Electrolytical production of Ni + Mo + Si composite coatings with enhanced content of Si

Ni + Mo + Si composite coatings were prepared by co-deposition of nickel with molybdenum and silicon powders from a nickel solution in which Mo and Si particles were suspended by stirring. The layers have been deposited on a carbon steel substrate (St3S) under galvanostatic conditions. The content of Si in deposited layers was about 2-5 wt.% depending on deposition current density and the value of electric charge. For comparison Ni + Mo composite coatings were obtained under analogous current conditions. Composite coatings of enhanced Si content (15 wt.%) were deposited from an electrolyte in which 40 g/dm³ of Si covered with electroless plated nickel was dispersed. Deposition current density was equal 0.1 A/cm² and the value of electric charge Q = 500 C/cm². The thickness of the coatings was about 100-300 μm depending on their kind, electric charge and the deposition current density. Surface and cross-section morphology were investigated by scanning electron microscope (SEM). All deposited coatings are characterized by great, developed surface area. No internal stresses causing their cracking were observed. Chemical composition of the layers was determined by X-ray fluorescence spectroscopy (XRF) method and quantitative X-ray analysis (QXRD). It was stated, that the content of molybdenum and silicon in Ni + Mo + Si coatings depends on deposition current density and the amount of the powder in bath. The results of structural investigation of the obtained layers by the X-ray diffraction (XRD) method show, that they consist in crystalline Mo or Mo and Si phases built into Ni matrix. Moreover, Ni + Mo + Si composite coatings were modified by thermal treatment. It has been found that the thermal treatment of Ni + Mo + Si composite coatings caused that the new phases (NiSi, Mo₂Ni₃Si and Ni₆Mo₆C_1.06) were obtained.     

Characterization of Ru/CeO2-Al2O3 catalysts and their Performance in CO2 Methanation

Ru/Al₂O₃ and Ru/CeO₂-Al₂O₃ samples were used as catalysts in CO₂ methanation. The catalysts were characterized by temperature-programmed reduction (TPR) and X-ray diffraction. The promoting effect of ceria on the cataytic activity of the catalysts under study in CO₂ methanation was observed.     

Comparison of two dosage regimens of the substrate for the [13C]methacetin breath test

The [¹³C]methacetin breath test ([¹³C]MBT) – a valuable non-invasive tool dedicated to the assessment of the liver metabolic capacity – still needs standardisation. The aim of this study was to check whether currently used dosage regimens of [¹³C]methacetin provide concordant [¹³C]MBT results in subjects with an atypical body constitution. Healthy volunteers: low body mass<55 kg (eight women), and high body mass>95 kg (eight large body frame men) were recruited. They underwent [¹³C]MBT on separate days, taking in random order [¹³C]methacetin: a fixed 75 mg dose (FX75), or a 1 mg kg^?1 body mass-adjusted dose (BMAD). Samples of expiratory air for ¹³CO₂ measurement were collected over 3 h. The maximum momentary ¹³C elimination in breath air occurred earlier and was higher following BMAD than with FX75 in the low body mass females (T _max 14.6±1.0 min vs. 22.1±2.4 min, p=0.019; D _max 41.9±2.9 % dose h^?1 vs. 36.6±3.6 % dose h^?1, p=0.071). In the high body mass men, T _max remained unchanged, whereas D _max was slightly higher with BMAD compared to FX75 (21.5±3.2 min vs. 23.0±3.0 min; 38.5±2.9 % dose h^?1 vs. 32.3±2.5 % dose h^?1). It is concluded that in subjects with a body constitution outside the general population average, the dosage of the substrate may affect some results of the [¹³C]MBT. The dosage-related differences appear, however, to be insignificant if the result of the [¹³C]MBT is reported as a cumulative ¹³C recovery in breath air.     

Integrated continuous flow polymerase chain reaction and micro-capillary electrophoresis system with bioaffinity preconcentration

An integrated and modular DNA analysis system is reported that consists of two modules: (i) A continuous flow polymerase chain reaction (CFPCR) module fabricated in a high T(g) (150°C) polycarbonate substrate in which selected gene fragments were amplified using biotin and fluorescently labeled primers accomplished by continuously shuttling small packets of PCR reagents and template through isothermal zones as opposed to heating and cooling large thermal masses typically performed in batch-type thermal reactors. (ii) μCE (micro-capillary electrophoresis) module fabricated in poly(methylmethacrylate) (PMMA), which utilized a bioaffinity selection and purification bed (2.9 μL) to preconcentrate and purify the PCR products generated from the CFPCR module prior to electrophoretic sorting. Biotin-labeled CFPCR products were hydrostatically pumped through the streptavidin-modified bed, where they were extracted onto the surface of micropillars. The affinity bed was also fabricated in PMMA and was populated with an array of microposts (50 μm width; 100 μm height) yielding a total surface area of ～117 mm(2). This solid-phase extraction (SPE) process demonstrated high selectivity for biotinylated amplicons and utilized the strong streptavidin/biotin interaction (K(d) = 10(-15) M) to generate high recoveries. The SPE selected CFPCR products were thermally denatured and single-stranded DNA released for injection into a 7-cm-long μCE channel for size-based separations and fluorescence detection. The utility of the system was demonstrated using Alu DNA typing for gender and ethnicity determinations as a model. Compared with the traditional cross-T injection procedure typically used for μCE, the affinity pre-concentration and injection procedure generated signal enhancements of 17- to 40-fold, critical for CFPCR thermal cyclers due to Taylor dispersion associated with their operation.     

New Core-Shell Type Polymeric Supports Based on the Amberlite XAD-4 Adsorbent: A Novel Synthesis Procedure

The chloromethyl groups have been introduced into commercial S/DVB copolymer matrixes via interpenetrating polymer networks (IPN) synthesis. The procedure involves impregnation of the Amberlite XAD‐4 adsorbent, with use of the vinylbenzyl chloride (VBC) and divinylbenzene (DVB) monomers mixture, and suspension polymerization process. The syntheses were evaluated by FT‐IR spectra and SEM analyses and furthermore by chlorine content determination as well as characterization of porous structure by nitrogen adsorption at liquid nitrogen temperature. Designed synthesis approach allowed determining organic and water phases composition. Furthermore, impact of an excess of the organic phase removal method has been investigated. Basing on the obtained results it could be stated that the chloromethyl groups, derived from VBC monomer, were successfully introduced into the XAD‐4 structure. Captured SEM images revealed significant changes in the beads' surface morphology after polymerization processes. The presented studies reveal designed and executed synthesis processes, which involve the use of a proper water phase and excess of organic phase removal. Observed changes in the beads' morphology suggest that introduced functionalities are concentrated on the porous surface of the XAD‐4 adsorbent.     

High-spin radical cations of alternating poly(m-p-anilines)

Three alternating poly(m-p-anilines) have been synthesized via palladium-catalyzed amination reactions. Polymers were oxidized to radical cations by the use of chemical and electrochemical methods. The presence of radical cations was manifested by the appearance of two new bands in UV-vis spectra and a strong EPR signal. Moreover, EPR spectra at low temperatures confirmed the formation of a high-spin state. The magnetization measurements of polymers oxidized to radical cations revealed the paramagnetic-type behavior with weak antiferromagnetic interactions. Radical cations underwent the degradation processes in the presence of air, which led to the decrease of spin concentration.     

Determination of cadmium and copper in galvanic coatings by means of atomic absorption

A demand arose to establish an analytical method to determine copper and cadmium in galvanic baths and coatings, induced with the possibility of application of an ethylenediamino bath for electrolytical preparation of Cu---Cd coatings. An atomic absorption method was adjusted to determine copper and cadmium in a bath in the presence of ethylenediamine and in Cu---Cd coatings. Using the new method, it was established that cadmium levels in coatings cannot be lower than 0.5%.     

Computational (MP2 and DFT) modeling of the substrate/inhibitor interaction with the LDH active pocket in the gas phase and aqueous solution: bimolecular charged (pyruvate/oxamate–guanidinium cation) and neutral adducts (pyruvic/oxamic acids–guanidine)

Two types of bimolecular adducts were studied for the substrate and inhibitor of lactate dehydrogenase (LDH), one type of adducts between ionic species, α‐keto‐carboxylates (pyruvate and oxamate) and the guanidinium cation, and the other type of adducts between neutral species, α‐ketocarboxylic (pyruvic and oxamic) acids and guanidine. Calculations were performed in the gas phase and aqueous solution using the MP2 and PCM methods and the 6‐31++G** basis set. Application of the DFT(B3LYP) and PCM methods led to similar results. A change of the adducts' preference was observed when proceeding from the gas phase to aqueous solution. This change is in good agreement with the acidity–basicity scales in both phases. Formation constant (K_HB) for adduct between neutral species is greater for pyruvic than for oxamic acid in the gas phase, whereas a reverse situation takes place in aqueous solution, where the K_HB value for adduct between ionic species is smaller for pyruvate than for oxamate. The water molecules favor interactions of more polar oxamate with the guanidinium cation. Stronger interaction with this cation, a model of the arginine fragment of the LDH pocket, suggests that oxamate (inhibitor of LDH) has stronger binding properties in aqueous solution than pyruvate (substrate of LDH). Copyright © 2008 John Wiley & Sons, Ltd.     

The electrodeposition and properties of Zn-Ni + Ni composite coatings

The Zn-Ni+Ni coatings were deposited under galvanostatic conditions at the current density range from 20 to 60 mA cm^?2. The influence of deposition current density on surface morphology, chemical and phase composition and corrosion resistance of obtained coatings, was investigated. Structural investigations were conducted by X-ray diffraction method. Surface morphology and surface chemical composition of the obtained coatings were determined by a scanning electron microscope. Studies of electrochemical corrosion resistance were carried out in the 5% NaCl solution, using potentiodynamic and Scanning Kelvin Probe (SKP) methods. A possibility of incorporation of nickel powder from a suspension bath to the Zn-Ni matrix, during galvanostatic deposition was demonstrated. The results of chemical composition analysis show that the Zn-Ni + Ni coatings contain approximately 15?C18% at Ni. It was found that surface morphology, surface chemical and phase composition of Zn-Ni + Ni coatings depend in small degree on deposition current density. However, the current density influences distribution of nickel powder on the surface of these coatings. The optimal values of current density on account of corrosion resistance, are found to be j = 40?C50 mA cm^?2.