Surface Sensitive Nickel Electrodeposition in Deep Eutectic Solvent

The first steps of nickel electrodeposition in a deep eutectic solvent (DES) are analyzed in detail. Several substrates from glassy carbon to Pt(111) were investigated pointing out the surface sensitivity of the nucleation and growth mechanism. For that, cyclic voltammetry and chronoamperometry, in combination with scanning electron microscopy (SEM), were employed. X-ray diffraction (XRD) and atomic force microscopy (AFM) were used to more deeply analyze the Ni deposition on Pt substrates. In a 0.1 M NiCl2 + DES solution (at 70 °C), the nickel deposition on glassy carbon takes place within the potential limits of the electrode in the blank solution. Although, the electrochemical window of Pt|DES is considerably shorter than on glassy carbon|DES, it was still sufficient for the nickel deposition. On the Pt electrode, the negative potential limit was enlarged while the nickel deposit grew, likely because of the lower catalytic activity of the nickel toward the reduction of the DES. At lower overpotentials, different hydrogenated Ni structures were favored, most likely because of the DES co-reduction on the Pt substrate. Nanometric metallic nickel grains of rounded shape were obtained on any substrate, as evidenced by the FE-SEM. Passivation phenomena, related to the formation of Ni oxide and Ni hydroxylated species, were observed at high applied overpotentials. At low deposited charge, on Pt(111) the AFM measurements showed the formation of rounded nanometric particles of Ni, which rearranged and formed small triangular arrays at sufficiently low applied overpotential. This particle pattern was induced by the ⟨111⟩ orientation and related to surface sensitivity of the nickel deposition in DES. The present work provides deep insights into the Ni electrodeposition mechanism in the selected deep eutectic solvent.This work has been financially supported by the MCINN-FEDER (Spain) through the projects CTQ2016-76221-P and TEC2014-51940-C2-2R. P.S. acknowledges MECD for the award of an FPU grant

Role of intrinsic flaws upon flexural behaviour of a thermoplastic modified epoxy resin

A bisphenol A-based epoxy resin (DGEBA) was modified with 15 weight percent polysulphone (PSU) and thermally cured using 4-4′diaminodiphenylsulphone (DDS). Starting from a homogeneous DGEBA/DDS/PSU mixture, the system developed a two-phase morphology upon network formation. Dynamic mechanical analysis (DMA), transmission optical microscopy (TOM) and scanning electron microscopy (SEM) studies showed that the system developed a co-continuous morphology consisting of two distinct domains. One of the domains was an epoxy rich matrix containing PSU particles while the other consisted of a dispersion of epoxy particles within a PSU rich phase. Flexural strength distributions of unmodified and thermoplastic modified epoxy resin were obtained by testing the materials in three-point bending according to the ASTM D790 protocol. The flexural behaviour of the epoxy resin was not improved by the presence of thermoplastic. In addition, the thermoplastic modified epoxy resin displayed a higher data scatter compared with the neat resin. The fracture mechanism of unmodified and thermoplastic modified epoxy resins was demonstrated to be sensitive to the intrinsic flaw distribution. The two-parameter Weibull model, which was used to analyse the experimental data, gave a good representation of the fracture loads distribution with regression coefficients of 0.99.Fil: Giannotti, Marina Inés. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Galante, Maria Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Oyanguren, Patricia Angelica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Vallo, Claudia Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentin

Morphology control in polysulfone-modified epoxy resins by demixing behavior

Polysulfone (PSu) was used as a modifier of epoxy/aromatic diamine formulations. Two epoxy monomers, based on diglycidyl ether of bisphenol A (DGEBA), were used. The cure agent was 4,4′-diaminodiphenylsulfone. PSu was miscible with DGEBA, as shown by the existence of a single glass-transition temperature within the whole composition range. The effect of PSu addition on the cure kinetics was investigated. The reaction rate of the epoxy-amine species was slightly lower in the presence of PSu. The morphology was analyzed by optical and scanning electron microscopy. A range of microstructures were obtained by control over the cure temperature, the amount of PSu incorporated, and the molecular weights of the epoxy resins. The variations in the morphology resulted from the different stages of demixing, which were arrested because of the different developments of the viscosity of the system. © 2003 Wiley Periodicals, Inc.Fil: Giannotti, Marina Inés. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Solsona, M.S.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Galante, Maria Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Oyanguren, Patricia Angelica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentin

Morphology profiles obtained by reaction-induced phase separation in epoxy/polysulfone/poly(ether imide) systems

The reaction-induced phase separation in epoxy/aromatic diamine formulations simultaneously modified with two immiscible thermoplastics (TPs), poly(ether imide) (PEI) and polysulfone (PSF), has been studied. The epoxy monomer was based on the diglycidyl ether of bisphenol A (DGEBA) and the aromatic diamine was 4,4′-methylenebis(3-chloro 2,6-diethylaniline) (MCDEA). Phase-separation conversions are reported for various PSF/PEI proportions for blends containing 10 wt% total TP. On the basis of phase-separation results, a conversion–composition phase diagram at 200 °C was compiled. This diagram was used to design particular cure cycles in order to generate different morphologies during the phase-separation process. It was found that, depending on the PSF/PEI ratio employed, a particulate or a morphology characterized by a distribution of irregular PEI-rich domains dispersed in an epoxy-rich phase was obtained for initially miscible blends. Scanning electron microscopy (SEM) characterization revealed that the PEI-rich phase exhibits a phase-inverted structure and the epoxy-rich matrix presents a bimodal size distribution of TP-rich particles. For PSF/PEI ratios near the miscibility limit, slight temperature change result in morphology profiles.Fil: Giannotti, Marina Inés. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Mondragon, I.. Universidad del País Vasco; EspañaFil: Galante, Maria Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Oyanguren, Patricia Angelica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentin

Morphology and fracture porperties relationship of epoxy-diamine systems simultaneously modified with polysulfone and poly(ether imide)

An epoxy-diamine system was simultaneously modified with two immiscible thermoplastic polymers, polysulfone (PSF) and poly (ether imide) (PEI), to develop tough materials without adding high quantities of modifiers, in order to avoid the processibility problems caused by the high initial viscosity of the mixtures. The mechanical behavior of blends containing 10 and 15 wt% total thermoplastic was analyzed and compared with the generated morphologies. The scanning electron micrographs (SEM) of the broken surfaces showed that when a small part of PEI is replaced by PSF, drastic changes in morphology, leading to co-continuity between the phases, occurred together with fracture (critical stress intensity factor, KIC) improvements. As an additional advantage, no noticeable decrease in the elastic modulus (E) of final materials was observed.Fil: Giannotti, Marina Inés. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Bernal, Celina Raquel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Oyanguren, Patricia Angelica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Galante, Maria Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentin

Tensile response and fracture and failure behavior of jute fabrics-fly ash-vinylester hybrid composites

In this work, hybrid materials consisting on a vinylester matrix simultaneaously reinforced with jute woven fabrics and flyash particles were prepared. The tensile response and the fracture and failure behavior of these hybrid composites were investigated. Thermal stability of these materials was also studied. The aim was to obtain an environmentally friendly hybrid material with a good balance of tensile and fracture properties at relatively low cost. The effect of a novel treatment for the jute fabrics on the hybrids mechanical and fracture properties was investigated. The best balance of tensile and fracture properties was obtained for the hybrid consisting of fabrics treated with alkali under stress and fly ashes which also exhibited relatively high thermal stability.Fil: Stocchi, Ariel Leonardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Mar del Plata. Instituto de Investigación En Ciencia y Tecnología de Materiales (i); ArgentinaFil: Lauke, Bernd. Leibniz Institute of Polymer Research Dresden; AlemaniaFil: Giannotti, Marina Inés. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Mar del Plata. Instituto de Investigación En Ciencia y Tecnología de Materiales (i); Argentina. Instituto de Salud Carlos III. Centro de Investigación Biomédica en Red en Bioingeniería, Biomateriales y Nanomedicina; EspañaFil: Vazquez, Analia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Tecnologías y Ciencias de la Ingeniería; ArgentinaFil: Bernal, Celina Raquel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Tecnologías y Ciencias de la Ingeniería; Argentin

Reaction-Induced Phase Separation in Epoxy/PSF/PEI Systems: 1. Phase Diagrams

Epoxy-aromatic diamine formulations are simultaneously modified with two immiscible thermoplastics (TPs), poly(ether imide) (PEI) and polysulfone (PSF), The epoxy monomer is based on diglycidyl ether of bisphenol A and the aromatic diamines (ADs) are either 4,4′-diaminodiphenylsulfone or 4,4′-methylenebis(3-chloro 2,6-diethylaniline). The influence of the TPs on the epoxy-amine kinetics is investigated. It is found that PSF can act as a catalyst. The presence of the TP provokes an increase of the gel times. Cloud-point curves (temperature vs. composition) are shown for epoxy/PSF/PEI and epoxy/PSF/PEI/AD initial mixtures. Phase separation conversions are reported for the reactive mixtures with various TP contents and PSF/PEI proportions. On the basis of phase separation and gelation curves, conversion-composition phase diagrams at constant temperature are generated for both systems. These diagrams can be used to design particular cure cycles to generate different morphologies during the phase separation process, which is discussed in the second part of this series. © 2004 Wiley Periodicals, Inc.Fil: Giannotti, Marina Inés. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Foresti, María Laura. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Mondragon, I.. Universidad del País Vasco; EspañaFil: Galante, Maria Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Oyanguren, Patricia Angelica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentin

Distance and Potential Dependence of Charge Transport Through the Reaction Center of Individual Photosynthetic Complexes

Charge separation and transport through the reaction center of photosystem I (PSI) is an essential part of the photosynthetic electron transport chain. A strategy is developed to immobilize and orient PSI complexes on gold electrodes allowing to probe the complex's electron acceptor side, the chlorophyll special pair P700. Electrochemical scanning tunneling microscopy (ECSTM) imaging and current–distance spectroscopy of single protein complex shows lateral size in agreement with its known dimensions, and a PSI apparent height that depends on the probe potential revealing a gating effect in protein conductance. In current–distance spectroscopy, it is observed that the distance-decay constant of the current between PSI and the ECSTM probe depends on the sample and probe electrode potentials. The longest charge exchange distance (lowest distance-decay constant β) is observed at sample potential 0 mV/SSC (SSC: reference electrode silver/silver chloride) and probe potential 400 mV/SSC. These potentials correspond to hole injection into an electronic state that is available in the absence of illumination. It is proposed that a pair of tryptophan residues located at the interface between P700 and the solution and known to support the hydrophobic recognition of the PSI redox partner plastocyanin, may have an additional role as hole exchange mediator in charge transport through PSI

Distance and Potential Dependence of Charge Transport Through the P700 Reaction Center of Photosystem I

Photoinduced charge separation and transport through photosystem I (PSI) is an essential part of the photosynthetic electron transport chain. To investigate charge exchange processes mediated by the P700 reaction center of PSI, we have developed a strategy to functionalize gold electrodes with PSI complexes that orients and exposes their luminal side to the electrolyte. Bulk photoelectrochemical measurements demonstrate that PSI remains functional in a wide sample potential range around 0 mV/SSC. Electrochemical scanning tunneling microscopy (ECSTM) imaging of individual complexes shows lateral sizes in agreement with the dimensions of PSI and an apparent height that is gated by the probe potential of ECTSM as reported for smaller globular redox proteins. This experimental setup enables ECSTM current-distance spectroscopic measurements that unequivocally correspond to the P700 side of PSI. In these conditions, we observe that the spatial span of the current is enhanced (the distance-decay rate β is reduced) through the solution at sample potential 0 mV/SSC and probe potential 400 mV/SSC. This process corresponds to hole injection into an electronic state that is available in the absence of illumination. We propose that a pair of tryptophan residues located near P700 and known to integrate the hydrophobic recognition site for plastocyanin may have an additional role as hole exchange mediator involved in charge transport through PSI.<br /