Electroless deposited Ni–Re–P, Ni–W–P and Ni–Re–W–P alloys

Coatings of electroless Ni–W–P, Ni–Re–P and Ni–W–Re–P alloys were plated in alkaline citrate baths containing amino alcohols, but not free ammonia ions. The reference Ni–P alloy was used as an intermediate layer in the sandwich: Ni–Me–P/Ni–P/substrate. An extremely homogeneous thickness distribution of all alloy components was found by applying scanning Auger electron spectroscopy (SAES(. The inclusion of refractory metals at the expense of nickel and without substantial change in phosphorus content was established. A non-oxidized state of the codeposited Re and W in Ni–W–P, Ni–Re–P and Ni–W–Re–P alloys was determined by means of X-ray photoelectron spectroscopy examination, as well as by SAES profiles, revealing the absence of oxygen throughout the coatings. All alloy films are amorphous and paramagnetic.     

Preparation and characterization of Mg–Al layered double hydroxides intercalated with benzenesulfonate and benzenedisulfonate

Mg–Al layered double hydroxides (Mg–Al LDHs) intercalated with benzenesulfonate (BS^–) and benzenedisulfonate (BDS^2–) ions were prepared by coprecipitation and characterized by X-ray diffraction, FT-IR spectroscopy, and chemical analyses. The intercalated BS^– and BDS^2– maintained their intrinsic molecular structures within the Mg–Al LDH interlayers. At low intercalation levels, the benzene ring of BS^– in BS · Mg–Al LDH was inclined at 30° relative to the plane of the brucite-like layers of Mg–Al LDH. With increasing BS^– content, the benzene ring adopted an additional configuration perpendicular to the Mg–Al LDH layers. In BDS-intercalated Mg–Al LDH, the benzene ring of BDS^2– was tilted at 26° relative to the plane of the Mg–Al LDH layers. Intercalation levels of BDS^2– were smaller than those of BS^– despite the greater charge density of BDS^2–, which was likely attributable to a greater degree of electrostatic repulsion between intercalated anions.     

Solid Solutions of Rare-Earth Cuprates and Their Electrical Properties

Mixed cuprates based on La–Sm, La–Gd, Pr–Y, Pr–Nd, and Sm–Gd oxides are synthesized, and their physicochemical properties are investigated. The electrical properties of the studied cuprates are interpreted within the model of oxidation–reduction reactions.     

Platinum-based Alloys as oxygen–reduction Catalysts for Solid–Polymer–Electrolyte Direct Methanol Fuel Cells

Electrocatalytic activities of various carbon-supported platinum-based binary, namely, Pt–Co/C, Pt–Cr/C and Pt–Ni/C, and ternary, namely, Pt–Co–Cr/C and Pt–Co–Ni/C, alloy catalysts towards oxygen reduction in solid–polymer–electrolyte direct methanol fuel cells were investigated at 70°C and 90°C both at ambient and 2bar oxygen pressures. It was found that Pt–Co/C exhibits superior activity relative to Pt/C and other alloy catalysts.     

Solubility of Apatite in Aluminosilicate Melts of the Albite–Diopside, Anorthite–Diopside, and Orthoclase–Diopside Systems

The liquidus surface temperatures, eutectic temperatures and compositions, phase crystallization fields, and phase separation regions are determined for the albite–apatite, anorthite–apatite, orthoclase–apatite, diopside–apatite, albite–diopside–apatite, anorthite–diopside–apatite, and orthoclase–diopside–apatite systems. The influence of the composition of the silicate melt on the solubility of apatite is described in a mathematical form. A program of calculating the limiting solubility of apatite in the silicate melt is developed.     

W-promoted Co–Mo–K/γ–Al2O3 catalysts for water–gas shift reaction

The effects of incorporating tungsten into the traditional Co–Mo–K/γ–Al₂O₃ catalysts on the catalytic performances for water–gas shift reaction were investigated. Activity tests showed that W-promoted Co–Mo–K/γ–Al₂O₃ catalysts exhibited higher activity than W-free Co–Mo–K/γ–Al₂O₃ catalyst. Raman and H₂-TPR studies indicated that part of the octahedrally coordinated Mo–O species on Co–Mo–K catalysts transformed into tetrahedrally coordinated Mo–O species in the presence of W promoter.     

Preparation of Pt–Ru–Co trimetallic nanoparticles and their electrocatalytic properties

Ternary Pt–Ru–Co nanoparticles are prepared by microemulsions procession. These resulting materials showed a homogenous alloy structure, the mono-dispersion and an average diameter of 2.7 ± 0.6 nm with a narrow particle size distribution. The composition of Pt–Ru–Co nanoparticles can be controlled by adjusting the initial metal salt solution and preparation conditions. Pt–Ru–Co ternary metallic nanoparticles can enhance catalytic activity towards methanol oxidation compared to Pt–Ru bimetallic nanoparticles.     

Electrode Properties of Selenide and Telluride Glasses in Solutions of Copper Salts

The Cu²⁺electrode function is studied for glasses in the systems Ge–As–Te, Cu–Ge–Te, Cu–As–Se, Cu–As–Te, Tl–Ge–Te, and Tl–As–Te. The selectivity of this electrode function in the presence of Fe²⁺and Fe³⁺ions is estimated. It is found that the Cu²⁺and Fe³⁺electrode functions are exhibited by membranes based on glasses initially containing no copper and iron. A systematic evaluation of this phenomenon is performed for the first time by the example of chalcogenide systems. The results obtained are explained in terms of the corrosion mechanism of the potential generation.     

Electrochemical corrosion study of Sn–3Ag–3Cu solder alloy in NaCl solution

The corrosion behaviour of Sn–3Ag–3Cu (at%) alloy was investigated in 0.1 M NaCl solution by potentiodynamic polarization and impedance spectroscopy measurements and compared with that of the Sn–3Ag–0.5Cu (at%) solder employed in the packaging of some microelectronic components and devices. Scanning electron microscopy (SEM) and electron probe microanalysis (EPMA) were used to characterize the samples prior to and after the electrochemical tests. Results showed that in NaCl solution the corrosion resistance of the Sn–3Ag–3Cu alloy was better than that of the Sn–3Ag–0.5Cu solder. The presence of tin oxychlorides or oxyhydroxychlorides was detected at the surface of both alloys investigated after the electrochemical tests. The better corrosion behaviour of the Sn–3Ag–3Cu alloy compared to the Sn–3Ag–0.5Cu solder can be ascribed to a more adherent and compact corrosion products layer.     

Studies on the conditions of synthesis of picolinic acid by heterogeneous catalytic oxidation of 2-picoline

Heterogeneous oxidation of 2-picoline over binary P–Ti, Sb–Ti, P–Sb, and V–Ti oxide catalysts was studied over the temperature range of 200–300°C. The vanadium–titanium catalysts based on titanium dioxide (anatase) were found to be the most selective for picolinic acid. With binary catalysts containing 20–50% of vanadium pentoxide, the selectivity for picolinic acid was 19–22% at the 36–74% conversion of 2-picoline. A distinguishing feature of these catalysts is regular surface stacking of V₂O₅ and TiO₂ crystallites.     

Transition metal-based cathodes for hydrogen evolution in alkaline solution: Electrocatalysis on nickel-based ternary electrolytic codeposits

Nickel-molybdenum-iron, nickel-molybdenum-copper, nickel-molybdenum-zinc, nickel-molybdenum-cobalt, nickel-molybdenum-tungsten and nickel-molybdenum-chromium ternary codeposits, obtained through electrodeposition on mild steel strips have been characterized with the objective of qualitatively comparing and assessing their electrocatalytic activities as hydrogen electrodes in alkaline solution. It has been concluded that their electrocatalytic effects for the hydrogen evolution reaction (h.e.r.) rank in the following order: Ni–Mo–Fe>Ni–Mo–Cu>Ni–Mo–Zn>Ni–Mo–Co Ni–Mo–W>Ni–Mo–Cr>Ni-plated steel. Further investigations on these electrocatalysts have revealed that the cathodic overpotential contribution to the electrolysis voltage can be brought down by 0.3 V when compared with conventional steel cathodes. The best and most stable hydrogen evolving cathode of these, namely Ni–Mo–Fe, exhibited an overpotential of about 0.187 V for over 1500 h of continuous electrolysis in 6 M KOH at 300 mA cm^–2 and 353 K. The salient features of the codeposits, such as physical characteristics, chemical composition, current-potential behaviour and the varying effects of the catalytic activation method were analysed with a view to correlating the micro-structural characteristics of the coatings with the hydrogen adsorption process. The stability under open circuit conditions, the tolerance to electrochemical corrosion and the long term stability of Ni–Mo–Fe codeposit cathodes were very encouraging. An attempt to identify the pathway for the h.e.r. on these codeposit cathodes was made, in view of the electrochemical parameters obtained experimentally.     

Mo–V–M–O (M = Te, W, Fe, Ga) catalysts for selective ammoxidation of propane

We report the incorporation of Ga, Fe, and W, well-known activity and selectivity promoters in lower alkane activation, into Te-free Mo–V–O M1 phase in order to improve its stability under propane ammoxidation conditions. The Mo–V–M–O (M = W, Fe, Ga) M1 phases displayed improved stability as compared to the parent Mo–V–Te–O M1 phase due to higher Tammann temperatures of M oxides and activity for direct conversion of propane to propene and acrylonitrile.     

Effect of P fertilizer on alleviating chloride toxicity in wheat

A pot study with four levels each P (control, 6.5, 13.0, 19.5 mg kg^–1) and Cl^– in irrigation water (control, 30, 60, 90me l^–1) was carried out to test Cl^– and P interaction on wheat. It has been found that optimum P nutrition alleviates the toxic effect of excess Cl^–. Highest P rate resulted in a significant yield increase upto a Cl^– level of 60me l^–1. Cl^– depressed P content in the plant only at a Cl^– level of 90me l^–1, while P rates had no major impact on the Cl^– concentration in the plant. Lower Cl^– concentration at higher P rates are rather a dilution effect than an antagonistic one. With optimum P supply higher Cl^– contents in the plants were tolerated than with a low P supply.     

Comparison of metathesis activity of catalysts prepared by anchoring of MoO2(acac)2 on various supports

The properties and olefin metathesis activity of molybdena–alumina, molybdena–silica–alumina and molybdena–silica catalysts prepared by anchoring of MoO₂(acac)₂ complex were compared. The specific activity obtained for molybdena–silica–alumina system is higher than that of molybdena–alumina and molybdena–silica catalysts. This statement concerns also the catalysts treated with tetramethyltin     

Electrochemical properties of Pb–Sb, Pb–Ca–Sn and Pb–Co3O4 anodes in copper electrowinning

Three types of anode, Pb–Sb, Pb–Ca–Sn and Pb–Co₃O₄, for copper electrowinning were investigated. The corrosion resistance, as evaluated by cyclic voltammetric (CV) measurements was higher for Pb–Co₃O₄ than for Pb–Sb and Pb–Ca–Sn. During prolonged electrowinning under galvanostatic conditions, the anodic reaction on the Pb–Co₃O₄ anode was depolarized by 0.053 V as compared to Pb–Sb, and by 0.106 V with respect to Pb–Ca–Sn. The composition and structure of the anodic layer were determined by XPS, X-ray and SEM analyses. The surface layer on the three anodes examined was composed mainly of PbSO₄, -PbO₂ and -PbO₂. Different structure of the surface layer was observed: loose and highly spread coral-like structure in the case of Pb–Sb; fibrous structure in the case of Pb–Ca–Sn and dense, fine-grained structure in the case of Pb–Co₃O₄.     

High temperature water–gas shift reaction over hollow Ni–Fe–Al oxide nano-composite catalysts prepared by the solution-spray plasma technique

The effect of Fe content in Ni–Fe–Al oxide nano-composites prepared by the solution-spray plasma technique on their catalytic activity for the high temperature water–gas shift reaction was investigated. The composites showed a hollow sphere structure, with highly dispersed Fe–Ni particles supported on the outer surface of the spheres. When the water–gas shift reaction was performed over an Ni–Al oxide composite catalyst without Fe, undesired CO methanation took place predominantly compared to the water–gas shift reaction, and significant amounts of hydrogen were consumed. When appropriate amounts of Fe were added to the Ni–Al oxide composite catalyst during the plasma process, methanation was suppressed remarkably, without serious loss of activity for the water–gas shift reaction. The catalyst was characterized by STEM, XRD and H₂ chemisorption measurements.     

Synergetic effect of combined use of Cu–ZnO–Al2O3 and Pt–Al2O3 for the steam reforming of methanol

Commercial Cu–ZnO–Al₂O₃ catalysts are used widely for steam reforming of methanol. However, the reforming reactions should be modified to avoid fuel cell catalyst poisoning originated from carbon monoxide. The modification was implemented by mixing the Cu–ZnO–Al₂O₃ catalyst with Pt–Al₂O₃ catalyst. The Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalyst mixture created a synergetic effect because the methanol decomposition and the water–gas shift reactions occurred simultaneously over nearby Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalysts in the mixture. A methanol conversion of 96.4% was obtained and carbon monoxide was not detected from the reforming reaction when the Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalyst mixture was used.     

Response to fertilization and nutrient deficiency diagnostics in peach palm in Central Amazonia

Peach palm (Bactris gasipaes Kunth) is increasingly grown in the tropics for its heart-of-palm and fruit. Determining fertilization response and diagnosing nutrient status in peach palm may require methods that consider the particularities in nutrient acquisition and recycling of perennial crops. Responses to nutrient additions, and the diagnostic value of soil and foliar analyses were examined in three field experiments with three-year old peach palm stands on Oxisols in Central Amazonia. To diagnose P-deficiency levels in soils, samples from 0–5 cm and 5–20 cm depth were analyzed for available P by different methods (Mehlich-1, Mehlich-3 and Modified Olsen). The second and fifth leaves were analyzed to assess N, P and K deficiencies. Field experiments involved several combinations of N (from 0 to 225 kg ha^–1 yr^–1), K (from 0 to 225 kg ha^–1 yr^–1) and P (from 0 to 59 kg ha^–1 yr^–1). Palms on control plots (unfertilized) and those receiving 225 kg ha^–1 yr^–1 N and 2 Mg ha^–1 of lime yielded between 4 and 19% of the maximum growth which was obtained with N, P and K applications. In one of the experiments, yield of heart-of-palm was positively related to N additions at the lowest levels of P (8.6 kg ha^–1 yr^–1) and K (60 kg ha^–1 yr^–1) additions. In one experiment, critical leaf N level was 2.5% for the second leaf and 2.2% for the fifth leaf. Some growth responses to P additions at constant N and K levels were observed (e.g., 797 kg ha^–1 yr^–1 of heart-of-palm with 39.3 kg ha^–1 yr^–1 of applied P, and 632 kg ha^–1 yr^–1 of heart-of-palm with 10.9 kg ha^–1 yr^–1 of applied P in one experiment, and 2334 kg ha^–1 yr^–1 of heart-of-palm with 39.3 kg ha^–1 yr^–1 of P and 1257 kg ha^–1 yr^–1 of heart-of-palm with 19.7 kg ha^–1 yr^–1 of P in another trial). In the experiment for fruit production from peach palm, total plant height did not respond to P additions between 19.7 and 59 kg ha^–1 yr^–1 and K additions between 75 and 225 kg ha^–1 yr^–1. Leaf P levels were found to be above the proposed critical levels of 0.23% for the third leaf and 0.16% for the fifth leaf. Plants in this experiment, however, showed evident symptoms of Mg deficiency, which was associated with a steep gradient of increasing Mg concentration from the fifth leaf to the second leaf. Standard leaf diagnostic methods in most cases proved less useful to show plant N and P status and growth responses to N and P additions. Soil P determined by common extractions was in general too variable for prediction of growth.     

Ultrafine Ni–Co–W–B amorphous alloys and their activities in benzene hydrogenation to cyclohexane

Quaternary Ni–Co–W–B amorphous alloys were prepared by chemical reduction of the aqueous solution of nickel and cobalt salts and sodium tungstate with potassium borohydride. The catalytic activities of the as-prepared materials were measured through liquid phase hydrogenation of benzene under moderate pressure. In comparison with Ni–Co–B, the as-prepared Ni–Co–W–B amorphous alloys showed superior activity, attributable to the promoting effect of tungsten on the microstructure of the alloys as revealed by XPS, XRD and DSC measurements.     

Effect of heat treatment on electroless ternary nickel–cobalt–phosphorus alloy

Ternary Ni–Co–P and binary Ni–P alloy coatings were deposited on mild steel panels from an alkaline bath in the presence and absence of cobalt sulfate using an electroless process. The effects of heat treatment on surface topography and crystal orientation of Ni–Co(11.17%)–P(3.49%) alloy coatings were studied in contrast to that of Ni–P ones. It was found that the as plated Ni–Co–P alloy is a supersaturated solid solution of P and Co dissolved in a microcrystalline Ni matrix with 111 preferred direction. Heat treatment induces structural changes. The formation of Ni₃P phase precipitates and recrystallization of nickel occur when the sample is treated at > 400 °C for one hour. It is observed that the Ni diffraction lines of treated Ni–Co–P alloy at > 400 °C are shifted to lower angles as compared to those of treated Ni–P or as plated Ni–Co–P alloys. The surface topography of Ni–Co–P alloy also changes with heat treatment temperature. The surface topography and crystal orientation were characterized by means of scanning electron microscopy and X-ray diffraction, respectively. The hardness and corrosion resistance, in 5 wt % NaCl solution, of heat treated Ni–Co–P samples were studied.