DSA-elektrodien testaaminen kulumisen arvioimiseksi

Työn tavoitteena oli tutkia eri mittausmenetelmillä metallipinnoitettujen elektrodien kulumista kulumiskokeiden aikana. Mittausmenetelminä olivat käytössä syklinen voltammetria, polarisaatiokäyrän määritys ja sähkökemiallinen impedanssispektrometria, jotka olivat offline-mittausmenetelmiä. Näiden menetelmien avulla pystyttiin seuraamaan yksittäisten elektrodien kulumista ajon aikana. Elektrodin pinnoitteen alkuaineiden pitoisuuksia tutkittiin myös elektronimikroskoopin röntgenspektrometrin avulla. Työn aikana tehdyissä kulumiskokeista havaittiin elektrodin kuluvan sitä nopeammin mitä suurempi on virrantiheys. Työssä tehtyjen elektronimikroskooppikokeiden avulla havaittiin, että harvinaisten metallien seostaminen pinnoitteeseen pidentää metallipinnoitetun elektrodin käyttöikää. Syklisen voltammetrian avulla pystyttiin seuraamaan elektrodin pinta-alan muuttumista ajon aikana. Työssä käytettyjen kulumiskokeiden avulla ei suoranaisesti pystytty määrittämään elektrodin jäljellä olevaa elinikää.

Structural factors impacting carrier transport and electroluminescence from Si nanocluster-sensitized Er ions.

We present an analysis of factors influencing carrier transport and electroluminescence (EL) at 1.5 µm from erbium-doped silicon-rich silica (SiOx) layers. The effects of both the active layer thickness and the Si excess content on the electrical excitation of erbium are studied. We demonstrate that when the thickness is decreased from a few hundred to tens of nanometers the conductivity is greatly enhanced. Carrier transport is well described in all cases by a Poole-Frenkel mechanism, while the thickness-dependent current density suggests an evolution of both density and distribution of trapping states induced by Si nanoinclusions. We ascribe this observation to stress-induced effects prevailing in thin films, which inhibit the agglomeration of Si atoms, resulting in a high density of sub-nm Si inclusions that induce traps much shallower than those generated by Si nanoclusters (Si-ncs) formed in thicker films. There is no direct correlation between high conductivity and optimized EL intensity at 1.5 µm. Our results suggest that the main excitation mechanism governing the EL signal is impact excitation, which gradually becomes more efficient as film thickness increases, thanks to the increased segregation of Si-ncs, which in turn allows more efficient injection of hot electrons into the oxide matrix. Optimization of the EL signal is thus found to be a compromise between conductivity and both number and degree of segregation of Si-ncs, all of which are governed by a combination of excess Si content and sample thickness. This material study has strong implications for many electrically driven devices using Si-ncs or Si-excess mediated EL.

Produção de dióxido de manganês eletrolítico para uso em baterias de lítio

The e phase of electrolytic manganese dioxide (EMD) is the structural form most easily converted in the LiMn2O4 spinel used as cathode in lithium batteries. Thus, employing titanium as anode, a study of electrolysis parameters was carried out in order to determine the best conditions to produce an e-EMD suitable for that spinel preparation. The influence of solution temperature (65oC and 90oC) and current density (between 1 mA/cm2 and 17.5 mA/cm2) on the anode potential and the EMD properties was investigated using an aqueous 2.0 mol/L MnSO4 + 0.30 mol/L H2SO4 solution. In any of the electrolysis conditions tested only the e-EMD structure was obtained, but its specific surface area varied with the applied current density and temperature. Drying the e-EMD at temperatures between 60oC and 120oC did not cause any phase changes. To produce a suitable EMD at the highest current density possible without passivation of the titanium anode, the best electrolysis parameters were determined to be 90oC and 15 mA/cm2. The e-EMD thus obtained had a specific surface area (BET) of ca. 65 m2/g.

Avaliação dos tratamentos eletroquímico e fotoeletroquímico na degradação de corantes têxteis

This paper presents the study of the oxidation of three textile dyes (Remazol black B, Remazol Brilliant Orange 3R and Remazol Golden Yellow RNL) using electrochemical and photoelectrochemical methods. In both methods, electrolysis experiments were performed at a current density of 50 mA cm-2 in an aqueous solution of each dye (30 mg L-1), using a photoelectrochemical flow-cell. For all the dyes studied, the photoelectrochemical method was demonstrated to be more efficient than the electrochemical one. Photoelectrochemical oxidation resulted in complete decoloration after 90 min of electrolysis and total organic carbon (TOC) removal reached up to 36%. It was observed that the dyes presenting chromophores at higher wavelengths are removed the quickest, which indicates that photosensitised (photoassisted) oxidation occurs. The level of color was reduced to levels below the standards presented in the literature, which indicates the viability of the photoelectrochemical process as part of the treatment of textile effluents.

A Novel Missense Mutation, I890T, in the Pore Region of Cardiac Sodium Channel Causes Brugada Syndrome

Brugada syndrome (BrS) is a life-threatening, inherited arrhythmogenic syndrome associated with autosomal dominant mutations in SCN5A, the gene encoding the cardiac Na₊ channel alpha subunit (Naᵥ1.5). The aim of this work was to characterize the functional alterations caused by a novel SCN5A mutation, I890T, and thus establish whether this mutation is associated with BrS. The mutation was identified by direct sequencing of SCN5A from the proband’s DNA. Wild-type (WT) or I890T Naᵥ1.5 channels were heterologously expressed in human embryonic kidney cells. Sodium currents were studied using standard whole cell patch-clamp protocols and immunodetection experiments were performed using an antibody against human Naᵥ1.5 channel. A marked decrease in current density was observed in cells expressing the I890T channel (from -52.0 ± 6.5 pA/pF, n=15 to 35.9 ± 3.4 pA/pF, n = 22, at -20 mV, WT and I890T, respectively). Moreover, a positive shift of the activation curve was identified (V½ =-32.0 ± 0.3 mV, n = 18, and -27.3 ± 0.3 mV, n = 22, WT and I890T, respectively). No changes between WT and I890T currents were observed in steady-state inactivation, time course of inactivation, slow inactivation or recovery from inactivation parameters. Cell surface protein biotinylation analyses confirmed that Nav1.5 channel membrane expression levels were similar in WT and I890T cells. In summary, our data reveal that the I890T mutation, located within the pore of Nav1.5, causes an evident loss-of-function of the channel. Thus, the BrS phenotype observed in the proband is most likely due to this mutation

Tratamento de resíduos de corante por eletrofloculação: um experimento para cursos de graduação em química

This paper describes the use of a simple experiment of electroflocculation for classroom in Chemistry. Parameters such as electrode material, current density and temperature direct influence the process efficiency. Due to the process low cost and efficient color removal, the methodology proposed has shown good potential for use in wastewater treatment. In addition, the proposed experiment allows discussion about environmental electrochemistry, introduction to concepts of water contamination by industry and university, and also about different alternatives in wastewater treatment used nowadays. Finally, the very easy operation make possible to easy adapt this experiment for high school and elementary school.

Copper electrodeposition on glassy carbon and highly oriented pyrolytic graphite substrates from perchlorate solutions

In present work, we analyzed the copper electrodeposition onto GCE (System I) and HOPGE (System II) from perchlorate solutions. The current density transients obtained from system I and II were well described through a kinetic mechanism that involves four different contributions: (a) a Langmuir type adsorption process, b) an electron transfer from Cu2+→Cu+, (c) a 3D nucleation limited by a mass transfer reaction and (d) a proton reduction process. It was observed that the values of the nucleation rate, the number of active nucleation sites were increased with the overpotential and they are bigger onto GCE in comparison with HOPGE.

Fatores que influenciam a formação da fase β-PbO2 em filmes eletrossintetizados galvanostaticamente sobre substrato de tecido de carbono

PbO2 films were electroformed onto carbon cloth substrates (twill woven type) in acid conditions using the nitrate precursor by changing the electrodeposition current density, temperature and pH, in order to optimize the formation of the β-PbO2 phase. The crystal structure and morphology of the PbO2 films were investigated using X-ray diffraction (XRD) and scanning electronic microscopy (SEM) techniques. The optimum conditions obtained for formation of the β-PbO2 were presented and discussed.

Desenvolvimento e uso do compósito de Nb2O5|Cu como revestimento aplicado por aspersão térmica sobre o aço AISI 1020 para proteção contra a corrosão pelo solo em estruturas enterradas

An Nb2O|Cu corrosion-resistant coating was developed and applied onto AISI 1020 steel substrate by Powder Flame Spray. A galvanostatic electrochemical technique was employed, with and without ohmic drop, in four different soils (two corrosively aggressive and two less aggressive). Behavior of coatings in different soils was compared using a cathodic hydrogen reduction reaction (equilibrium potential, overvoltage and exchange current density) focusing on the effect of ohmic drop. Results allow recommendation of Nb2O5|Cu composite for use in buried structure protection.

Oxidação eletroquímica do herbicida tebutiuron utilizando eletrodo do tipo DSA

Tebuthiuron (TBH) is a herbicide widely used in different cultures and known for its toxic effects. Electrochemical methods are promising for removing pollutants such as pesticides. This study showed the degradation of TBH using a DSA® anode operated at current densities of 50 to 200 mA cm-2. Removal presented pseudo-first order kinetics while high-pressure liquid chromatography (UV detection) showed two peaks, ascribed to degradation intermediates. The maximum percentage of total organic carbon removed was 12.9%. Ion chromatography revealed that higher concentrations of nitrate and nitrite ions formed with increasing current density.

Kinetical study about the cobalt electrodeposition onto polycrystalline platinum

An electrochemical study of Co electrodeposition onto polycrystalline Pt from an aqueous solution containing 10-2 M CoCl2 + 1 M NH4CI (pH = 9.3) was conducted at overpotential conditions. The current density transients showed two maxima that corresponded to two nucleation and growth processes. The entire transient behavior was adequately predicted considering the contribution to the total current of four different processes: a Langmuir-type adsorption process, a diffusion-controlled two-dimensional instantaneous nucleation, and two three-dimensional nucleation and growth processes.

Avaliação da atividade antimicrobiana de soluções de flumequina submetidas aos processos eletroquímico e foto-eletroquímico

Flumequine degradation by electrochemical and photo-electrochemical processes was evaluated in this study. The antimicrobial activity of the solutions subjected to the electrochemical processes was monitored during the assays. The experiments were carried out using DSA® (dimensionally stable anode) electrode. The influence of current density was investigated for the 7.5 to 45 mA cm-2 range. The photo-electrochemical process was more efficient for degrading flumequine (85%) and reducing solution antimicrobial activity. For both processes, the residual antimicrobial activity decreased as flumequine degradation increased. The reaction intermediate m/z 244 (5-methyl-1-oxo-6,7-dihydro-1H,5H-pyrido[3,2,1-ij]quinoline-2-carboxylic acid) was identified.

AVALIAÇÃO DE PROPRIEDADES FÍSICAS E QUÍMICAS DE ELETRODEPÓSITOS DE Ni-W-P OBTIDOS EM CÉLULA DE HULL

Ni–W–P electrodeposits were synthesized in a Hull cell in order to simulate the obtainment under industrial conditions. Complete coverage of panels was accomplished by applying total currents of 1.0 and 2.0 A. Panels obtained with a current of 1.0 A appeared brighter. The best compositional uniformities, as determined by Energy Dispersive Spectrometer (EDS) occurred in the current density ranges of 0.6 to 3.0 A dm−2 and 1.6 to 6.0 A dm−2 obtained with 1.0 and 2.0 A, respectively. However, the best morphological characteristics, as determined by Scanning Electro Microscope (SEM), were observed in those obtained with a total current of 1.0 A. Analysis of corrosion resistance by Electrochemical Impedance Spectroscopy (EIS) and Potentiodynamic Linear Polarization (PLP) in NaCl have shown significant variations in the amount of corrosion potential, polarization resistance, and even total impedance. The alloys exhibited amorphous character (XRD) and crystallized above 400 °C to Ni and Ni3P phases, and possibly Ni–W, with a subsequent increase in hardness. The results suggest that under industrial conditions, current density variations due to the large and complex geometric shapes of substrates lead to formation of distinct alloys. Furthermore, these materials are potential substitutes for chromium deposits in many applications.

DESENVOLVIMENTO DE EXPERIMENTO DIDÁTICO DE ELETROGRAVIMETRIA DE BAIXO CUSTO UTILIZANDO PRINCÍPIOS DA QUÍMICA VERDE

In this paper, we describe the development of low-cost teaching experiments of electrogravimetry for undergraduate students using principles of green chemistry. Copper was electrochemically deposited on brass under an electrical current density of 50 mA cm−2 from acidic solutions containing nitrate anions. Color changes at the brass electrode and of the solution were observed, indicating that the reduction of copper ions had occurred. The deposition efficiency values were between 92.8% and 93.8%, and the electrochemical efficiency values were between 85.6% and 86.5%. There was no significant contribution from parallel reactions. These experimental conditions facilitated the didactic exploration of gravimetric and electrochemical concepts. Following the principles of green chemistry, the experiments produced no toxic substances, all the materials could be recycled, and the energy consumption was the lowest. For this reason, this experiment was considered to be very interesting for didactical purposes.

Magnetic sputtering of complex oxides

HTSC materials are relevant in modern microelectronics, because of their transformation from the normal state to the superconducting. That is why the idea of producing HTSC in industrial amounts is actual nowadays. To decrease cost of their production it is important to use magnetron sputtering systems which give the best results for essential parameters. Modeling is the simplest and the fastest way to determine optimum sputtering condition. This thesis concentrates on determination the phases of the whole sputtering process and to find out basic factors of each phase using the modeling. It was find out, that the main factors which influence on the mode of occurrence of the initial stages are the current density of the magnetron discharge and the pressure of sputtering gas. With the modeling also velocity dependences were obtained for YBCO and SmFeAsO. These were compared and difference between them was examined. To support represented model comparison was made with experimental results. This showed that the model gives good results, very similar to the experimental ones. The results of this work were published in annual conference of the finnish physical society.