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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Materialwissenschaft und Werkstofftechnik 13 (1982), S. 274-285 
    ISSN: 0933-5137
    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: The Formation of Surface Films and the Corrosion Resistance of the Silicon Containing Austenitic Steel X 2 CrNiSi 18 15 in Nitric AcidsThe oxide layers consist of two parts: the lower one is mainly Croxide, the upper one is SiO2. ESCA and AAS measurements were made in order to study the formation of the surface layer on the austenitic steel X2 CrNiSi 18 15 in nitric acids. A film, which is chromium oxide, is formed first. On top of this film a second film consisting of SiO2 grows. The elements nickel and manganese are not found in the formation of the oxide films. Immediately below the oxide layer the steel is enrichened with chromium and depleted of iron.In order to find the in some cases very small corrosion rates (5 · 10-5 mm · a-1) in a reproducible manner, the amounts of iron, chromium and nickel which had been dissolved were measured by means of the AAS method as a function of time.For stationary samples apparent activation energies of 65.2 kJ/Mol (azeotropic nitric acid) and 37.5 kJ/Mol (highly concentrated nitric acid), respectively, were found. These data confirm the assumption that the corrosion rate is determined by reactions at the phase boundaries.No appreciable influence of the flow velocity on the corrosion rate was detected.
    Notes: Mit Hilfe von ESCA- und AAS-Messungen wurde die Ausbildung der Deckschicht auf dem austenitischen Stahl X 2 CrNiSi 18 15 in Salpetersäuren untersucht. Es entsteht eine chromoxidreiche Deckschicht, über der sich eine SiO2-Schicht befindet. Nickel und Mangan sind am Aufbau der Oxidschichten nicht beteiligt. Unter der Oxidschicht wurde eine Chromanreicherung bzw. Eisenverarmung im Stahl nachgewiesen.Um die teilweise sehr geringen (bis 5 · 10-5 mm · a-1) Abtragungsraten reproduzierbar erfassen zu können, wurde in Lösung gegangenes Eisen, Chrom und Nickel in Abhängigkeit von der Beanspruchungsdauer mittels AAS bestimmt.Für ruhende Werkstoffproben ergaben sich scheinbare Aktivierungsenergien von 65,2 kJ/Mol (azeotrope Salpetersäure) bzw. 37,5 kJ/Mol (hochkonzentrierte Salpetersäure); diese Werte bestätigen die Annahme einer geschwindigkeitsbestimmenden Phasengrenzreaktion. Ein nennenswerter Einfluß der Fließgeschwindigkeit auf die Korrosion war nicht nachweisbar.
    Additional Material: 20 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 305-310 
    ISSN: 1434-1948
    Keywords: Ab initio calculations ; Carbene homologues ; Boron ; Isoelectronic analogues ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: While Arduengo-type carbenes are now well established for the Group IVa elements carbon, silicon and germanium, they are experimentally unknown for the isoelectronic anions with the Group IIIa elements boron, aluminum, gallium, and indium. In the present quantum chemical investigations, the bonding features of this class of compounds are explored. As a result, they are predicted to be stable species with sizeable singlet-triplet energy separations and electron affinities. Hence, they may be considered as valid targets for experimental investigations. An analysis of the electron density distribution in the case of boron and aluminum reveals a strongly polar B-N bond for the former, and a half Al-N bond with positive charge at the aluminum, emphasizing the donor-acceptor formulation for the latter.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1193-1198 
    ISSN: 1434-1948
    Keywords: Boron ; Triazaboroles ; Heterocycles ; Halogens ; Cyanides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3,4-Dihydro-2,4-diphenyl-2H-1,2,4,3-triazaboroles 3a, 3b, and 4 were synthesized by cyclocondensation of N1,N3-diphenylformamidrazone (1) with dibromophenylborane, dibromomethylborane, and boron trichloride. 3-Chloro-3,4-dihydro-2,4-diphenyl-2H-1,2,4,3-triazaborole (4) was converted into 3,4-dihydro-2,4-diphenyl-2H-1,2,4,3-triazaborole (5) by treatment with LiAlH4. The corresponding 3-cyanato and 3-cyano derivatives 6 and 7 resulted from the reaction of 4 with AgOCN and AgCN, respectively. Compound 7 was transformed into the bis(1,2,4,3-triazaborolyl)oxane 8 by silver oxide. Compounds 1-8 were characterized by elemental analyses and spectroscopic methods (1H, 11B, and 13C NMR; IR; MS). The molecular structure of 8 was established by single-crystal X-ray diffraction analysis.
    Additional Material: 2 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Electroanalysis 8 (1996), S. 1034-1039 
    ISSN: 1040-0397
    Keywords: Rotating disk electrode ; Digital simulation ; Mass transport ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The transport equation for the rotating disk electrode is solved numerically with appropriate boundary conditions for reversible and nonreversible redox reactions. A comparison of the computational mode with experimentel data is presented. The adaption of a steady state under variations of experimental parameters ν (scan rate) and ω (angular frequency of rotation) is investigated. It is shown that a triangular voltage scan can be used to indicate the attainment of a steady state in every zone of the current-voltage curve.
    Additional Material: 5 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Electroanalysis 9 (1997), S. 1403-1408 
    ISSN: 1040-0397
    Keywords: Digital simulation ; Potential step experiment ; Extrapolation method ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For large values of the model diffusion coefficient the Crank-Nicolson scheme produces poor numerical results, if it is used for the simulation of a potential step experiment. On the other hand the Backward Euler or fully implicit scheme, not suffering from this drawback, is of lower accuracy. We apply the extrapolation method introduced by Morris et al. to the simulation of Cottrellian diffusion and to a simple catalytic mechanism. The extrapolation method, does not show the oscillating behavior of numerical solutions and is of higher accuracy than the fully implicit scheme. Comparison to other implicit difference schemes are presented. The extrapolation schemes show superior results for the diffusional problem and for the short time behavior of the catalytic mechanism.
    Additional Material: 6 Ill.
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  • 6
    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 resistance of austenitic and ferritic stainless alloys in 20 to 75% nitric acid as a function of temperature and concentrationA series of stainless austenitic and ferritic materials was exposed for 100 days to boiling nitric acid which contained no corrosion products; the corrosion rates and depths of the grain boundary attack were observed.Provided the structure is precipitation-free, the following are suitable for long-term exposure; the austenitic steels X 2 CrNi 1912, X1 CrNi 25 21, X1 CrNiMoN 25 222 and X1 NiCrMoCu31274, the practically Mo-free and Cu-free development steel X1 NiCr31 27, and the highly Mo-alloyed variant X1 NiCrMoCu 31275. In the case of alloy NiCr21 Mo it is advisable to limit the concentration and/or the temperature of the nitric acid. The “superferrite” X1CrNiMoNb2842, the Japanese steel X1 CrNiNb 30 2 and the austenitic steels X2 CrNiMoN 1713 3 and X1 CrNiMoN 25 22 2 in the version with high nickel content are unsuitable.Thus, as an alloying element, molybdenum does not always impair the resistance of stainless steels to nitric acid.The decisive factor affecting the corrosion rates is the chromium content of the material.The temperature-dependent function of the corrosion in azeotropic nitric acid conforms to Arrhenius relations. The concentration-dependent function of the corrosion in 20 to 75 (80)% nitric acid can be described by a hyperbolic equation. An exception is formed by X1 CrNiSi 1815; here the corrosion rate increases with the concentration of the acid until the azeotropic point is reached; then, owing to the formation of a surface film, it falls until the acid becomes highly concentrated.
    Notes: Eine Reihe nichtrostender austenitischer und ferritischer Werk-stoffe wurde 100 d lang in siedender, korrosionsproduktfreier Salpetersäure beansprucht; hierbei wurden Abtragungsraten und Tiefen des Korngrenzenangriffs verfolgt.Für Langzeitbeanspruchung sind, ein ausscheidungsfreies Gefüge vorausgesetzt, geeignet: die austenitischen Stähle X 2 CrNi 1911,X1 CrNi 25 21,X1 CrNiMoN 25 222,X1 NiCrMoCu 3127 4 sowie die praktisch molybdän- und kupferfreie Entwicklungsgüte X1 NiCr3127 und die hochmolybdänlegierte Variante X1NiCrMoCu31275. Bei der Legierung NiCr21Mo empfiehlt sich eine Begrenzung der Salpetersäure-Konzentration und/oder der Temperatur. Nicht geeignet sind der “Superferrit” X1 CrNiMoNb2842, die japanische Sorte X1CrNiNb302 sowie die austenitischen Stähle X 2 CrNiMoN 1713 3 und X1 CrNiMoN 25 22 2 in der hochnickelhaltigen Version.Das Legierungselement Molybdän wirkt sich somit nicht in allen Fällen schädlich auf die Salpetersäureständigkeit nichtrostender Qualitäten aus.Entscheidend für die Höhe der Abtragungsraten ist die Höhe des Chrom-Gehaltes des Werkstoffes.Die Temperaturabhängigkeit der Korrosion in azeotroper Salpetersäure folgt Arrhenius-Beziehungen. Die Konzentrationsabhängigkeit der Korrosion in 20 bis 75 (80)%iger Salpetersäure läßt sich durch einen Hyperbel-Ansatz beschreiben; eine Ausnahme bildet X1 CrNiSi 18 15: mit zunehmender Säurekonzentration steigt die Abtragungsrate bis zum Azeotrop-Punkt an und fällt dann bis zur hochkonzentrierten Säure infolge Deckschichtbildung ab.
    Additional Material: 30 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 42 (1991), S. 559-569 
    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 of austenitic stainless steels in (condensing) nitric acid containing chloridesThe corrosion parameters involved in the behaviour of austenitic stainless steels and nickelbase alloys in chloride containing nitric acid are being stated.Investigation of the corrosion resistance of the austenitic stainless steel 1.4306, ESR grade for application in nitric acid, in nitric acid condensates containing small amounts of chlorides. The condensates were formed from boiling nitric acids of molarities 6 to 10 containing 15 to 45 mg chlorides/1.The calculated corrosion rates of 〈 1 μm/y can be considered rather small. Especially in cases of insufficient wetting of the heat exchanger surfaces, however, local roughening and pitting corrosion is to be expected, mostly under rust-colored, chloride-containing deposits. The intensity of pitting corrosion increases with increasing chloride contents of the nitric acid solutions that evaporate.The sealing surfaces consisting of steel 1.4306 and PTFE did not exhibit any crevice corrosion.Nitric acid grade ESR-1.4306 definitely does not suffice requirements as described in this paper. It is suggested to use stainless steels which exhibit an improved resistance against chlorides and, at the same time, a high resistance against nitric acid attack. The following steel grades may be considered: X 1 CrNi 25 21 (Mat. No. 1.4335), X 2 CrNiMoN 25 22 2 (Mat. No. 1.4466) and/or X 1 NiCrMoCuN 31 27 4 (Mat. No. 1.4563).
    Notes: Die Parameter der Korrosion nichtrostender austenitischer Stähle und Nickelbasis-Legierungen in chloridhaltigen Salpetersäuren werden beschrieben.Untersucht wurde das Korrosionsverhalten des nichtrostenden austenitischen Stahls W.-Nr. 1.4306 als Salpetersäure-Qualität in ESU-Güte bei Beaufschlagung mit schwach chloridhaltigen Salpetersäure-Kondensaten. Die Kondensate bildeten sich aus siedenden 6 bis 10 M Salpetersäuren mit 15 bis 45 mg Chlorid/1.Die errechneten Abtragungsraten sind mit 〈 1 μm/a zwar gering, jedoch ist - vornehmlich bei nur geringer Kondensat-Bespülung der Wärmetauscherflächen - mit örtlichen Aufrauhungen und mit Lochkorrosion, meist unter rostfarbenen, chloridhaltigen Belägen, zu rechnen. Die Lochkorrosionsintensität nimmt mit steigendem Chloridgehalt der zu verdampfenden Salpetersäure-Lösungen zu.An den aus W.-Nr. 1.4306 und PTFE gebildeten Dichtflächen trat keine Spaltkorrosion auf.W.-Nr. 1.4306 (in Salpetersäure-Qualität und ESU-Güte) ist bei den hier beschriebenen Anwendungen überfordert; es wird vorgeschlagen, nichtrostende Stähle mit verbesserter Chlorid-Beständigkeit bei gleichzeitig hoher Salpetersäure-Beständigkeit zu verwenden, wobei an die Stahlsorten X 1 CrNi 25 21 (W.-Nr. 1.4335), X 2 CrNiMoN 25 22 2 (W.-Nr. 1.4466) und/oder X 1 NiCrMoCuN 31 27 4 (W.-Nr. 1.4563) gedacht wird.
    Additional Material: 19 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 41 (1990), S. 308-329 
    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 of aluminium and aluminium alloys in nitric acidA literature survey was made to show the suitability of aluminium and aluminium alloys in contact with highly concentrated nitric acid, particularly with regard to the corrosion behaviour of weld joints made using various welding processes.The corrosion resistance of Al99.5 in nitric acid was investigated as functions of temperature and acid concentrations. The linear corrosion rates are plotted in an Arrhenius diagram. Decreasing nitric acid concentrations are causing a parallel shift of the lines in the Arrhenius diagram towards higher corrosion rates.Starting with A199.5, the corrosion rates in nitric acid at and above 99.8 concentration decrease as the A1 contents of the materials increase. Doping with copper should be avoided.After exposure of wrought as well as continuously cast A1 and A1 alloys to highly concentrated technical grade nitric acid at 30 °C (1 year test period), the corrosion behaviour of a number of alloys was comparable to that of pure aluminium grades.
    Notes: Auswertung des Schrifttums über die Eignung von Aluminium-Werkstoffen zur Handhabung von hochkonzentrierter Salpetersäure, vornehmlich im Hinblick auf das Korrosionsverhalten von nach unterschiedlichen Verfahren hergestellten Schweißverbindungen.Untersuchungen zur Temperatur- und Konzentrationsabhängigkeit der Korrosion von Al99,5 in Salpetersäuren. Die linearen Abtragungsraten ordnen sich in ein Arrhenius-Diagramm ein, wobei abnehmende Salpetersäure-Konzentrationen eine Parallel-Verschiebung der Geraden im Arrhenius-Diagramm in Richtung höherer Abtragungsraten bewirken.Ausgehend von Al99,5 verringern sich die Abtragungsraten in ≥ 99,8%iger Salpetersäure mit zunehmendem Al-Gehalt der Werkstoffe; Kupfer-Dotierungen sind zu vermeiden.Nach der Auslagerung von Al-Werkstoffen (Knetwerkstoffe und Strangguß) in technischer, auf 30°C erwärmter hochkonzentrierter Salpetersäure zeigten (Prüfdauer: 1 Jahr) eine Reihe von Legierungen ein den Reinaluminium-Sorten vergleichbares Korrosionsverhalten.
    Additional Material: 15 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 35 (1984), S. 401-406 
    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: Hydrolysis of o-dichlorobenzene-water-mixtures In neutral to acid conditions and its importance when selecting materials of constructionWater-saturated o-dichlorobenzene and o-dichlorobenzene-watermixtures were investigated for hydrolysis under neutral and acid conditions and the exclusion of light. Some measurements were also taken in presence of iron oxides and also metallic iron.Chloride ion generation grows with increasing temperatures and - at 175 °C - also with time. The greatest chloride ion generation was observed when water saturated o-dichlorobenzene reacted in the presence of iron oxides.In the presence of sulfuric acid the maximum chloride ion generation was detected at 175 °C and a sulfuric acid concentration of 3 · 10-3 mol/l.The hydrolysis products were monochlorobenzene and o-chlorophenol.The chloride ion generation from o-dichlorobenzene in neutral and slightly acid media is important when selecting materials of construction for chemical equipment.
    Notes: Die Hydrolyse von wassergesättigtem o-Dichlorbenzol und von o-Dichlorbenzol-Wasser-Gemischen wurde unter Lichtausschluß im neutralen und im sauren Bereich untersucht. Die Messungen wurden teils in Gegenwart von Rost bzw. metallischem Eisen durchgeführt.Die Chlorid-Abspaltung steigt mit zunehmender Temperatur und - bei 175 °C - auch mit zunehmender Beanspruchungsdauer an. Die höchste Chlorid-Abspaltung wurde bei wassergesättigtem o-Dichlorbenzol in Gegenwart von Rost gefunden.In Anwesenheit von Schwefelsäure tritt bei 175 °C ein Maximum der Chlorid-Abspaltung bei einer Schwefelsäure-Konzentration von 3 · 10-3 mol/l auf.Als Hydrolyseprodukte waren lediglich Monochlorbenzol und o-Chlorphenol nachweisbar.Die Chlorid-Abspaltung aus o-Dichlorbenzol im neutralen und schwach sauren Bereich ist bei der werkstofflichen Auslegung entsprechender Bauteile zu beachten.
    Additional Material: 6 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 37 (1986), S. 74-82 
    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 of the alloy AlMg 2 Mn 0,8 in highly-concentrated nitric acidThe purpose of the study was to investigate the corrosion of the alloy AlMg 2 Mn 0.8 in highly-concentrated nitric acid at temperatures between 5 °C and 50°C.The corrosion rates follow the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ \lg \ {\rm w}_{{\rm lin}} = - {\textstyle{{3170} \over {\rm T}}} + 9.1; $$\end{document} the apparent activation energy was calculated to be -60.8 kJ/mol.The ratio of the dissolved alloy components aluminum and magnesium indicates that magnesium had accumulated near the surface of the metal before the exposure to nitric acid. This finding is confirmed by surface analysis.
    Notes: Untersucht wird die Korrosion der Legierung AlMg 2 Mn 0,8 in hochkonzentrierter Salpetersäure bei Temperaturen zwischen 5 und 50°C.Die Abtragungsraten folgen der Arrhenius-Beziehung \documentclass{article}\pagestyle{empty}\begin{document}$$ \lg \ {\rm w}_{{\rm lin}} = - {\textstyle{{3170} \over {\rm T}}} + 9,1; $$\end{document} die scheinbare Aktivierungsenergie ergibt sich zu -60.8 kJ/mol.Aus dem Verhältnis der in Lösung gegangenen Legierungsanteile Aluminium und Magnesium ist abzuleiten, daß Magnesium vor der Salpetersäure-Beanspruchung in der Metalloberfläche angereichert ist. Dieser Befund wird durch oberflächenanalytische Untersuchungen bestätigt.
    Additional Material: 17 Ill.
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