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  • 1
    Electronic Resource
    Electronic Resource
    Alterungseffekte von monomolekularen Oxidschichten auf Au (1978)
    Springer
    Colloid & polymer science 256 (1978), S. 183-183 
    Details
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01679275
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  • 2
    Electronic Resource
    Electronic Resource
    Investigations of nonlinear processes by transients: kinetics of dissolution of inhibitor layers on copper (1993)
    Springer
    Journal of applied electrochemistry 23 (1993), S. 606-614 
    Details
    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The dissolution of inhibitor layers of AHT (3-amino-5-heptyl-1,2,4-triazole) on copper wires in 0.5m H2SO4 was studied by potentiostatic current and capacity transients in a time range from 10 µs to 1000 s. The potential dependent transients show three characteristic regions corresponding to different transfer controlled processes. For short periods an almost constant current of inhibited corrosion through a metastable inhibitor layer is observed. In the second region the dissolution of this layer causes a strong increase in copper corrosion, which was taken as a direct measure of the desorption process. The electrode capacity,C, increases correspondingly. The dissolution itself is not accompanied by a notable charge transfer and, hence, cannot directly be monitored. The last region is dominated by an almost constant active copper dissolution current. The layer dissolution in the second region starts with an inhomogeneous nucleation process. Initially, holes are generated stochastically in the AHT layer and form nuclei of corrosion pits on the copper surface. Based on this model the complete transients can be calculated.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00721952
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  • 3
    Electronic Resource
    Electronic Resource
    Principles of electrocatalysis and inhibition by electrosorbates and protective layers (1979)
    Springer
    Journal of applied electrochemistry 9 (1979), S. 255-267 
    Details
    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Electrocatalysis or inhibition of electrode processes of a reactant R at the metal electrode M is due to the presence of surface layers S. These can be electrostatically adsorbed ions, covalently bound electrosorbates, neutral molecules or layers of oxides and salts, respectively. The influence of layers is caused by electrostatic or chemical interaction between S and R, by a geometric separation of M and R or, in thicker layers, by electronic effects. The influence depends strongly on the type of reaction which can be an outer-sphere electron transfer reaction (ETR), an ion transfer reaction (ITR) or a reaction with formation or breakage of chemical bonds (CBR). Typical examples are discussed for all types of layers and reactions with special emphasis on the type of interaction. Maximum effects are about two orders of magnitude for the electrostatic effect and geometric blocking and about three orders of magnitude for chemical and electronic effects. The theoretical interpretation by changing the pre-exponential factors, activation energies, activity coefficients of the activated complex and transfer coefficients is discussed, but evidence is rare and more detailed experiments are suggested.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00616095
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  • 4
    Electronic Resource
    Electronic Resource
    Electrochemical investigations of the autophoretic coating process (1991)
    Springer
    Journal of applied electrochemistry 21 (1991), S. 877-884 
    Details
    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Autophoretic coating (AC) is a complex chemical process consisting of various electrochemical partial reactions such as metal corrosion, hydrogen evolution and peroxide and oxygen reduction. While the redox potential of the bath is very positive, about 0.6V, the coating process takes place at about −0.2 V dependent on the bath composition. The low conductivity of the bath is necessary to maintain the dispersion, but it hinders the kinetic investigations. Nevertheless potentiodynamic polarization curves show that the diffusion limited peroxide reduction and the corrosion of iron are the most important reactions. From the corrosion current density a maximum weight loss of 0.1 mg cm−2 is estimated for a standard film of 20 μm thickness. Hydrogen evolution is almost negligible during the first period of dipping. This conclusion can be justified by measurements in the hydrogen permeation cell. The partial current densities are not influenced by various emulgators, but the dispersion catalyses the hydrogen evolution and inhibits the anodic corrosion. The diffusion of peroxide is hindered. Potentiostatic measurements in various solutions show the role of ferrous ions deriving from corrosion in the case of iron or by reduction of ferric ions in the case of gold. Measurements at a disc electrode show that the cathodic reactions are dominated by diffusion and migration.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01042454
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  • 5
    Electronic Resource
    Electronic Resource
    Inhibitors of passive corrosion - application of a new test with thin oxide films (1981)
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 32 (1981), S. 13-18 
    Details
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Inhibitoren der passiven Korrosion - Anwendung einer neuen Untersuchungsmethode mit dünnen OxidschichtenEine neue Methode, Inhibitoren der passiven Korrosion zu untersuchen, wird vorgestellt. Potentiodynamische Stromspannungs- und Kapazitätskurven wurden im System Au/Fe2+ in Gegenwart von Inhibitoren aufgenommen. Veränderungen bei der Bildung und Reduktion des γ-FeOOH, des Goldoxids and bei der Sauerstoffentwicklung ermöglichen Aussagen über die Intensität und den Mechanismus der Inhibition.Vorzugsweise warden organische Stickstoffverbindungen untersucht. Pentylamin war ohne Einfluß auf oxidbedeckte Elektroden, während Benzimidazol und seine Derivate starke Inhibitionswirkung zeigten. Die Kapazitätsdaten lassen sich als Reihenschaltung der Kapazitäten von Oxid und Inhibitorschicht deuten. Die Inhibitionswirkung beruht wahrscheinlich auf einer Adsorption des Inhibitors an der Oxidoberfläche. Diese Adsorptionsschicht behindert den Durchtritt hydratisierter Ionen, ist aber ohne Einfluß auf Reaktionen adsorbierter Wassermoleküle, wie z. B. die Sauerstoffentwicklung.Die Anwendbarkeit der Untersuchungsmethode auf andere Systeme wird diskutiert.
    Notes: A new method to test the inhibitors of passive corrosion is presented. Potentiodynamic i(ε)- and C(ε)-curves are recorded in the system Au/Fe2+, inhibitor. The investigations of formation and reduction of the FeOOH-layer, of gold oxide and the oxygen evolution allow estimations of the inhibition efficiency and mechanism.Some organic nitrogencompounds are tested. Pentylamine is ineffective for oxide surfaces, but benzimidazole and its derivates show inhibition effects. The capacity data can be evaluated using a condensor model of a connection in series of the oxide and the inhibitor layer. The detailed discussion shows that adsorption at the film surface is most probable. Such layers inhibite the transfer of hydrated ions, but reactions of water molecules are not influenced, e.g. oxygen evolution.The applicability of this method to other systems is discussed.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/maco.19810320104
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  • 6
    Electronic Resource
    Electronic Resource
    Passivity of Nickel electrodes in presence of the inhibitor PABDedicated to Professor Dr. rer. nat. Hans-Jürgen Engell on the occasion of his 60th birthday (1985)
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 36 (1985), S. 381-388 
    Details
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Die Passivität von Nickel-Elektroden in Gegenwart des Inhibitors PABDie Passivität von Nickelelektroden wurde in An- und Abwesenheit des Inhibitors 2-Pentyl-Aminobenzimidazol (PAB) untersucht. Bei hohen Potentialen ist die Elektrode mit einem dicken Film von NiOOH bedeckt. Verschiedene Zustände des 3-wertigen Oxidfilmes können unterschieden werden: ohne Inhibitor (3o), mit einer äußeren Schicht des Inhibitors (3out), mit einem fast konstanten Konzentrationsprofil im gesamten Film (3tot) und mit einem diffusionsbedingten Konzentrationsgradienten des Inhibitors im Film (3diff).Unter stationären Bedingungen können die Filme 3o, 3out und 3tot durch die Geschwindigkeit der anodischen Sauerstoffentwicklung und die Elektrodenkapazität unterschieden werden. Darüberhinaus nimmt die Reduktions- und Reoxidationskapazität der Elektrode von 3o über 3out zu 3tot ab.Wenn der Film 3o in Gegenwart von PAB reduziert und reoxidiert wird, sinkt die Redoxkapazität ebenso wie die Elektrodenkapazität wegen einer Bildung von 3diff. Die Wirkungsweise des Inhibitors wird sowohl der Bildung eines dicken Polymerfilmes auf dem Oxid als auch eines Nickelhydroxid/PAB-Komplexes zugeschrieben. Der äußere Polymerfilm hat eine gute Protonenleitfähigkeit und ist vermutlich elektronenleitend. Die anodische Sauerstoffentwicklung findet an der inneren Phasengrenze zwischen Oxid- und PAB-Film statt.Die Inhibition der lokalen Korrosion ist vermutlich der Bildung des äußeren Polymerfilmes zuzuschreiben. XPS-Untersuchungen beweisen die angenommenen Konzentrationsprofile von PAB in und auf dem Oxid.Der PAB-Film enthält viel Wasser; innerhalb des Passivfilmes führt PAB zu einer Substitution von O2- durch OH-.
    Notes: The passivity of nickel electrodes is investigated at high potentials in absence and presence of the inhibitor 2-pentyl-aminobenzimidazole (PAB). At high potentials, the electrode is covered by a thick film of NiOOH. Various states of the 3-valent oxide film can be distinguished: Without inhibitor (3o), with an outer layer of inhibitor (3out), with an almost constant concentration profile in the total film (3tot) and a concentration gradient of inhibitor in the film caused by diffusion (3diff). Under steady state conditions, the films 3o, 3out and 3tot can be distinguished by the rate of anodic oxygen evolution, and the electrode capacity. Moreover, the reduction and reoxidation capacity of the electrode decreases from 3o to 3out and 3tot. If the film 3o is reduced and reoxidized in presence of PAB, the redox capacity decreases simultaneously with the electrode capacity due to the formation of 3diff. The role of the inhibitor is due to the formation of a thick polymer film on top of the oxide as well as to the formation of a nickel hydroxide/PAB complex. The outer polymer film has a good proton conductivity and presumably a good electron conductivity. It is concluded that the anodic oxygen evolution takes place at the inner boundary between the oxide and PAB film. The inhibition of local corrosion is probably due to formation of the outer polymer film. XPS measurements verify the expected concentration profiles of PAB in the oxide and on top of it. The PAB-film contains a lot of water, and within the passive film PAB causes a substitution of O2- by OH-.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/maco.19850360903
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  • 7
    Electronic Resource
    Electronic Resource
    Korrosionseigenschaften dünner Schichten im System Ti—B—N (1992)
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 43 (1992), S. 511-519 
    Details
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Corrosion properties of thin coatings in the Ti—B—N systemThin titanium nitride TiN, boride TiB2 and boronitride Ti(B, N) hard coatings were deposited on titanium substrates by the PVD-process Magnetron-Sputter-Ion-Plating (MSIP). They were characterized by X-ray diffractometry, SEM and WDX-analysis. With increasing B-content the Vickers hardness of the coatings increases. Photoelectron spectroscopic measurements show that all coatings are covered in atmosphere by thin oxid layer.Titanium nitride is electrochemically in 1 N sulphuric acid stable up to 1.3 V (SHE), above 1.3 V it becomes oxidized to titanium oxide TiO2 and nitrogen N2. The oxidation products were detected with XPS. Corrosion tests in nitric acid HNO3 show that the corrosion resistance of titanium nitride is lower than the resistance of titanium. The corrosion of titanium boride and titanium boronitride in sulphuric acid is more intensive compared to titanium nitride. The borides cannot be passivated, but dissolve completely by anodic polarization.
    Notes: Dünne metallische Hartstoffschichten aus TiN, TiBN, TiB2 wurden durch die PVD-Technik des reaktiven Hochleistungskathodenzerstäubens auf Titangrundwerkstoff abgeschieden und durch Röntgenstrukturanalyse und Elektronenrasteraufnahmen charakterisiert. Die Härte der Schichten wächst mit zunehmendem Borgehalt. Photoelektronenspektroskopische Untersuchungen belegen, daß alle Schichten an Luft mit einer dünnen Oxidschicht bedeckt sind. Elektrochemisch ist TiN in 1 N H2SO4 bis 1,3 V (SHE) stabil, oberhalb 1,3 Verfolgt Oxidation zu TiO2 und N2. Die Oxidationsprodukte lassen sich mit XPS nachweisen. Korrosionstests in HNO3 zeigen, daß die Korrosionsstabilität von TiN deutlich geringer als von Ti ist. Die Korrosion von TiBN und TiB2 ist bei der Oxidation von H2SO4 wesentlich größer als bei TiN. TiB2 läßt sich nicht passivieren, sondern löst sich anodisch vollständig auf.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/maco.19920431102
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  • 8
    Electronic Resource
    Electronic Resource
    Systematic investigation on the corrosion of iron under conditions relevant to Storage of nuclear waste (1996)
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 47 (1996), S. 475-485 
    Details
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Systematische Untersuchungen zur Korrosion von Eisen unter EndlagerbedingungenKorrosionstests im Autoklaven (170°C, 30 h) wurden an Stahlproben in chloridhaltiger Q-Lauge sowie zum Vergleich auch in Phthalat- und Boratpuffer-Lösungen (pH 4,9 bzw. 8,4) durchgeführt. Die Proben wurden anschließend mit einer Vielzahl von elektrochemischen, optischen und UHV-Methoden untersucht. Eine systematische Abfolge sowohl nicht-modifizierender als auch modifizierender Verfahren wurde angewendet, um sämtliche Messungen an einer minimalen Anzahl von Proben durchführen zu können.Im Korrosionstest bei pH 8,4 (Boratpuffer) bildet sich eine homogene passivierende Schicht aus, die in ihren optischen und halbleitenden Eigenschaften der anodisch gebildeten Oxidschicht (+1 V, 25°C) ähnlich ist. Bei Auslagerung im Phthalatpuffer (pH 4,9, 170°C, 30 h) konnte keine Bildung einer Sperrschicht festgestellt werden; die Oberfläche ist von einer dicken Ausfällungsschicht bedeckt. Bei Auslagerung in Q-Lauge bildet sich eine Ausfällungsschicht von Fe—Mg-Oxichloriden aus, und es findet großflächige Korrosion statt.
    Notes: Corrosion tests were performed on steel samples in q-brine (pH 4.9), and for comparison in phthalate buffer (pH 4.9) and borate buffer (pH 8.4) at 170°C for 30 h in an autoclave. The samples were subsequently investigated by a wide variety of electrochemical, optical and UHV methods. A systematical combination of both non-modifying and modifying methods was employed to allow for all measurements to be performed on a small number of samples.In borate buffer (pH 8.4), a thick (200 nm), homogeneous passivating oxide layer is found to build up on iron under test conditions (170°C, 30 h), resembling the anodic oxide layer (+ 1 V, 25°C) with respect to its optical and n-semiconducting properties. No evidence for a barrier-type layer is found for samples treated in phthalate buffer (pH 4.9) at 170°C for 30 h. The iron surface is covered by a precipitate layer in this case. In the chloridic q-brine, a precipitate layer of Mg-Fe-oxichlorides is formed and large-scale active corrosion is observed.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/maco.19960470902
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  • 9
    Electronic Resource
    Electronic Resource
    Corrosion and passivity of Hastelloy C4 in a high salinity brine (1996)
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 47 (1996), S. 146-153 
    Details
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Korrosion und Passivität von Hastelloy C4 in einer kochsalzhaltigen LaugeKorrosion und Passivität von Hastelloy C4 in Q-Lauge, einer magnesiumchloridreichen Lauge von pH 4,5 bei Raumtemperatur, wurden mit potentiostatischer und potentiodynamischer (i(U) und C(U)) Polarisation untersucht. Die Legierung verhält sich bei Raumtemperatur passiv. Bei Temperaturen ab 60°C und Potentialen oberhalb von 0,2 V SHE bildet sich keine zusammenhängende, schützende Deckschicht mehr aus. ESCA-Messungen zeigen eine Schichtdicke von 1 nm; die Schicht besteht aus Chrom- und Molybdänoxiden. Bei 200°C steigt die Schichtdicke auf 20 nm nach 4 Tagen an und es werden Mg2+-Einschlüsse aus dem Elektrolyten gefunden. Messungen mit einer rasternden Bezugselektrode in verdünnter NaCl zeigen eine homogene Potentialverteilung senkrecht zu Schweißnähten, was darauf hindeutet, daß Bulk, Wärmeeinflußzone und Naht gleiche elektrochemische Eigenschaften haben und somit keine erhöhte Korrosionsanfälligkeit zu erwarten ist.
    Notes: Corrosion and passivity of Hastelloy C4 in Q-brine, a magnesium chloride rich brine of pH 4.5 at room temperature, was studied by potentiodynamic (i(U) and C(U)) or potentiostatic polarisation. While the alloy rests passive at room temperature, no coherent, protecting passive layer is formed at temperatures above 60°C and potentials exceeding 0.2 V SHE. XPS analysis shows that at the rest potential and temperatures below 110°C, the oxide layer is about 1 nm thick and composed of chromium and molybdenum oxides without incorporation of Mg2+ or Cl- from the electrolyte. At 200°C, its thickness increases 20 nm after 4 days and Mg+ inclusions are found. Across the weld, Scanning Reference Electrode measurements in dilute NaCl showed a homogeneous potential distribution indicating that bulk material, heat affected zone and weld have the same electrochemical properties.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/maco.19960470305
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  • 10
    Electronic Resource
    Electronic Resource
    Electronic properties of oxide layers on Fe20Cr in comparison with FeDedicated to Prof. Dr. K. E. Heusler on the occasion of his 60th birthday (1991)
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 42 (1991), S. 179-186 
    Details
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Elektronische Eigenschaften von Oxidschichten auf Fe20Cr-Legierungen im Vergleich mit EisenZur Untersuchung der elektronischen Eigenschaften von Passivschichten auf Fe20Cr wurden C(U)- und ETR-Messungen bei pH 8,4 durchgeführt. Der Vergleich mit den Ergebnissen am reinen Eisen zeigt, daß beide Systeme mit den gleichen Modellen beschrieben werden können, so daß die Modelle, die für die Oxidschichten auf reinem Eisen entwickelt wurden, auf die Passivschichten auf Fe20Cr übertragen werden können. Eine Modifizierung muß lediglich durch die Berücksichtigung zusätzlicher Oberflächenladungen erfolgen, die mit der transpassiven Auflösung des Cr korreliert werden können.Nahe des Flachbandpotentials Ufb erfolgen die kathodischen ET-Reaktionen durch einen Tunnelprozeß durch die Raumladungsrandschicht. Die anodischen Reaktionen werden durch einen Poole-Frenkel-Mechanismus kontrolliert. Dabei ist der geschwindigkeitsbestimmende Schritt der Transport zwischen zwei Resonanzzentren, die als Donatoren ND verstanden werden können.
    Notes: The electronic properties of passive layers on Fe20Cr were examined at pH 8.4 by C(U)- and ETR-measurements and compared with the experiments on Fe. The behaviour of both systems can be explained with the same models. This means, that electronic models which were developed for passive layers on Fe can be transferred to the passive layers on Fe20Cr. The band structure must be modified by surface charge due to the transpassive dissolution of Cr.The cathodic ET-reaction is determined by the tunnelling through the space charge layer at potentials close to Ufb. The anodic electron transfer reaction is controlled by a Poole-Frenkel effect for both systems, where the rate limiting step is the transport between the resonance centres, which are given by the donor concentration ND.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/maco.19910420406
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