Conducting carbon/polymer composites as a catalyst support for proton exchange membrane fuel cells

Carbon/poly(3,4‐ethylene dioxythiophene) (C/PEDOT) composites are synthesized by in situ chemical oxidative polymerization of EDOT monomer on carbon black in order to decrease carbon corrosion that occurred in carbon‐supported catalysts used in proton exchange membrane fuel cell. The effects of different dopants including polystyrene sulfonic acid, p‐toluenesulfonic acid and camphorsulfonic acid with the addition of ethylene glycol or dimethyl sulfoxide on the properties of the composites are investigated. The synthesized composites are characterized by X‐ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, surface area analysis and scanning electron microscope. Electrical conductivity is determined by using the four‐point probe technique. Electrochemical oxidation characteristics of the synthesized C/PEDOT composites are investigated by cyclic voltammetry by applying 1.2 V for 24 h. The composite prepared at 25 °C with p‐toluenesulfonic acid and ethylene glycol shows the best carbon corrosion resistance. Platinum‐supported catalyst by using this composite was prepared using microwave irradiation technique, and it was seen that the prepared catalyst did not significantly lose its hydrogen oxidation and oxygen reduction reaction activities after electrochemical oxidation. Copyright © 2013 John Wiley & Sons, Ltd.     

Star-shaped hexaaryltriindoles small molecules: Tuning molecular properties towards solution processed organic light emitting devices

We present a series of differently substituted star-shaped hexaaryltriindoles with tunable light-emitting properties. The deep blue emission is unchanged by donor peripheral substituents while an increasing acceptor character produces a reduction of the optical gap, an increased Stokes shift and eventually leads to the appearance of a new electronic level and to the simultaneous deep blue (413 nm) and green (552 nm) emission in solution. Quenching by concentration increases with the acceptor character but is lower as the tendency of these compounds to aggregate is stronger. Solution processed thin films present optical and morphological qualities adequate for device fabrication and similar electronic structure compared to solutions with an emission range from 423 nm up to 657 nm (red), demonstrating the possibility of tuning the energy levels by chemical functionalization. We have fabricated and characterized single-layer solution processed organic light emitting diodes (OLED) to investigate the influence on transport and emission properties of the substituting species. We analyzed the I–V response using a single-carrier numerical model that includes injection barriers and non-uniform electric-field across the layer. As a result, we obtained the electric field dependence of the mobility for each device. Best results are obtained on the most electron rich derivative functionalized with six donor methoxy groups. This material shows the highest emission efficiency in solid state, due to aggregation-induced enhancement, and better transport properties with the highest mobility and a very low turn-on voltage of 2.8 V. The solution processed OLED devices produce stable deep blue (CIE coordinates (0.16, 0.16)) to white (CIE coordinates (0.33, 0.3)) emission with similar luminous efficiencies.     

An efficient ZnS-UV photocatalysts generated in situ from ZnS(en)0.5 hybrid during the H2 production in methanol–water solution

Highly active ZnS-UV was obtained in situ from ZnS(en)_0.5 hybrid during the hydrogen formation using a methanol–water solution under UV irradiation. X-ray diffraction patterns and UV spectroscopy for both ZnS-UV and ZnS-400 obtained from the calcination of the ZnS(en)_0.5 hybrid showed similar structural and photophysical properties; however, the efficiency of the ZnS-UV semiconductor was 7 times higher (4825 μmol h⁻¹ g⁻¹) compared to the ZnS-400. The highest H₂ production was obtained using a UV lamp of very low intensity (2.2 mW cm⁻¹) and it is attributed to a quantum size effect caused by the slow elimination of ethylenediamine (en) in the structural ZnS layer during the UV irradiation.     

Experimental analyses of the poly(vinyl chloride) foams' mechanical anisotropic behavior

Assessing a full set of mechanical properties is a rather complicate task in the case of foams, especially if material models must be calibrated with these results. Many issues, for example anisotropy and heterogeneity, influence the mechanical behavior. This article shows through experimental analyses how the microstructure affects different experimental setups and it also quantifies the degree of anisotropy of a poly(vinyl chloride) foam. Monotonic and cyclic experimental tests were carried out using standard compression specimens and non‐standard tensile specimens. Results are complemented and compared with the aid of a digital image correlation technique and scanning electron microscopy analyses. Mechanical properties (e.g., elastic and plastic Poisson's ratios) are evaluated for compression and tensile tests, for two different material directions (normal and in‐plane). The material is found to be transversely isotropic. Differences in the results of the mechanical properties can be as high as 100%, or even more depending on the technique used and the loading direction. Also, the experimental analyses show how the material's microstructure behavior, like the evolution of the herein identified “yield fronts” and a “spring back” phenomenon, can influence the phenomenological response and the failure mechanisms as well as the hardening curves. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Effects of salt mixtures on Spanish green table olive fermentation performance

This work investigates the effect of sodium, potassium, and calcium chloride salts on the performance of Spanish green table olive fermentation using a simple centroid mixture design. The presence of calcium chloride hindered the diffusion of all sugars and delayed the period required to reach their respective maximum concentrations in brines. Such effects can prevent tumultuous processes and gas pocket spoilage. Acetic acid was present at low concentrations in all treatments but was not generated during fermentation. The production rate of lactic acid was either decreased or delayed by the presence of calcium chloride but adequate final conditions were always reached. The chemometric analysis classified treatments into groups according to the presence of calcium chloride and disclosed a stimulating effect of potassium on lactic acid production. Therefore, these techniques can be a useful tool to investigate olive fermentation performance. According to the results, acceptable Spanish green table olives can be produced using salt mixtures, with the subsequent reduced sodium content in the final products. The results obtained in this study could also be of interest for other fermented vegetables.     

Assessment of the bioavailability of toxic and non-toxic arsenic species in seafood samples

Bioavailability of total arsenic, toxic (arsenite, As(III); and arsenate, As(V)), and non-toxic (monomethylarsonic acid, MA; dimethylarsonic acid, DMA; arsenobetaine, AB; and arsenocholine, AC) arsenic species has been assessed in different raw seafood samples (white fish, cold water fish and molluscs) by using an in vitro model that combines simulated gastric and intestinal digestion/dialysis methods. Correlations between arsenic species bioavailability and seafood nutrient contents (fat and protein) have also been established. Total arsenic content in seafood samples, and dialyzable and non-dialyzable fractions, were analyzed by inductively coupled plasma – mass spectrometry (ICP–MS) after a microwave-assisted acid digestion treatment. The determination of the different arsenic species concentrations in the samples (after an optimised matrix solid phase dispersion (MSPD) approach) and in the dialyzable fraction was done by high performance liquid chromatography (HPLC) coupled to ICP-MS as a selective detector. Accuracy of the procedure (total arsenic determination) was assessed by analyzing DORM-2 and BCR-627 certified reference materials. The accuracy of the in vitro procedure was established through a mass-balance study. After statistical evaluation (95% confidence interval), good accuracy of the whole in vitro process, for total arsenic and for arsenic speciation, was observed. High dialyzability percentages for total arsenic and for arsenic species were found (i.e. from 84.6 ± 1.7% to 106 ± 2.6%). Bioavailability of arsenic exhibits a negative correlation with the fat content of the seafood. However, no correlation was observed between the bioavailable fraction of total arsenic and arsenic species and the protein content of the seafood studied.     

Current concepts: tissue engineering and regenerative medicine applications in the ankle joint

Tissue engineering and regenerative medicine (TERM) has caused a revolution in present and future trends of medicine and surgery. In different tissues, advanced TERM approaches bring new therapeutic possibilities in general population as well as in young patients and high-level athletes, improving restoration of biological functions and rehabilitation. The mainstream components required to obtain a functional regeneration of tissues may include biodegradable scaffolds, drugs or growth factors and different cell types (either autologous or heterologous) that can be cultured in bioreactor systems (in vitro) prior to implantation into the patient. Particularly in the ankle, which is subject to many different injuries (e.g. acute, chronic, traumatic and degenerative), there is still no definitive and feasible answer to ‘conventional’ methods. This review aims to provide current concepts of TERM applications to ankle injuries under preclinical and/or clinical research applied to skin, tendon, bone and cartilage problems. A particular attention has been given to biomaterial design and scaffold processing with potential use in osteochondral ankle lesions.     

Dispersive Liquid–Liquid Microextraction Followed by Capillary High-Performance Liquid Chromatography for the Determination of Six Sulfonylurea Herbicides in Fruit Juices

In this study a simple, rapid, and efficient method has been developed for the determination of six sulfonylurea herbicides (SUHs): triasulfuron, metsulfuron-methyl, chlorsulfuron, flazasulfuron, chlorimuron-ethyl, and primisulfuron-methyl in commercial grape and apple juice samples, using dispersive liquid–liquid microextraction coupled with capillary high-performance liquid chromatography with diode array detection. Various parameters that influence the extraction efficiency, such as the type and volume of extraction and disperser solvents, sample pH, and salt addition, were investigated and optimized. Under the optimum conditions, limits of detection and quantification of the method were in the ranges of 2–9 and 8–29 μg L^?1, respectively, lower than the maximum residue limits set by the European Union for the raw fruits, such as grape and apple. The intra- and inter-day relative standard deviations varied from 1.0 to 8.2 and 1.8 to 9.8 %, respectively, with recoveries between 72.0 and 109.5 % for commercial grape (both white and red) and apple juice samples, showing satisfactory accuracy for the determination of SUHs in fruit juices.     

Harvesting of river flow energy for wireless sensor network technology

River courses play a vital role in preserving unpolluted ecosystems. On the other hand, networks of sensor nodes can be used to measure characteristic parameters in the environment such as temperature, pressure, humidity or the concentration of pollutants. In the framework of the EU FP7 project “GOLDFISH”, technical competences of a consortium of 11 institutions are hence employed in designing, manufacturing, validating and operating wireless sensors nodes for tracking pollution in remote rivers. The sensor network is composed of sensor clusters located underwater and gateways on the riverbank with long-distance communication links to the central management and monitoring station. Each sensor node is composed of active electronic devices that have to be constantly powered. Batteries can generally be used for this purpose, but problems may occur when they are to be recharged or replaced, especially in the case of large networks placed in scarcely accessible locations. State-of-the-art energy harvesting technologies can hence constitute a viable powering solution. The possibility to use different small-scale river flow energy harvesting principles is thoroughly studied in this work by the University of Rijeka GOLDFISH team: a miniaturized hydro-generator, a ‘piezoelectric eel’ and a hybrid solution of a rotating shaft plucking a piezoelectric beam. The first two concepts are validated experimentally in a flow channel and in real river conditions. The miniaturized hydro-generator with suitable power management electronics is finally embedded into the wireless sensor node deployed into the river, allowing the GSM transmission of collected data to be successfully performed.     

An Analysis of Intermetallic Bonding between a Ring Carrier and an Aluminum Piston Alloy

This paper presents the results of an analysis of the formation of an intermetallic bond between a ring carrier and an aluminum piston alloy. The ring carrier is made of austenitic cast iron (Ni-Resist) to increase the wear resistance of the first ring groove and is applied in highly loaded diesel engines. The most important thing is that the Ni-Resist (ferrous) must be bonded with a non-ferrous piston material during the casting of the piston. A metallographic investigation using an optical microscope in combination with the SEM/EDS analysis of the quality of the intermetallic bonding layer was done. The test results show that if the proper conditions are met, then the preparation of the ring carrier can be made successfully, as can the formation of the metal connection between the two materials of different qualities.