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  • 1
    ISSN: 1572-8838
    Keywords: de-alloying ; Raney® ; selective dissolution ; structure ; zinc additive
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Addition of zincate to the leach liquor for the preparation of skeletal copper increases the copper surface area; however it does not stabilize the structure against rearrangement. The leaching kinetics have been studied using a rotating disc electrode (RDE) at 269–293 K in 2–8 M NaOH and 0.0005–0.1 M Na2ZnO2. Zincate ions precipitate as zinc oxide, due to the local consumption of hydroxide ions near the leach front as the aluminium dissolves. This oxide hinders the aluminium dissolution, slowing the leaching rate. It also hinders copper dissolution/redeposition and prevents copper diffusion, thus reducing the structural rearrangement significantly, and causing the formation of a much finer copper structure with increased surface area. The zinc oxide redissolves as the leach front passes, releasing the copper to rearrange once more, thereby allowing the surface area to decrease with time. The activation energy for leaching was found to be 84 ± 6 kJ mol−1.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Journal of applied electrochemistry 29 (1999), S. 1085-1094 
    ISSN: 1572-8838
    Keywords: dealloying ; focussed ion beam ; selective dissolution ; skeletal catalysts ; structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Raney® copper is an active hydrogenation catalyst formed by the selective dissolution of aluminium from a Cu–Al alloy. The structure of Raney® copper is presented in a series of images taken using a focussed ion beam miller (FIB). The images show a structure consisting of a uniform three-dimensional network of fine copper ligaments. A rotating disc electrode, used to control the diffusion layer, enabled a study of the kinetics of the leaching reaction at 269–303 K in 2–8 m NaOH. Under these conditions, the reaction rate was constant and independent of hydroxide concentration. The activation energy for leaching was determined as 69±7 kJ mol−1. The mixed corrosion potential of the dissolving alloy has been related to the exposed copper surface area, which in turn is dependent on the leaching rate and the mechanism of rearrangement. The overall mechanism of formation/rearrangement of the Raney® copper structure was found to be mainly dissolution/redeposition of copper atoms, with surface or volume diffusion, or possibly both, playing a minor role.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Journal of applied electrochemistry 30 (2000), S. 1097-1102 
    ISSN: 1572-8838
    Keywords: chromium dopant ; de-alloying ; Raney® copper catalysts ; selective dissolution ; structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The addition of chromate to the leach liquor for the preparation of skeletal copper increases and stabilizes the copper surface area and slows the leaching rate. The kinetics have been studied using a rotating disc electrode (RDE) at 269–293 K in 2–8 M NaOH and 0–0.1 M Na2CrO4. The rate of leaching was found to be constant with time, with an activation energy of 74 ± 7 kJ mol−1. By monitoring the kinetics and free (mixed) corrosion potential, it was possible to elucidate the mechanistic effect of chromate causing the increased surface area. Chromate was found to deposit on the copper surface as chromium(III) oxide, hindering the leaching reaction as well as the dissolution/redeposition of copper, the main mechanism of structural formation/rearrangement for skeletal copper. This blocking of the surface resulted in a finer structure, with a corresponding larger surface area. It also stabilised the surface area by minimizing the rearrangement. The effect of chromate was found to reach a limit at around 0.03 M Na2CrO4.
    Type of Medium: Electronic Resource
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