Direct-Ink-Writing of Electroactive Polymers for Sensing and Energy Storage Applications

Considering the high levels of materials used in the fields of electronics and energy storage systems, it is increasingly necessary to take into consideration environmental impact. Thus, it is important to develop devices based on environmentally friendlier materials and/or processes, such as additive manufacturing techniques. In this work, poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) are prepared by direct-ink-writing (DIW) by varying solvent evaporation temperature and fill density percentage. Different morphologies for both polymers are obtained, including dense films and porous membranes, as well as different electroactive β-phase content, thermal and mechanical properties. The dielectric constant and piezoelectric d₃₃ coefficient for dense films reaches up to 16 at 1 kHz and 4 pC N⁻¹, respectively for PVDF-HFP with a fill density of 80 and a solvent evaporation temperature of 50 °C. Porous structures are developed for battery separator membranes in lithium-ion batteries, with a highest ionic conductivity value of 3.8 mS cm⁻¹ for the PVDF-HFP sample prepared with a fill density of 100 and a solvent evaporation temperature of 25 °C, the sample showing an excellent cycling performance. It is demonstrated that electroactive films and membranes can be prepared by direct-ink writing suitable for sensors/actuators and energy storage systems.     

Hydrogen-helium scattering cross-sections for transmission elastic recoil detection analysis

¹H(,p) ⁴He scattering cross-sections were determined for the 6.5–13 MeV (incident energy) range, thereby extending the energy range for such data beyond that available in the literature. These values are essential for the further development of hydrogen concentration profiling by the transmission elastic recoil detection technique, of particular interest in the design of surface-engineered hydrogen contamination barriers for steels.     

In vivo aging of gutta‐percha dental cone

Gutta‐percha cone is the most widely used material for root canal filling. The in vivo aging of this cone focus on the degradation of its main organic component, trans‐1,4‐polyisoprene, was studied. Aged cones (25 samples) from 2 to 30 years of root canal filling were extracted from different patients in the occasion of retreatment by mechanical way. The information about the aging time was given by the patients. Gel‐permeation chromatography (GPC) and infrared spectroscopy (FTIR) were the analytical techniques used. Polyisoprene degrades with time of aging, but in a slow process. Decrease in polymer molar mass from 5.7 × 10⁵ to 1.7 × 10⁵ g/mol was observed in polyisoprene from cone after 30 years of root canal filling and inside a noninfected tooth. In tooth with caries and periodontal infection, the decrease in molar mass is higher (4.6 × 10⁴ g/mol in cone with 10 years of aging). The production of carbonyl and hydroxyl groups in the aged material indicates that the process is oxidative, even in closed teeth. In these cases, the oxygen could be provided from tissue fluid. The degradation mechanism is complex and depends on many factors, besides time of root canal filling. The dental problem caused by the aging could be the production and migration of cytotoxic substances to periodontal ligament and the reduction on the canal sealing property due to the polymer weight loss. Both of them could contribute to the root canal treatment failure. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100:4082–4088, 2006     

Surface Pretreatments of Silicon Nitride for CVD Diamond Deposition

The efficiency of different surface pretreatments (four standard chemical etchings and four diamond powder abrasive procedures) on silicon nitride (Si₃N₄) substrates for chemical vapor deposition (CVD) of diamond has been systematically investigated. Blank Si₃N₄ samples were polished with colloidal silica (∼0.25 μm). Diamond nucleation and growth runs were conducted in a microwave plasma chemical vapor deposition apparatus for 10 min and 6 h, respectively. Superior results concerning nucleation density ( N _d∼ 10¹⁰ cm⁻² after 10 min), film uniformity, and grain size (below 2 μm after 6 h) were obtained for the mechanically microflawed samples, revealing that chemical etchings (hot and cold strong acids, molten base or CF₄ plasma) are not crucial for good CVD diamond quality on Si₃N₄.     

Influence of the composition of the binder and the carbonation on the zeta potential values of hardened cementitious materials

Electroosmotic experiments have been carried out on eight different mixes of hardened cementitious matrixes including concrete, mortar and pastes, different types of binders, carbonated and non-carbonated specimens and different test conditions. From these trials, the zeta potential values have been determined and the optimum experimental parameters and devices have been established. In addition, the influence of the composition of the binder on the zeta potential has been quantified indicating that higher amounts of Al₂O₃ in the binder lead to higher positive values of zeta potential, while the SiO₂ acts just on the opposite side. This has been explained in terms of the different i.e.p. (isoelectric point) for both oxides. Concerning the influence of carbonation, it increases the absolute value of the zeta potential toward more negative values; this behaviour has been attributed to the influence of the specifically adsorbed Ca²⁺ in the negative sites of the surface in the non-carbonated samples.     

Land Use Effect on the CN Model Parameters in a Tropical Dry Environment

Dry tropical forests account for over 1,000,000 km², and there is still lack of knowledge on their hydrologic processes. The curve number (CN) hydrologic model developed by the Natural Resources Conservation Service (NRCS) is widely applied for runoff determination in various parts of the world, but not so in tropical semiarid regions. This study analyzes the impact of land use changes on the CN model in a tropical semiarid environment, in two catchments of native dry tropical forest and thinned dry tropical forest land use from 2009 to 2012. The CN model was calibrated and validated for the NRCS recommended initial abstraction ratio λ = 0.2, and for λ evaluated from rainfall and runoff data. A reliability analysis was performed using Monte Carlo simulation. Model goodness-of-fit was assessed with statistical criteria. A total of 42 and 40 rainfall-runoff events were analyzed for the native and thinned dry tropical forest, respectively. Characteristic λ values of 0.15 and 0.11 were determined for the two respective catchments. Although CN values were similar for both land uses, CN_λ=0.20 = 80 and CN_{median λ} = 77, the thinned catchment showed a higher CN model parameters variability. The CN model was more sensitive to variations of CN values than to those of λ. This study showed that no matter the vegetation management in a dry tropical forest environment, modeled runoff is not affected by λ, but rather affected by CN, which represents soil, landuse and management.     

Effect of the reaction conditions on the properties of poly(4,4′-diphenylether-1,3,4-oxadiazole)s

Summary Poly(4,4-diphenylether-1,3,4-oxadiazole)s have been prepared by polycondensation of 4,4-diphenylether dicarboxylic acid and hydrazine sulphate, HS, in poly(phosphoric acid), PPA, under different reaction condictions. The products were characterized by viscometry, gel permeation chromatography, ¹H-NMR spectrometry and thermogravimetric analysis. Dense membranes have been prepared and submitted to gas transport and wide angle X-ray diffraction, WAXD, experiments. The differences found in permeability and selectivity parameters, as well as in density and WAXD results, are discussed in terms of their solution viscosities and hydrazide repeat unit contents.     

Catalysts based in cerium oxide for wet oxidation of acrylic acid in the prevention of environmental risks

Acrylic acid is a refractory compound for the non-catalytic wet oxidation (WO) process and can seriously damage the environment when released in industrial effluents. Oxidation of acrylic acid by catalytic wet oxidation (CWO) was studied in slurry conditions in a high-pressure batch reactor at 200 °C and 15 bar of oxygen partial pressure. Several solid cerium-based catalysts prepared in our laboratory were used (Ag/Ce, Co/Ce, Mn/Ce, CeO, MnO) and evaluated in terms of activity, selectivity and stability. Mn/Ce shows the higher activity in 2 h with 97.7% reduction of total organic carbon (TOC) followed by: MnO(95.5%)>Ag/Ce(85.0%)>Co/Ce(65.1%)>CeO(61.2%). Attempts were also carried out to analyze the influence of different Mn/Ce molar ratios. High percentages of Mn lead to practically total organic carbon concentration (TOC) abatements while low ratios lead to the formation of non-oxidizable compounds. Acrylic acid was readily degraded by all the catalysts pointing out the high importance of using a catalytic process. pH was an indicator of the reaction pathway and acetic acid was found as the major reaction intermediate compound; however it is completely oxidized after 2 h with exception for Co/Ce, CeO and MnO. Carbon adsorption and leaching of metals were poorly found for Mn/Ce indicating high stability. The catalyst microstructure after the reaction was analyzed and formation of whiskers of β-MnO₂ (or less probably MnOOH) were observed at the catalyst surface. Therefore, Mn/Ce revealed to be a promising catalyst for the treatment of effluents containing acrylic acid; nevertheless, its commercialization depends on further research.     

Electrocatalytic oxidation of ethanol on Pt–Mo bimetallic electrodes in acid medium

Pt–Mo alloy electrocatalysts were prepared by an arc-melting furnace process to investigate the origin of their enhanced activity toward ethanol oxidation. Two Mo contents were chosen in zones of the binary phase diagram where they are supposed to form either a pure alloy mixture or a solid solution. Pt–Mo alloy catalysts were more active than Pt-alone. Gradual Mo dissolution at the electrode surface was observed after voltammetric and chronoamperometric measurements. The dissolved Mo contributed to the catalytic effect of the electrode as underpotentially deposited (upd) adatoms. This dissolution probably also leads to an increase in the electrode surface roughness. Low molybdenum content in the electrode material enhances the activity toward ethanol oxidation when compared to Pt-alone. Ethanol oxidation was also investigated by in situ infrared reflectance spectroscopy in order to determine the presence of adsorbed intermediates like CO species. Acetaldehyde, acetic acid and CO₂ were also found by spectroscopic experiments.     

A web-based platform for biosignal visualization and annotation

With the advent of wearable sensing and mobile technologies, biosignals have seen an increasingly growing number of application areas, leading to the collection of large volumes of data. One of the difficulties in dealing with these data sets, and in the development of automated machine learning systems which use them as input, is the lack of reliable ground truth information. In this paper we present a new web-based platform for visualization, retrieval and annotation of biosignals by non-technical users, aimed at improving the process of ground truth collection for biomedical applications. Moreover, a novel extendable and scalable data representation model and persistency framework is presented. The results of the experimental evaluation with possible users has further confirmed the potential of the presented framework.