Operando infrared spectroscopy of the fuel cell membrane electrode assembly Nafion–platinum interface

The Nafion–Pt interfaces in membrane electrode assemblies of operating fuel cells were studied by operando infrared spectroscopy. The potential dependence of atop adsorbed CO peak frequencies were measured over the potential range of 0–600 mV (vs. NHE) at 60 °C. Complex Stark tuning of peak frequencies arise from a combination of potential dependent coverage effects, and changes in the extent of back-donation from the metal d-band to the renormalized 2π^∗ MO of CO_ads. The Nafion–Pt interface was studied at higher potentials (initiating at open circuit) by examining platinum reflectivity as a function of electrode potential. The oxygen reduction onset-current is coincident with the observance of a 2% step-increase in Pt reflectivity and emergence of Nafion–Pt interface spectra.     

Effect of the doping time of the 1‐butyl‐3‐methylimidazolium ionic liquid cation on the Nafion membrane proprieties

Nafion membranes were prepared by incorporating in the polymer matrix the 1‐butyl‐3‐methylimidazolium (BMI⁺) ionic liquid cation at different doping levels. Increasing the doping time of the membranes with the ionic liquid results in increased incorporation of the BMI⁺ cation but a decrease in the bulk conductivity. The thermogravimetric analysis shows that the BMI⁺ cation incorporation increases the thermal stability of the membranes. The higher discharge efficiency of the fuel cell at 80°C was obtained by using Nafion membrane after 15 minutes of doping in the ionic liquid solution.     

SEM and AFM characterization of surface of two RMGICs for degradation before and after modification with bioactive glass ceramic

Objectives: The aim of this study was to evaluate the effect of bioactive glass–ceramic particles (Biosilicate®) addition on surface nanoroughness and topography of Resin-modified glass ionomer cements (RMGICs).

Methods: Experimental materials were made by incorporating 2 wt% of Biosilicate® into Fuji II LC® (FL) and Vitremer® (VT) powders. Disks of RMGICs (with and without Biosilicate®) measuring 0.5 cm (diameter) × 0.5 mm (thickness) were fabricated and polished. Samples were stored at 37 °C in dry or immersed in distilled water for 30 days. Digital images (20 × 20 μm) from the surfaces were obtained by means of an atomic force microscopy. Three images were acquired for each sample, and four nanoroughness measurements were performed in each image. Nanoroughness (Ra, nm) was assessed by Nanoscope Software V7. Data were analyzed with ANOVA and Student–Newman–Keuls multiple comparisons (p < 0.05). SEM images were obtained for surface topography analysis.

Results: FL was significantly rougher than VT (p < 0.05) in wet and dry conditions. The addition of Biosilicate® increased the surface roughness in VT and decreased in FL, regardless of the storage media (p ≤ 0.05). No differences existed between materials and storage conditions after Biosilicate® addition. Significance: The Biosilicate® particles addition produced changes on the surface nanoroughness of the RMGICs. These changes depended on the particles size of the original cements in dry conditions. In water storage, dissolution of the Biosilicate® particles, a silica-rich gel formation, and a hydroxyl carbonate apatite precipitation on the surface of the materials changed the nanoroughness surface. FL was the roughest in both conditions.

Significance: The Biosilicate® particles addition produced changes on the surface nanoroughness of the RMGICs. These changes depended on the particles size of the original cements in dry conditions. In water storage, dissolution of the Biosilicate® particles, a silica-rich gel formation, and a hydroxyl carbonate apatite precipitation on the surface of the materials changed the nanoroughness surface. FL was the roughest in both conditions.     

Effect of self-etching dual-curing universal adhesive system application on bond strength of dentin resinous liners dentin

Purpose: The aim of this study was to evaluate the influence of previous application of an adhesive system on bond strength of resinous liner materials to dentin. Methods: Ninety bovine incisors crowns had a 6 × 6 mm area of dentin exposed, with minimum of 2 mm thickness. They were embedded in acrylic resin, and the dentin was polished with P600 SiC sandpaper for 30 s to standardize the smear layer. The specimens were divided into 6 groups (n = 15) according to the application or not of a self-etching system (Futurabond U – Voco) and the type of resinous liner used: A+Ionoseal (adhesive and Ionoseal – Voco); Ionoseal (Ionoseal only); A+Vitrebond (adhesive and Vitrebond – 3M/ESPE); Vitrebond (Vitrebond only); A+Ionosit (adhesive and Ionosit – DMG) and Ionosit (Ionosit only). Adhesives were used following manufacturer’s instructions, and the liner materials were applied inside a 2-mm-depth matrix and light-cured for 20 s. The bond strength was measured by microtensile test, using a universal testing machine with a cross-speed of 1 mm/min. Data were analyzed using one-way ANOVA and Tukey’s test (p < 0.05). Results: The adhesive system application increased bond strength of all liners tested. Ionoseal presented the highest bond strength when the adhesive system was used and exhibited similar performance to Vitrebond without adhesive. Ionosit without adhesive showed the smallest bond strength compared with the other liners tested. Conclusion: The application of an adhesive system prior to the use of the resinous liners improved the bond strength to dentin and should be preconized.     

Electrophoretic co-deposition of Bi2O3–multiwalled carbon nanotubes coating as supercapacitor electrode

Nafion is suggested as an efficient assistant in preparing supercapacitor by employing nanoparticles. In this work, using a bi-additive of 0.10-mM NaOH + 0.10 g L⁻¹ Nafion, Nafion-assisted electrophoretic co-deposition of Bi₂O₃–multiwalled carbon nanotubes (MWCNTs) coating is successfully realized in ethanol solvent. The capacitance performances of the electrophoretic coatings in 6.0-M KOH electrolyte are investigated by cyclic voltammetry and galvanostatic charge–discharge techniques. Comparing with Bi₂O₃ coating prepared with electrophoretic deposition (EPD) by employing other additive (such as polyethyleneimine), the Bi₂O₃ coating prepared by Nafion-assisted EPD shows a better capacitance performance. Benefiting from the improvement in coating conductivity caused by MWCNTs, with a small additional amount of 4.0 wt.%, the Bi₂O₃–MWCNTs coating exhibits an amazing 164% increase of mass-specific capacitance (473 F g⁻¹ at the current density of 1.0 A g⁻¹) in comparison with pure Bi₂O₃ coating (179 F g⁻¹ at the current density of 1.0 A g⁻¹). The cyclic stability test exhibits excellent capacitance retention of 88.7% over 3000 cycles at a constant current density of 10.0 A g⁻¹. This work combines the advantages of MWCNTs, Nafion, and EPD to provide a facile route for preparing Bi₂O₃-based coating as a high-performance supercapacitor electrode.     

新型含硅全氟磺酸膜性能研究

采用纳米原位复合技术制备了Nafion/SiO~2复合膜,TG—DSC(热失重-差热)分析表明Nafion1135/SiO~2复合膜比Nafion1135膜具有较高的含水和保水能力;溶胀率测试表明Nafion1135/SiO~2复合膜能明显降低膜的溶胀形变,其形变能力只有Nafion1135膜的1/4;110℃时,Nafion1135/SiO~2复合膜的电阻率只有Nafion1135膜的1/2。     

Nafion干燥器GASS处理系统在“超低排放”CEMS中的工程应用研究

燃煤电厂在推广"超低排放"CEMS气态污染物监测系统监测低量程SO2和NOx中,低温、高湿度的烟气条件是极为严峻的挑战。Nafion干燥管独特的气态膜除湿、能保留目标气体的特点,为冷干直抽法CEMS提出了一个样气处理的新方案。Nafion管为核心的GASS样气处理系统,集絮凝过滤、除酸雾、Nafion管干燥和在线酸性气体露点监测为一体,可彻底解决冷干直抽法CEMS中冷凝水析出和低量程SO2易溶于冷凝水的难题,是一种创新的冷干直取法CEMS样气处理技术。通过实验室试验,手持式CEMS应用实验,和嘉兴发电厂8号机组"超低排放"CEMS的应用,证明GASS样气处理系统非常适合在燃煤电厂"超低排放"CEMS中应用。     

Viscoelastic properties and morphology of sulfonated poly(styrene-b-ethylene/butylene-b-styrene) block copolymers (sBCP), and sBCP/[silicate] nanostructured materials

Self-assembled organic/inorganic hybrid materials were created via domain targeted sol-gel reactions of tetraethylorthosilicate in solution with sulfonated poly(styrene-b-[ethylene-co-butylene]-b-styrene) (sSEBS) copolymers. Dynamic mechanical analyses (DMA) of these hybrid materials suggest that the silicate component preferentially incorporates within the sulfonated polystyrene (PS) domains. An irreversible order-order transition (OOT) for unmodified SEBS, sSEBS, and the organic/inorganic hybrids was identified using DMA in shear mode. The OOT temperature increases with sulfonation as well as by adding a silicate phase by the sol-gel process. The DMA results imply a morphological shift with sulfonation, and reflect modified interactions within and between phases. Atomic force microscopy (AFM) indicated a shift from hexagonally packed cylinders in unmodified SEBS to a lamellar morphology in the sulfonated materials, but silicate incorporation did not affect the morphology or domain dimensions. The latter result is evidence for sol-gel polymerization templating in a self-assembly process. The phase-separated morphology is stable up to the degradation temperature of the polymer and thermogravimetric analysis revealed that the degradation temperature is unaffected by silicate incorporation. Small angle X-ray scattering data are in harmony with the structures revealed by AFM in terms of degree of order and scale of features. These results are largely rationalized in terms of chain mobility restrictions due to hydrogen-bonding interactions between different sulfonated PS blocks, an increase in the PS-ethylene/butylene block mixing parameter, increased interfacial surface tension and chain restrictions posed by inserted silicate nanostructures in the case of the hybrid materials.     

ESR and FTIR studies on electron beam‐irradiated low‐density polyethylene blends

Low‐density polyethylene (LDPE) composites modified with a resin based on ethylene/methacrylic acid copolymer (surlyn) and/or citric acid were electron beam‐irradiated and investigated by electron spin resonance (ESR) at room temperature. ESR studies were carried out directly after irradiation and after various time intervals up to 72 h postirradiation. The irradiated samples showed the ESR spectrum of seven lines that was assigned to the formation of allyl radical. The nature and yield of the allyl radical of the different LDPE samples were analyzed as a function of time after irradiation. Also, the radical concentration, decay, decay rate, and kinetics of radical decay were evaluated. Fourier transform infrared (FTIR) analysis at a series of different temperatures upon cooling from room temperature to ?175°C and the reverse heating to +125°C was also carried out. The structural changes while cooling and heating of LDPE samples were investigated using FTIR spectrometry. The results showed that cooling of unirradiated LDPE samples to ?175°C results in a decrease of the intensities of IR bands. However, heating the samples from ?175°C up to +125°C led to a consequence increase in the intensities of the IR bands. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3461–3469, 2007