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  • 1
    ISSN: 1573-4889
    Keywords: alloy oxidation ; solid-solution scales ; oxygen activity profile
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A simplified method to calculate the oxygen activity profiles in solid-solution scales formed on binary alloys is proposed. This is based on Wagner's theoretical analysis but involves the solution of a single first-order differential equation by a process of successive approximations using the experimental data on the profiles of the scale composition. The agreement between the oxygen activity profiles calculated by this procedure and those obtained by the more general treatment is satisfactory for the systems examined. The method can therefore be used to obtain rapidly an approximate oxygen activity profile when the conditions for the application of the theory are satisfied.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1573-4889
    Keywords: corrosion of pure metals ; simultaneous oxidation and sulfidation ; reaction mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract During the reaction of a pure metal with complex atmospheres containing both oxygen and sulfur, the formation of sulfide mixed with oxide is often observed at high temperature, contradicting thermodynamic predictions. The mechanism proposed so far to explain the formation of a duplex scale at the scale surface assumes a change in composition of the gas phase in a boundary layer next to the scale-gas interface and a reaction of the metal with the molecules of the two elements. This model is shown to be unable to explain the observed amounts of the less stable phase and the reaction rates when sulfur dioxide is the prevailing reacting species and is substituted by the assumption of a direct reaction with the SO2 molecules. The thermodynamic equivalence of the two approaches is also pointed out.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 13 (1979), S. 181-195 
    ISSN: 1573-4889
    Keywords: copper-manganese alloys ; oxidation ; scale composition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation behavior of copper-manganese alloys (2–35 wt. % Mn) in pure oxygen at 760 Torr was investigated at 100° intervals between 550 and 850°C. Gravimetric measurements of the oxidation kinetics have been combined with microstructural studies of the reacted samples in order to evaluate the reaction mechanisms. The scales formed on Cu-2Mn, Cu-5Mn, Cu-10Mn are always composed of three different layers; in any case manganese is present only in the inner layer. The scales formed on Cu-20Mn and Cu-35Mn are composed of two layers, both containing manganese, with a more Cu-rich outer layer. In all the samples internal oxidation in combination with external scale formation is observed.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 12 (1978), S. 205-214 
    ISSN: 1573-4889
    Keywords: alloys ; selective oxidation ; transient state
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Analytical solutions for the concentration profile and the surface concentration of an oxidizable component during the selective oxidation of a binary alloy following pseudoparabolic kinetics are examined, assuming a fixed alloy-scale boundary. A solution similar to that already proposed for rate control by metal transfer across the metal-scale interface can be obtained also assuming diffusion control. In the case of formation of a metal-deficit scale growing mainly by cation diffusion it is shown that oxidation is controlled by the diffusion in the alloy. The rate law is found to be pseudoparabolic, although different from that usually found in practice, leading to negative intercepts in a parabolic plot. Positive intercepts cannot be obtained if the regression of the alloy interface during oxidation is disregarded.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 30 (1979), S. 114-123 
    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: Beständigkeit von α-Bronzen gegen HochtemperaturkorrosionDie Oxidation von CuSn-Legierungen mit bis 13 Gew.-% Zinn in Sauerstoff (1 atm) wurde im Temperaturbereich 550 bis 800 °C im Abstand von jeweils 50 °C untersucht; dabei wurden die kinetischen Gesetzmäßigkeiten sowie die Morphologie und das Gefüge des Zunders mit physikalischen Methoden ermittelt, um die beiden Aspekte des Oxidationsverhaltens zu korrelieren. Die Oxidationsgeschwindigkeit einer Legierung mit 3% Zinn liegt bei 550 und 600 °C unter der von Kupfer, oberhalb 600 °C jedoch darüber. Der Einfluß des Zinnzusatzes erstreckt sich auf die Wechselbeziehung zwischen verschiedenen die Reaktionsgeschwindigkeit beeinflussenden Faktoren, wobei aber das Gesamtergebnis von der Temperatur abhängig ist. Bei höheren Zinngehalten ist die Oxidationsgeschwindigkeit immer geringer als die von reinem Kupfer; als Ursache hierfür wird die Bildung einer Zinndioxidschicht als unterste Zone im Zunder angenommen. Diese Schicht ist zwar dünn und gewöhnlich auch diskontinuierlich, doch verlangsamt sie die Diffusion des Kupfers nach außen. Auch die höchste unter Berücksichtigung den Hochtemperaturlöslichkeit in Kupfer erreichbare Zinnkonzentration reicht noch nicht aus, um eine kontinuierliche, dicke und ausheilungsfähige Zinndioxidschicht auf der Legierungsoberfläche zu erzeugen; trotzdem wird dadurch eine deutliche Abnahme der Oxidationsgeschwindigkeit erreicht.
    Notes: The oxidation of Cu-Sn alloys containing up to 13 wt% Sn in oxygen (1 atm) has been studied in the temperature range 550 °C to 800 °C at 50 °C intervals; the investigation involved the study of the kinetics and of the morphology and structure of the scales by appropriate physical methods, with the aim of correlating the two aspects of the oxidation behaviour. The oxidation rate of a 3 wt% Sn alloy is lower than for pure Cu at 550 and 600 °C, but higher above 600°C. The effect of the tin addition is related to the interplay of many different factors affecting the reaction rate, the overall result depending on temperature. The rate of oxidation of the more concentrated alloys, however, is always lower than that of pure Cu. This result is attributed to the formation of an SnO2 layer at the base of the scale which, although thin and usually discontinous, slows down the outward diffusion of copper. The highest tin concentration allowed by its high temperature solubility in copper is not sufficient to produce a continous thick healing layer of SnO2 at the alloy surface, but nevertheless it produces a pronounced decrease of the oxidation rate.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 30 (1979), S. 179-185 
    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 Korrosion von Eisen in reinem SO2 unter verschiedenen Drücken bei 700°CDie Reaktion zwischen Eisen und reinem SO2 wurde unter verschiedenen Drücken bei 700 °C untersucht. Die Versuche unter statischen Bedingungen zeigten eine große Streuung der kinetischen Daten; umgekehrt lieferten die Versuche unter Normaldruck in strömendem SO2 weitgehend reproduzierbare Ergebnisse. Diese Ergebnisse unterschieden sich jedoch in einigen Punkten von denen früherer Untersuchungen. Mögliche Deutungen werden diskutiert. Schließlich wurde die Bildung von Eisensulfid außerhalb der Bedingungen thermodynamischer Stabilität untersucht, wobei die Möglichkeit einer direkten Reaktion des Metalls mit SO2 statt mit dessen Dissoziationsprodukten betrachtet wird.
    Notes: The reaction between iron and pure SO2 under different pressures at 700 °C has been studied. The experiments carried out under static conditions showed a large scatter of kinetic data while the runs in flowing SO2 at atmospheric pressure produced fairly reproducible results under convenient conditions. They differ, however, in some aspects from previous results for the same system; possible reasons for this effect are discussed. Finally, the formation of iron sulfide beyond the conditions of thermodynamic stability is examined by considering the possibility of the direct reaction of the metal with SO2 rather than with the dissociation products of the latter.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 26 (1975), S. 831-835 
    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: Oxidation von Mangan in reinem Sauerstoff bei niedrigen Drücken bei 550 und 650 °CDie Verfasser untersuchten die Oxidation von Mangan in reinem Sauerstoff bei 550 und 650 °C unter verschiedenen Drücken. In allen Fällen entstanden zwei Schichten verschiedener Dicke und Zusammensetzung. Die äußere Schicht zeigt nach einer von den experimentellen Bedingungen abhängigen Versuchsdauer Blasenbildung, verbunden mit Abplatzen; diese Effekte ergeben sich auch aus den Änderungen der kinetischen Kurven. Der erste Teil der Oxidation folgt immer einem parabolischen Zeitgesetz mit einer vom Sauerstoffdruck abhängigen Geschwindigkeitskonstante. Dieser Effekt wird auf die Diffusionskontrolle des Oxidwachstums durch die äußere Magnetitschicht zurückgeführt. Um die beobachtete Abhängigkeit der parabolischen Konstante von dem Sauerstoffdruck zu erklären, wird dieses Oxid als ein elektronischer Leiter mit vorwiegender Kationendiffusion betrachtet. Die Behandlung der parabolischen Oxidation von Wagner wird modifiziert, um die Anwesenheit von zwei Kationen im Mn3O4 zu berücksichtigen. Der abschließende Ausdruck für Kt stimmt gut mit den experimentellen Ergebnissen überein, wenn die Diffusion den neutralen kationischen Leerstellen zugeschrieben wird. Dieser Mechanismus ist andererseits angesichts der verhältnismäßig niedrigen Arbeitstemperaturen zulässig.
    Notes: Oxidation of manganese in pure oxygen has been studied at 550 °C and 650 °C under different pressures. In all cases we observed the formation of two oxide layers of different thickness and composition. The outer layer undergoes blistering and spalling after a time depending on the experimental conditions as shown also by a change in the kinetic curves. However, the first stage of oxidation follows always a parabolic law, with a rate constant depending on the oxygen pressure. This effect is attributed to a control of the oxide growth by the diffusion through the outer Mn3O4 layer.To explain the observed dependence of the parabolic constant on the oxygen pressure, the oxide is assumed to be an electronic conductor with prevailing cation diffusion. Wagner's treatment of the parabolic oxidation is modified to take into account the presence of two kinds of cations in Mn3O4. The final expression of Kt shows a reasonable agreement with the experimental results, if the diffusion is attributed to the neutral cation vacancies; this mechanism is also justified by the relatively low working temperatures.
    Additional Material: 6 Ill.
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