A new polymer electrolyte poly(acrylonitrile)-dimethylsulphoxide-salt for electrochemical capacitors

The PAN-DMSO-Et₄NBF₄ and PAN-DMSO-Et₄NTf (Tf is triflate ion) electrolytes were prepared as white, turbid foils with a thickness in the range of 0.1-0.5 mm, using the casting technique. Room temperature conductance of the electrolytes, detected from ac impedance experiments, was at the level of 8 and 14 mS cm⁻¹ for Et₄NBF₄ and Et₄NTf salts, respectively. The electrochemical stability window of approximately 2.6-2.8 V was estimated using a glassy carbon electrode. Temperature dependence of the conductivity is of the Arrhenius-type for both electrolytes, with an activation energy of approximately 34 kJ mol⁻¹. The double-layer capacitors built with these electrolytes, serving both as separators and activated carbon powder (ACP) binders, showed a specific capacity of 50 F g⁻¹ of carbon material. Capacitors were assembled by sandwiching the PAN-DMSO-salt electrolyte between two PAN-salt-DMSO-ACP-AB electrodes and pressing across the system; the resulting devices had a coin-like shape with 8 mm diameter and thickness between 2.0 and 2.5 mm.     

Effect of Stoichiometry on Properties of Rare-Earth-Based Hydrogen Storage Alloy for Nickel-Metal Hydride Secondary Battery

Effect of stoichiometry on microstructures, electrochemical properties and PCT characteristics of the alloys MI(Ni0.71Co0.15-Al0.06Mn0.08)x (MI=Lanthanum-rich Michmetal, x=4.6~5.2) have been investigated. The lattice constants a, c, and cellvolumes of non-stoichiometric alloys are bigger than those of the stoichiometric alloy. With the increasing stoichiometry x,the value of a decreases, and the value of c and cell volume increases except for those of the stoichiometric alloy; the plateaupressure of PCT curve, discharge capacity and cycling stability all increase. The alloy with x=5.2 shows the highest dischargecapacity and the best cycling stability among the studied alloys.     

Analysis of spontaneous electrochemical oscillations by energy distribution technique

Analysis of non-stationary electrochemical oscillations emerges utilization of the techniques allowing an observation of time evolution of their parameters such as instantaneous frequency, amplitude or frequency band. An algorithm of extraction of these parameters can be based on one of linear or quadratic time-frequency representations of oscillations record. In this paper, the authors present representatives of such transformations (Choi-Williams and Cone-shaped) originating from one of the most popular joint time-frequency energy distribution—Wigner-Ville distribution. Short introduction to the mathematics of the topic discussed is provided, then the authors present an example of application in the analysis of current oscillations of copper dissolution process.     

EIS evaluation of the filiform corrosion of aluminium coated by a cataphoretic paint

Filiform corrosion is mainly considered as a cosmetic attack and is undesirable in most applications. The initiation and propagation of the filaments are related to different parameters such as the presence of defects, the permeability of the coating to water and oxygen, the adherence of the paint system and the presence of salts.

The aim of this work is to study the behaviour of painted aluminium samples towards filiform corrosion or delamination. The 6082 Aluminium alloy was selected and the samples were covered with a cataphoretic epoxy primer without lead (PPG Industries France). Prior to the application of the electrocoat, the samples were pre-treated by a commercial Zr/Ti or chromate conversion treatment or simply etched with a commercial acid etching product.

Filiform corrosion was studied by the normalized test (ISO/DIS 4623): painted and scratched samples were inoculated in HCl and exposed in a constant humidity chamber at 40 °C and 82% RH for 3 weeks. After exposure the samples were subjected to a visual and optical microscopic examination.

Electrochemical impedance spectroscopy was used to study the sensitivity to filiform corrosion. The operating mode of this test is similar to the normalized one. The samples were scratched before inoculation for 1 h in HCl and then exposed to the humidity chamber for a maximum of 4 days. The samples were tested by EIS in an acidified 0.1 M Na₂SO₄ electrolyte solution. The resulting impedance spectra were analyzed with an appropriate equivalent electrical circuit which allows the evaluation of the exposed metallic surface area, directly related to the extent of filiform corrosion or delamination. Different parameters were varied: the exposure time in the humidity chamber; the immersion time in the electrolyte sulphate solution as well as its pH and the coating thickness.     

Carbon nanofibers as hydrogen adsorbing materials for power sources

Porous carbon nanofibers are synthesized by CVD method from acetylene with use of iron-containing catalysts. Activation of the nanofibers in melted potassium hydroxide results in increasing surface area from initial 300–400 m² g⁻¹ to 1700 m² g⁻¹. As follows from XRD data, activated nanofibers do not contain regular packages of graphene layers, but retain high electric conductivity. Deposition of copper improves electrochemical hydrogen storing characteristics of carbon nanofibers. Carbon nanomaterials obtained can be used as hydrogen storing materials in batteries instead of hydride forming metals.     

LASER ENHANCED ELECTROCHEMICAL MACHINING PROCESS

An experimental apparatus was designed and built for the hybrid process of laser enhanced electrochemical machining (ECM). Comparison experiments had been done between solely ECM and laser enhanced ECM. The machining performance of hybrid process was investigated and compared with solely ECM. The principle of the hybrid process was exposed by analyzing the microstructure of machining surface. The results show that the hybrid process has advantages in machining accuracy, surface quality, and machining efficiency.     

Determination of instantaneous corrosion rates and runoff rates of copper from naturally patinated copper during continuous rain events

Instantaneous corrosion rates of naturally patinated copper of varying age (16 months, 138 and 145 years) have been determined during continuous rain events in the laboratory with electrochemical impedance spectroscopy using a two-electrode cell. The two-electrode cell was found to yield the same information in bulk rainwater as a conventional three-electrode cell.Relatively constant corrosion rates, between 0.2 and 0.6 μm/y, were determined for samples having a two-layer structure with an inner brownish layer of cuprous oxide and an outer greenish layer of basic copper salts (138, 145 years). Samples with cuprous oxide as the dominating phase of the patina (16 months) showed higher and somewhat increasing corrosion rates during a rain event (from 0.6 to 1.2 μm/y). During a continuous rain event, corrosion rates were found to be approximately 10 (brownish patina) and 25 times (greenish patina) lower than corresponding instantaneous runoff rates. The first flush phenomena of the runoff process, with an increased concentration during first flush and a relatively constant concentration during steady state, was indirectly seen as an increase in solution conductivity during the first rain volume followed by relative constant value. The contribution of the concentration in the first flush to the total annual runoff rate was significant for panels having a greenish layer (138, 145 years) whereas it was negligible for panels having a brownish layer (16 months).     

Accumulation of amplified target DNAs using thiol/biotin labeling, S1 nuclease, and ferrocene-streptavidin-magnetic system and a direct detection of specific DNA signals with screen printed gold electrode

Combinations of PCR-based amplification platform using 5′ thiolated and biotinylated specific primers, S1 nuclease-PCR products treatment, ferrocene-streptavidin (Fc-Stv)-magnetic binding for DNA accumulation, and screen printed gold electrode for the DNA allocation, were applied to Hoechst 33258-induced DNA aggregation and signals induction system for direct signals detection and DNA quantification in food samples. Thiolated and biotinylated at each 5′ terminus enabled DNA purification through S1 nuclease treatment for primers and non-specific DNA elimination and enabled DNA trapping with a ferrocene-streptavidin-magnetic system. This facilitated the accumulation of target DNAs at higher concentration, resulting in enhanced signals. After allocation of DNA on the surface of gold electrode via thiol binding, intensity of DNA signals through these treatments could be measured directly after being induced by Hoechst 33258. Wider amplitude changes in anodic current peaks between negative and positive samples (increasing from 3.70 to 10.10 μA) compared with those applied with no treatment combinations (decreasing from 3.92 to 1.23 μA) were observed. This enhancement of the signals allowed a greater efficiency of DNA quantification. When this combination was used for GMOs content estimation in reference samples, results revealed an improved accuracy from 66% to 96%. The combined biosensor system, although more costly than the standard Hoechst 33258/carbon electrode system, provided an alternative choice for DNA quantification, offering labor-free immobilization of probe onto electrode surface, easy test administration, and efficient semi-quantitative test without expensive instruments.     

Kinetics of DyNi2 film growth by electrochemical implantation

Electrochemical implantation was performed at Ni electrodes to form DyNi₂ films at 0.55 V (vs. Li⁺/Li), 0.62 V, and 0.70 V for 0.5-5.0 h in a molten LiCl-KCl-DyCl₃ (0.50 mol%) system at 700 K. It was found that the DyNi₂ films grew linearly with time with coulomb efficiency of about 100%. The obtained growth rates were higher at more negative potentials, i.e., 0.47 μm min⁻¹ at 0.55 V, 0.32 μm min⁻¹ at 0.62 V, and 0.14 μm min⁻¹ at 0.70 V. On the analogy of the metal oxide growth, the observed rapid and linear growth of DyNi₂ films may be explained by the existence of the outer and inner DyNi₂ layers.     

Effect of Organic Additives on Electrochemical Surface Precipitation and Polymorphism of CaCO3

The inhibition effect of three organic additives on the precipitation and polymorphism of CaCO₃ deposited on gold surfaces was investigated using electrochemical and microscopic techniques. Additives, two polyacrylic acid (PAA) polymers with different molecular weights (Mw 2100, Mw 30,000), and 1,2,4,5‐benzenetetracarboxylic acid (BTCA), were either added to the solution before or during deposition. In the presence of 100 ppm of one of the three additives in solution, almost no scale was observed on the surface for at least 24 hours. In the presence of lower concentrations of PAA Mw 2100, only distorted calcite crystals were obtained while with PAA Mw 30,000 the polymorph was spherical vaterite. A mixture of calcite and vaterite was observed with the BTCA additive. Addition of the polymers inhibits further nucleation and growth even if added after partial deposition of CaCO₃ while BTCA has no effect once nucleation has started. The results indicate that the inhibit ion effect of the PAA polymers is due to adsorption on the electrode surface while the effect of BTCA is related to chelation of calcium ions in solution.