Structural and electrochemical characterization of mechanochemically synthesized calcium zincate as rechargeable anodic materials

Hydrated calcium zincate was synthesized by mechanical ball milling of ZnO and Ca(OH)₂ in water at room temperature. The structural and electrochemical properties of this material used as rechargeable anodic material were examined by microelectrode voltammetry, charge–discharge measurements and structural analysis. The results showed that during mechanical milling, ZnO, Ca(OH)₂ and H₂O reacted rapidly to form Ca[Zn(OH)₃]₂ · 2H₂O which was subsequently transformed to a stable structure CaZn₂(OH)₆ · 2H₂O. Since this composite oxide has lower solubility in KOH solution (<35 wt %) and better electrochemical reversibility than ZnO-based negative materials, the zinc anodes using this material can overcome the problems of shape changes and dendritc formation, and therefore exhibit improved cycling life.     

Effects of a small addition of Mn on the corrosion behaviour of Zn in a mixed solution

The effects of a small addition of Mn (0.4 wt%) on the corrosion behaviour of pure Zn (99.995 wt%) in a mixed solution (0.1 M NaCl + 0.1 M Na₂SO₄ + 0.01 M NaHCO₃, pH 8.4) were investigated by electrochemical impedance spectroscopy (EIS), potentiodynamic polarization and X-ray photoelectron spectroscopy (XPS). The electrochemical impedances of both Zn and Zn–0.4Mn have been successfully fitted with a suitable EIS equivalent circuit model. Fitted impedance results revealed that 0.4 wt% Mn improved both the pore resistance and charge transfer resistance of Zn in the mixed solution. As a result, both anodic and cathodic reaction rates were reduced. X-ray photoelectron spectroscopy (XPS) analysis showed that the corrosion films formed in the mixed solution consisted of zinc oxide (ZnO), zinc hydroxide (Zn(OH)₂) and zinc hydrozincite (Zn₅(CO₃)₂(OH)₆). The role of small addition of Mn is that it promotes the precipitation of hydrozincite in the pores of corrosion film. An “alleviation of local acidification” mechanism is proposed to explain the investigated results.     

Passivity and Corrosion of Cu–<Emphasis Type="BoldItalic">x</Emphasis>Zn (<Emphasis Type="BoldItalic">x</Emphasis> = 10–40 wt%) Alloys in Borate Buffer Containing Chloride Ions

The electrochemical behaviour of Cu–xZn alloys and of Cu and Zn metals was studied by cyclic voltammetry and chronopotentiometry in borate buffer, pH = 9.2, with and without the addition of chloride ions in the range from 0.01 m to 1 m. In general, the shape of voltammograms of four Cu–xZn alloys with 10 – 40 wt.% of zinc resembles that of copper more than that of zinc. With increasing zinc content several characteristics of zinc are observed. In borate buffer containing chloride anions, Cu–xZn alloys are susceptible to pitting corrosion. The breakdown potential, E_b, at which the current density in the passive region starts to increase abruptly, becomes more negative with increasing zinc content in the alloy. The general relationship E_b = a + b log c_NaCl held in all cases, with constants a and b, however, being dependent on the zinc content of the alloy and on the chloride concentration. The corrosion resistance of Cu–xZn alloys was less than that of copper metal but significantly greater than that of zinc.     

Zinc equilibria in submerged sodic soils as influenced by application of amendments

In a pot culture experiment, the effect of gypsum (50% of soil requirement), pyrites (equivalent to gypsum), farmyard manure (0.5 g per 100g soil) and Zn (10mg Zn kg^–1 soil) on Zn equilibria in Ghabdan and Langrian series of sodic soils was studied. The equilibrium soil solutions collected anaerobically after 1, 14, 28, 42, 56, 70 and 84 days of submergence were analysed for pH, EC, HCO₃ and Zn. Submergence markedly decreased soil solution pH and Zn up to 14 days and thereafter, the former slightly increased and the latter continued to decrease. Addition of amendments decreased soil solution pH in the order gypsum, pyrites and farmyard manure (FYM) and increased Zn concentration in the order FYM, gypsum and pyrites. The values of Zn potential (pZn + 2pOH) were within the range of pKsp for Zn(OH)₂-Zn²⁺ (aq) from 16 to 84 days of submergence in Ghabdan soil and from 9 to 42 days of submergence in Langrian soil, where later it shifted to ZnCO₃-Zn²⁺ (aq) system. Addition of FYM, pyrites and gypsum shortened the period of predominant existence of Zn(OH)₂-Zn²⁺ (aq) system to 40, 30 and 12 days in Ghabdan soil and 30, 20 and 6 days in Langrian soil respectively. After these periods the system was saturated with respect to ZnCO₃-Zn²⁺ (aq) except gypsum treatment where Zn-soil (unknown solid phases) -Zn²⁺ (aq) system controlled the solubility of Zn after 38 and 28 days of submergence of Ghabdan and Langrian soil respectively.     

Development of long-lived high-performance zinc-calcium/nickel oxide cells

The addition of Ca(OH)₂ to the zinc electrode of Zn/KOH/NiOOH cells was investigated in order to determine its effect on the rate of zinc active material redistribution (shape change) and cell cycle-life performance. Cells of equal mass and capacity, and therefore the same specific energy, containing 0, 10, 25, and 40 mol% Ca(OH)₂ in their zinc electrodes were constructed and tested. The Ca(OH)₂ and Zn(OH) ₄ ^2– -supersaturated KOH solution formed a calcium-zincate complex during the discharge half-cycle. The solubility of this complex is less than that of ZnO, and the lower zinc species solubility leads to a slower rate of Zn redistribution, thereby extending the cell cycle life. The best cells tested were those with 25%-Ca(OH)₂ electrodes, which lost capacity at a rate of 0.13%/cycle, compared to 0.47%/cycle in calcium-free control cells constructed in the same manner. Also, zinc active material utilization in the calcium-containing electrodes showed a dramatic improvement, compared to the calcium-free zinc electrodes.     

High speed zinc electrowinning system using a hydrogen anode and a rotating aluminium disc cathode

The performance of a novel high speed zinc electrowinning system using a hydrogen anode and an aluminium rotating disc cathode (1 m diam.) was investigated under various experimental conditions. This new type of zinc electrowinning system was continuously operated at a current density of 70 A dm^–2, which is twelve times higher than that usually employed. Current efficiency is 90% at 50 A dm^–2 in an electrolyte containing 60 g dm^–3 Zn + 160 g dm^–3 H₂SO₄, the zinc purity being at least 99.999%. The energy usage of the system is 1650 kWh per tonne of zinc, 380 m³ of H₂ gas being required.     

Diffusional kinetics of metalliding zinc into solid copper

The process of incorporation of zinc into a copper cathode has been experimentally studied in a molten salt system at 381±2° C and at various current densities. The process is shown to be kinetically controlled by the diffusion of Zn into the solid matrix. A galvanostatic pulse titration technique has been used to determine the chemical diffusion coefficient at various alloy compositions, and an exponential relationship has been found between the diffusivity and the third power of the zinc concentration in the alloy. This relationship was then used in the diffusion equation within the solid matrix and a numerical integration was performed. Very good agreement was found between the calculated and experimental data for Zn interfacial concentration versus time. The same calculation procedure was used to determine zinc concentration profiles in the alloys.Nomenclature c _A concentration of the diffusing metal (mol cm^–3) - D _AB chemical diffusion coefficient of A into B (cm² s^–1) - E cell e.m.f. (mV) - F Faraday number - i current density (A cm^–2) - t time (s) - V _M alloy molar volume (cm³ mol^–1) - x linear dimension in the diffusion direction (cm) - X zinc mass fraction in the alloy - z ionic valence of Zn - stoichiometric ratio Zn/Cu     

Electrodeposition and characterization of thin layers of Zn–Co alloys obtained from glycinate baths

An alkaline bath containing CoSO₄ · 7H₂O, ZnSO₄ · 7H₂O, Na₂SO₄ and NH₂CH₂COOH is proposed for the deposition of thin layers of Zn–Co alloys onto steel substrates. Electrodeposition was carried out at 0.216–1.080 A dm^–2, pH 10 and 10–55 °C. The influence of bath composition, current density and temperature on galvanostatic cathodic polarization, cathodic current efficiency and alloy composition was studied. Different proportions of the two metals were obtained by using different deposition parameters, but at all Zn(II)/Co(II) ratios studied, preferential deposition of zinc occurred and anomalous codeposition took place. Increasing the bath temperature enhanced the cobalt content in the deposit. X-ray diffraction measurements indicated that the phase structure of the deposits was controlled by the applied current density. The Co₅Zn₂₁ phase was formed at low current density, while the CoZn₁₃ phase was formed at high current density. The potentiodynamic dissolution of the coatings showed that they contained Zn–Co alloy of different content and structure.     

Evaluation of electroactive intermediate states in anodic O2 evolution at chemically formed nickel oxide: Comparison with behaviour at nickel metal anodes

The behaviour of the kinetically involved intermediate states arising in the electrocatalysis of anodic oxygen evolution at chemically formed, high-area nickel oxide (NiO·OH) films on nickel metal as substrate is examined by means of analysis of potential (V) decay transients, following interruption of anodic polarization currents at various overpotentials. The potential decay behaviour is treated in terms of the dependence ofV(t) on log (time,t), and of ln (–dV/dt) as f[V(t)]. The pseudocapacitance associated with the potential-dependence of the coverage or surface density of the overpotential-deposited species involved as intermediates in the reaction at the oxide electrode surface is evaluated jointly from the potential decay and Tafel polarization behaviour, following procedures developed recently.In anodic O₂ evolution on oxide surfaces, such as NiO·OH, the intermediate states in the kinetics of the reaction are to be identified as OH or O species coupled with potential-dependent Ni(III) and Ni(IV) oxidation states of nickel, and the surface density of these states can be evaluated experimentally.The results obtained for anodic O₂ evolution on the chemically formed nickel oxide films are compared with the behaviour at anodically formed thin oxide films on nickel metal.     

Detection of Magnesium Oxide in the Ashes of a Burnt Cellulosic Fabric Treated by Magnesium Chloride Hexahydrate as a Flame-Retardant

The authors investigated the effect of magnesium chloride hexahydrate [Mg Cl₂ · 6H₂O] as a nondurable finish on the flammability of 100% cotton fabric (woven construction, weighing 144 g/m². The laundered bone-dried, weighed fabrics were impregnated with various concentrations of the aqueous aforementioned salt solutions by means of squeeze rolls and drying in an oven at 110°C for 30 min. The specimens were then cooled in a desiccator, re-weighed with an analytical balance, and kept under standard conditions before the fulfillment of the vertical flame test. The optimum add-on values to impart flame-retardancy expressed in g anhydrous magnesium chloride hexahydrate per 100 g fabric were about 6.73% to 8.30%. The ashes of the treated specimens were subjected to X-ray diffraction analysis (XRD), and the result was compared with data for MgO powder. The existence of MgO was detected in the ashes. The results obtained for magnesium chloride hexahydrate are in favor of the “Gas Theory,” “Free Radical Theory,” and also “Dust or Wall Effect Theory.”     

High speed zinc electrowinning using a hydrogen gas-diffusion electrode

The feasibility of a high speed zinc electrowinning cell using a Pt catalyzed hydrogen gas-diffusion electrode as an anode is investigated. This new type of zinc-winning cell is operated at a current density of 1.0 A cm^–2, which is 20 times higher than usually employed in conventional methods. Current efficiency is 86% at 0.5 A cm^–2 in an electrolyte containing 60 gl^–1 Zn+270 gl^–1 H₂SO₄, the zinc purity being at least 99.999%. The energy usage of the system is 1400 kWh and 380 m³ H₂ gas per ton of zinc.     

Response of chickpea (Cicer arietinum) to zinc fertilization and its critical level in soils of semi-arid tropics

In a greenhouse experiment the response of chickpea (Cicer arietinum) to zinc fertilization was examined using 27 soils from the semi-arid tropics. The critical level of DTPA extractable soil Zn was evaluated. Zinc additions to the soil increased the dry matter yield of six weeks old plant shoot, grain and straw significantly at the 5 mg kg^–1 level, but tended to decrease it at the 10 mg kg^–1 level.The DTPA extractable Zn of the soils ranged from 0.28 to 1.75 ppm and was negatively correlated at 1 per cent level with pH (r = – 0.81) and positively with organic carbon (r = 0.79) and Olsen's P (r = 0.63). The per cent yield increase or decrease over zero zinc ranged from 67 to – 16 in respect of grain yield and was positively correlated with available Zn (r = 0.86^**). Zinc concentration in plants was greatly increased with the application of Zn and accumulation of Zn was higher in grain than straw. The critical level of available zinc in soil below which plant response to Zn fertilization may be expected was 0.48 mg Zn kg^–1 soil. Soils between 0.48 to 0.70 mg kg^–1 of DTPA extractable Zn appear boarderline and a negative response to applied Zn was observed in soils of high Zn category. The results show the suitability of DTPA soil test for demarcating soils on the basis of plant response to zinc fertilization.     

Preparation and properties of raney nickel electrodes on Ni-Zn base for H2 and O2 evolution from alkaline solutions Part I: electrodeposition of Ni-Zn alloys from chloride solutions

Experimental results for the electrodeposition of Ni-Zn alloys from chloride solutions, with addition of H₃BO₃ and without other additives, in a laboratory cell with a perforated nickel sheet cathode and with recirculating electrolyte are presented. The dependence of the zinc content in the alloy on the following operating conditions was investigated: cathodic current density, 1.0–20.0 A dm^–2; temperature, 35–65°C; pH 1.5–5.5; total molarity,M _tot=M _Ni ²⁺ +M _Zn ²⁺ =1.1–2.8 M; and, molar ratio,P=M _Ni ²⁺ /M _Zn ²⁺ =1.0–15. Depending on the operating conditions the Zn content in the alloy varied over the range 22–88 mol%. In separate experiments galvanostatic polarization curves were measured in the direction of increasing and then decreasing cathodic current density in the range 0.1–20.0 A dm^–2 with all other operating conditions as used for electroplating experiments. In all cases significant hysteresis effects were observed. It was found that the current efficiency for the electrodeposition of Ni-Zn alloys from chloride solutions as a function of the zinc content in the alloy showed a sharp minimum of about 55% atX _Zn=55 mol % irrespective of other operating conditions.     

A highly efficient Cu/ZnO/Al2O3 catalyst via gel-coprecipitation of oxalate precursors for low-temperature steam reforming of methanol

The impact of preparation methods on the structure and catalytic behavior of Cu/ZnO/Al₂O₃ catalysts for H₂ production from steam reforming of methanol (SRM) has been reported. The results show that the nanostructured Cu/ZnO/Al₂O₃ catalyst obtained by a novel gel-coprecipitation of oxalate precursors has a high specific surface area and high component dispersion, exhibiting much higher activity in the SRM reaction as compared to the catalysts prepared by conventional coprecipitation techniques. It is suggested that the superior catalytic performance of the oxalate gel-coprecipitation-derived Cu/ZnO/Al₂O₃ catalyst could be attributed to the generation of “catalytically active” copper material with a much higher metallic copper specific surface as well as a stronger Cu–Zn interaction due to an easier incorporation of zinc species into CuC₂O₄ · x H₂O precursors as a consequence of isomorphous substitution between copper and zinc in the oxalate gel-precursors.     

XRD Analysis of Burnt Cotton Fabric Impregnated by Ammonium Iron (II) Sulfate Hexahydrate as a Flame-Retardant

Ammonium iron (II) sulfate hexahydrate [(NH₄)₂Fe(SO₄)₂ · 6H₂O] as a nondurable finish was deposited onto cotton fabric, and its uniformity was ensured by means of squeeze rolls. By using a vertical flame test the optimum add-on values to impart flame-retardancy to the fabric was determined to be about 23.62–25.82%. The XRD analysis of ashes of impregnated samples showed the existence of iron (III) oxide. Hence it can plausibly be deduced that a reduction-oxidation reaction occurred during the combustion of the treated specimens and other elements presented in the aforementioned salt and converted to gaseous products, that is, SO₂, H₂O, CO₂, and NH₃, were eliminated during the combustion process. Hence “Gas theory” could play a significant role in justifying its flame-retardancy action. On the other hand, the presence of Fe₂O₃ dust in the consumed ashes proves the Dust or Wall effect suggested by Jolles and Jolles.     

Response of pearl-millet to zinc fertilization in relation to DTPA extractable zinc

The response of pearl-millet (Pennisetum americanum) grown on forty eight diverse soils to applied zinc fertilization was examined in a screenhouse experiment. The DTPA-extractable soil zinc ranged from 0.34 to 1.42 mg kg^–1. In many of the soils yield was increased by the addition of zinc and there were large differences in the size of the response. The critical level of zinc in soil and plant — below which response to applied zinc may be expected — was determined by a graphical method. The values found were 0.65 and 18 mg kg^–1, respectively. Bray's percent yield was positively and significantly related with both soil Zn (r = 0.88) and plant Zn (r = 0.72).     

Electrochemical characteristics and structural changes of molybdenum trioxide hydrates as cathode materials for lithium batteries

Several characteristics of MoO₃·2H₂O and MoO₃·H₂O, such as thermal behaviour and conductivity and the electrochemical behaviour and structural changes associated with discharge and charge have been investigated. The suitability of these substances as new cathode materials for non-aqueous lithium batteries has been assessed. MoO₃·H₂O, having only one coordinated water molecule, showed a discharge capacity of about 400 Ah kg^–1 of acid weight and a discharge potential around 2.5 V vs Li/Li⁺. This capacity was much higher than the 280 Ah kg^–1 of anhydrous MoO₃.MoO₃·H₂O showed good charge-discharge cyclic behaviour at a capacity below l e^–/Mo while keeping the original layered lattice on cycling. In addition, the crystal system of MoO₃·H₂O was found to be changed from a monoclinic system to orthorhombic with lattice parameters ofa=0.5285 nm,b=1.0824 nm,c=0.5237 nm on discharge to 0.5 e^–/Mo.This paper was originally presented at the Fall 1987 Meeting of the Electrochemical Society, Inc. held at Honolulu, Hawaii (Proceedings of the Symposium on Primary and Secondary Ambient Temperature Batteries, PV88-6, p. 484–493 (1987).     

Preparation and electrochemical characteristics of a new Li-Mn-V-O system formed from heat-treatment of a MnO2, NH4VO3 and LiNO3 mixture

New quarternary oxides (Li₂O) _x · MnO₂ · yV₂O₅ (x = 0.125 0.25, y = 0.125 0.25), formed by heating mixtures of MnO₂, NH₄VO₃ and LiNO₃ at various Li/Mn and V/Mn atomic ratios and at different temperatures (300 400 °C in air, have been characterized by X-ray diffraction, X-ray photoelectron spectroscopy (ESCA) and infrared spectroscopy. The quarternary oxide with x = 0.25 and y = 0.25 showed a discharge capacity of 220 A h (kg oxide)^–1 and an energy density of ca. 600 W h (kg oxide)^–1 at a current density of 0.20 mA cm^–1 in 1 m LiClO₄-propylene carbonate at 25 °C. When charge-discharge cycling with the (Li₂O) · MnO₂ · 0.25V₂O₅ electrode was performed at a constant capacity of 30 A h (kg oxide)^–1 and at a constant current density of 0.10 0.20 mA cm^–2, the electrode sustained over 100 cycles at a high mean discharge potential of ca. 3 V vs Li/Li⁺.This paper was originally presented at the 183rd meeting of the Electrochemical Society (Honolulu, Hawaii, 1993).     

Analysis of the stability of a take-up-winding mechanism

The coincidence of the frequency of operation of the yarn spreader with the intrinsic frequency of oscillations of the system (resonance phenomenon) is the cause of loss of stability of the take-up winding mechanism in one of its operating regimes. Damping of the thread tension sensor with a damping coefficient of 7·10^–2 N·m·sec can be introduced or a sensor signal filter with a time constant of no less than 0.33 sec can be used at the feed into the regulator to ensure the stability of the system.St. Petersburg State University of Design and Technology. Translated from Khimicheskie Volokna, No. 4, pp. 54–55, July–August, 1995.     

Voltammetric and Raman microspectroscopic studies on artificial copper pits grown in simulated potable water

Artificial copper pits were prepared by electrochemically oxidising 60–80 m diameter copper wires embedded in an epoxy resin over periods of 12–14 h. The electrolyte matrix consisted of various combinations of approximately 40 ppm unbuffered solutions (pH = 6–8) of sodium salts of Cl^–, HCO₃ ^– and SO₄ ^2– that are similar in concentration to what are found in potable water supplies in many metropolitan areas throughout the world. It was found that in the concentrations used for the study, HCO₃ ^– and to a lesser degree Cl^– had a positive affect on preventing pit growth under potentiostatic control, with both anions causing passivation of the copper metal. On the other hand, SO₄ ^2– was found to be very aggressive to copper dissolution and led to the formation of relatively deep pits (about 0.5 mm). Raman microspectroscopic analyses were performed on the freshly prepared undried caps that formed at the top of the pits and allowed the identification of several corrosion products by a comparison with standard copper mineral samples. The most complicated cap structure was observed in the presence of all three anions with distinct regions of the pit corresponding to cuprite (Cu₂O), eriochalcite (CuCl₂ · 2H₂O), atacamite and/or botallackite [Cu₂Cl(OH)₃] and brochantite [Cu₄(SO₄)(OH)₆].