayer reference materials consisting of a ～400-nm-thick Irganox 1010 matrix with ～1 nm marker layers of Irganox 3114 at depths of ～50, 100, 200, and 300 nm. In accordance with a previous report, argon cluster sputtering is shown to provide effectively constant sputtering yields through these reference materials. The work additionally demonstrates that molecular secondary ions may be used to monitor the depth profile and depth resolutions approaching a full width at half maximum (fwhm) of 5 nm can be achieved. The participants employed energies of 2.5 and 5 keV for the argon clusters, and both the sputtering yields and depth resolutions are similar to those extrapolated from C(60)(+) cluster sputtering data. In contrast to C(60)(+) cluster sputtering, however, a negligible variation in sputtering yield with depth was observed and the repeatability of the sputtering yields obtained by two participants was better than 1%. We observe that, with argon cluster sputtering, the position of the marker layers may change by up to 3 nm, depending on which secondary ion is used to monitor the material in these layers, which is an effect not previously visible with C(60)(+) cluster sputtering. We also note that electron irradiation, used for charge compensation, can induce molecular damage to areas of the reference samples well beyond the analyzed region that significantly affects molecular secondary-ion intensities in the initial stages of a depth profile in these materials.     

Fabrication and fluorescence properties of multilayered core–shell particles composed of quantum dot,gadolinium compound,and silica

A preparation method for multilayered quantum dot/silica/gadolinium compound/silica (QD/Si/Gd/Si) core–shell particles is proposed. Silica (Si)-coated quantum dot (QD/Si) core–shell particles were prepared by a Stöber method at room temperature in water/ethanol solution with TEOS and NaOH in the presence of QD nanoparticles. Succeeding gadolinium compound (Gd)-coating of the QD/Si core–shell particles was performed by a homogeneous precipitation method using Gd(NO₃)₃, urea, and polyvinylpyrrolidone in the presence of the QD/Si particles, which resulted in production of multilayered QD/silica/gadolinium compound (QD/Si/Gd) core–shell particles. For Si-coating of the QD/Si/Gd particles, the Stöber method was performed at room temperature in water/ethanol solution with TEOS and NaOH in the presence of the QD/Si/Gd particles. Consequently, Si-coated QD/Si/Gd, i.e., multilayered QD/Si/Gd/Si, core–shell particles were obtained. The QD/Si/Gd/Si particles revealed strong fluorescence, which was almost comparable to the QD particles with no shells. These particles are expected to be harmless to living bodies, and have dual functions of magnetic resonance imaging and fluorescence.     

Analysis of vibration waveforms of electromechanical response to determine piezoelectric and electrostrictive coefficients

We developed a possible method to determine both coefficients of piezoelectricity (d) and electrostriction (M) at the same time by a waveform analysis of current and vibration velocity in the resonance state. The waveforms of the current and vibration velocity were theoretically described using the equations of motion and piezoelectric constitutive equations, considering the dissipation effect. The dissipation factor of the d coefficient and M coefficient is dielectric loss tangent tan δ. The waveforms measured in all of the ceramics, such as Pb(Zr,Ti)O(3) (PZT), Pb(Mg,Nb)O(3) (PMN), and 0.8Pb(Mg(1/3)Nb2/3)O(3)-0.2PbTiO(3) (PMN-PT), were well fitted with the calculated waveform. This fitting produced both the d and M coefficients, which agreed with those determined via the conventional methods. Moreover, the respective contributions of both piezoelectricity and electrostriction to the d value determined in the resonance-antiresonance method were clarified.     

Polyelectrolyte and carbon nanotube multilayers made from ionic liquid solutions

The inevitable contact of substrates with water during the traditional practice of layer-by-layer assembly (LBL) creates problems for multiple potential applications of LBL films in electronics. To resolve this issue, we demonstrate here the possibility of a LBL process using ionic liquids (ILs), which potentially eliminates corrosion and hydration processes related to aqueous media and opens additional possibilities in structural control of LBL films. ILs are also considered to be one of the best "green" processing solvents, and hence, are advantageous in respect to traditional organic solvents. Poly(ethyleneimine) (PEI) and poly(sodium styrenesulfonate) (PSS) were dispersed in a hydrophilic IL and successfully deposited in the LBL fashion. To produce electroactive thin films with significance to electronics, a similar process was realized for PSS-modified single-walled carbon nanotubes (SWNT-PSS) and poly(vinyl alcohol) (PVA). Characterization of the coating using standard spectroscopy and microscopy techniques typical of the multilayer field indicated that there are both similarities and differences in the structure and properties of LBL films build from ILs and aqueous solutions. The films exhibited electrical conductivity of 10(2) S m(-1) with transparency as high as 98% for visible light, which is comparable to similar parameters for many carbon nanotube and graphene films prepared by both aqueous LBL and other methods.     

Extreme‐Performance Rubber Nanocomposites for Probing and Excavating Deep Oil Resources Using Multi‐Walled Carbon Nanotubes

The scarcity of oil resources is going to become one of the main factors threatening the stability of the global economy. To avoid an energy crisis in the future, it is essential to increase oil extraction in much deeper wells, experiencing higher temperatures and pressures. Exploring these deeper areas will demand novel and robust materials. Rubber sealants, or O‐rings, are especially key components in enabling the probing and production of oil in deeper wells, so that higher temperature and pressure reservoirs are reached. In this account, it is demonstrated that carbon nanotubes homogeneously and randomly dispersed in rubber matrices, are able to generate durable sealants that operate satisfactorily at extremely high temperatures and pressures (e.g., 260 °C and 239 MPa). The key issues in these novel composites are: i) the nanotube surface‐control and reactivity, ii) the used of multi‐walled carbon nanotubes (MWNTs)‐embedded in fluorinated rubber, and iii) the formation of a cellulation structure. This rubber nanocomposite with a cellulation structure and having extreme performance leads to a balanced pressure resistance, sealing ability, thermal resistance, and durability, which can contribute to doubling the current average global oil recovery efficiency.     

Improving the Solubility of Artificial Ligands of Streptavidin to Enable More Practical Reversible Switching of Protein Localization in Cells

Chemical inducers that can control target‐protein localization in living cells are powerful tools to investigate dynamic biological systems. We recently reported the retention using selective hook or “RUSH” system for reversible localization change of proteins of interest by addition/washout of small‐molecule artificial ligands of streptavidin (ALiS). However, the utility of previously developed ALiS was restricted by limited solubility in water. Here, we overcame this problem by X‐ray crystal structure‐guided design of a more soluble ALiS derivative (ALiS‐3), which retains sufficient streptavidin‐binding affinity for use in the RUSH system. The ALiS‐3–streptavidin interaction was characterized in detail. ALiS‐3 is a convenient and effective tool for dynamic control of α‐mannosidase II localization between ER and Golgi in living cells.