Density functional theoretical study of Cun, Aln (n = 4–31) and copper doped aluminum clusters: Electronic properties and reactivity with atomic oxygen

A DFT study of the electronic properties of copper doped aluminum clusters and their reactivity with atomic oxygen is reported. Firstly we performed calculations for the pure Cun and Aln (n = 4, 9, 10, 13, 25 and 31) clusters and we determined their atomization energy for some frozen conformations at the B3PW91 level. The calculated work functions and M–M (M = Cu, Al) bond energies of the largest clusters are comparable with experimental data. Secondly, we focused our attention on the change of the electronic properties of the systems upon the substitution of an Al atom by a Cu one. This latter stabilizes the system as the atomization energy of the 31- atoms cluster increases of 0.31 eV when the substitution is done on the surface and of 1.18 eV when it is done inside the cluster. We show that the electronic transfer from the Al cluster to the Cu atom located at the surface is large (equal to 0.7 e) while it is negligible when Cu is inserted in the Aln cluster. Moreover, the DOS of the Al31 and Al30Cu systems are compared. Finally, the chemisorption energies of atomic oxygen in threefold sites of the Al31, Cu31 and Al30Cu clusters are calculated and discussed. We show that the chemisorption energy of O is decreasing on the bimetallic systems compared to the pure aluminum cluster

Modelling the corrosion behaviour of Al2CuMg coarse particles in copper-rich aluminium alloys

The corrosion behaviour of 2024 aluminium alloy in sulphate solutions was studied; attention was focused on the influence of coarse intermetallic Al2CuMg particles on the corrosion resistance of the alloy. Model alloys representative of the aluminium matrix and of Al2CuMg coarse intermetallics were synthesized by magnetron sputtering. Open-circuit potential measurements, current–potential curve plotting and galvanic coupling tests were performed in sulphate solutions with or without chlorides. Further explanations were deduced from the study of the passive films grown on model alloys in sulphate solutions. The results showed that model alloys are a powerful tool to study the corrosion behaviour of aluminium alloys

Intergranular Corrosion of 2024 Alloy in Chloride Solutions

Experiments were performed to determine the propagation kinetics of intergranular corrosion on 2024 aluminum alloy immersed in 1 and 3 M chloride solutions. Tests consisting of immersion in a corrosive solution followed by optical observations on sectioned samples were carried out. This method was found to be time consuming and led to a lack of reproducibility due to the random nature of the corrosion attacks. Another method proved to be more efficient; it consisted of measuring the load to failure on precorroded tensile specimens vs preimmersion time in an aggressive environment. This method was found to allow the mean depth of the corrosion defects to be determined. Further, in 1 and 3 M chloride solution, intergranular corrosion led to the formation of a nonbearing zone, the thickness of which was equal to the mean depth of the corrosion defects. This corroded zone explained the premature failure of the specimens when a uniaxial tensile stress was applied

Statistical Study of the Corrosion Behavior of Al2CuMg Intermetallics in AA2024-T351 by SKPFM

A statistical study combining atomic force microscopy, scanning Kelvin probe force microscopy (SKPFM), and energy-dispersive spectroscopy was carried out on more than 300 Al2CuMg intermetallic particles of AA2024 alloy to determine their corrosion behavior in chloride-containing solutions. The combination of these three techniques allowed the correlation of the dissolution depth of the S-phase particles to their SKPFM potential and their chemical composition. This study also revealed that SKPFM measurements must be carried out with many precautions, but it is a powerful tool for the study of localized corrosion

Corrosion behaviour of brazing material AA4343

This paper is part of a work devoted to corrosion of brazed AA4343/AA3003/AA4343 materials on water side of automotive heater cores. The microstructure of the superficial resolidified AA4343 brazing material has been previously characterised [1] and [2]. It is composed of large (Al) grains separated by valleys containing multiphase deposits of (Al), Si and α-Al(Mn,Fe)Si. The present study focuses on its electrochemical behaviours in neutral water–ethylene glycol mixtures at different temperatures with and without chloride ions. Three types of behaviour are revealed: (i) passivation, (ii) defective passivation and (iii) pitting corrosion at the corrosion potential. The defective passivation is investigated in greater depth. The results show that Si needles do not participate in the corrosion progress whereas the α-Al(Mn,Fe)Si particles are preferential sites for corrosion attacks. α-Al(Mn,Fe)Si particle/matrix interactions are responsible of the defective passivation at valleys level where the α-Al(Mn,Fe)Si phase particles are mainly concentrated. Increasing the temperature enhances this reactivity whereas addition of ethylene glycol decreases it and favours a transition from defective passivation to passivation for ethylene glycol content higher than 55%

Combination of AFM, SKPFM, and SIMS to Study the Corrosion Behavior of S-phase particles in AA2024-T351

The dissolution mechanism of S-phase particles in 2024-T351 aluminum alloy at open-circuit potential in chloride-containing sulfate solutions was investigated using atomic force microscopy (AFM), scanning Kelvin probe force microscopy (SKPFM), and secondary ion mass spectroscopy (SIMS). The combination of the three techniques allowed the correlation between SKPFM measurements and the corrosion behavior of AA2024 to be confirmed, leading to a better understanding of the electrochemical behavior of S-phase particles. A three-step mechanism for the dissolution and accompanying processes occurring near S particles was proposed: (i) preferential aluminum and magnesium dissolution, (ii) galvanic coupling between the copper-enriched particles and the surrounding matrix, leading to an increased passivity of the matrix around the particles, and (iii) copper deposition around the corroded particles

Galvanic corrosion of aluminium–copper model alloys

Galvanic coupling between different α and θ phase-containing model Al–Cu alloys, deposited by magnetron sputtering, has revealed that the anodic α phase did not suffer corrosion and remained in the passive state in sulphate solution. Conversely, sulphate ions induced pitting of the cathodic θ phase. Pitting susceptibility of the cathode increased when the difference between the copper content of the anode and cathode increased. Similar observations were made for all the galvanic couples; further, the higher the copper content of a phase, then the greater its susceptibility to pitting

Corrosion behaviour of brazed multilayer material AA4343/AA3003/AA4343: Influence of coolant parameters

This paper is the second part of a work devoted to corrosion in brazed AA4343/AA3003/AA4343 materials on the water side of automotive heater cores. In the first part of the study [S. Tierce, N.Pébère, C. Blanc, C. Casenave, G. Mankowski, H. Robidou, Electrochim. Acta 52 (2006) 1092], corrosion initiation in the surface layer (i.e. the residual cladding) has been investigated. It has been associated to defective sites in the passive film covering the alloy. The defective sites are linked to a-Al(Mn,Fe)Si particles built up during brazing process. Interactions between a-Al(Mn,Fe)Si particles and the matrix are responsible for the observed behaviour. The present study focuses on the propagation of corrosion through the material in neutral water–ethylene glycol mixtures with and without chlorides. Comparison of the electrochemical behaviour of the three layers of the brazed material (i.e. the residual cladding, the "band of dense precipitates (BDP)" and the core material) revealed that the residual cladding was nobler than the BDP and the core material and thus that the corrosion should propagate through the inner layers due to galvanic coupling: the inner layers constitute the anode and the residual cladding the cathode. Increasing the ethylene glycol content in the water–ethylene glycol mixture decreased the rate of consumption of the materials whereas addition of chloride ions increased it. Mass variation measurements of brazed material in different solutions containing the degradation products of ethylene glycol showed that only glycolate ions had a slight detrimental effect. Corrosion tests performed in heater core tubes allowed the propagation mechanisms to be confirmed

Koreferat zu Kirstein/Schäfer - Erzeugt das Verbrauchsgüterkaufrecht Marktversagen?

Das Referat konzentriert sich auf die Frage, ob das Verbrauchsgüterkaufrecht europäischer Provenienz Marktversagen erzeugt. Dabei kommt es zu einem Ergebnis, welches der bisherigen Einschätzung und Bewertung eher widerspricht: Signalling ist weiterhin möglich, und im Ergebnis wird kein Marktversagen bewirkt. Dieser Befund mag für Ökonomen überraschend sein, denn sie stehen der Verbrauchsgüterkaufrichtlinie im Grundansatz skeptisch gegenüber. Unausgesprochen zugrundegelegt sind solcher Skepsis liberale Vorstellungen vom Marktgeschehen, welche die Privatautonomie über alles stellen und Eingriffe in die Privatautonomie von vornherein mit Misstrauen betrachten. Der Befund ist dagegen aus juristischer Sicht nicht kontraintuitiv. Man konnte mit ihm rechnen. Die Realität ist der beste Beleg: Die Märkte für B2C-Verkäufe sind nicht zusammengebrochen. Sie existieren weiter. Dies ist auch kaum verwunderlich. Denn Konsumenten haben weiterhin Bedarf, und Anbieter bemühen sich weiterhin, diesen Bedarf zu decken.