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  • oxidation  (425)
  • Springer  (425)
  • American Institute of Physics (AIP)
  • American Meteorological Society
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  • 2000-2004  (64)
  • 1995-1999  (216)
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  • Springer  (425)
  • American Institute of Physics (AIP)
  • American Meteorological Society
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  • 101
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1657-1669 
    ISSN: 1572-8943
    Keywords: activation energy ; combustion ; differential scanning calorimetry ; kinetics ; lignite ; oxidation ; thermogravimetric analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal analysis increasingly being used to obtain kinetic data relating to sample decomposition. This work involves a comparative study of several methods used to analyse DSC and TG/DTG data obtained on the oxidation of Beypazari lignite. A general computer program was developed and the methods are compared with regard to their accuracy and the ease of interpretation of the kinetics of thermal decomposition. For this study, the ratio method was regarded as the preferred method, because it permits the estimation of reaction order, activation energy and Arrhenius constant simultaneously from a single experiment.
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  • 102
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    Journal of thermal analysis and calorimetry 52 (1998), S. 327-340 
    ISSN: 1572-8943
    Keywords: aging ; DTA-TG ; oxidation ; polypropylene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Several samples of polypropylene were studied by thermal analysis. The photo-oxidation and the aging of polypropylene films showed a mass loss more than 7% in heating from 20 to 220°C (5°C min-1), cooling to 20°C and reheating to 220°C. The authors observed also a decrease of the melting and crystallization temperatures. The non aged samples or these ones with preservatives are thermo-oxidised and presented an exothermic peak at about 200°C in DTA heating. The DTA-TG simultaneous apparatus is very useful in the study of polypropylene oxidation by making comparative trials according to a well definite procedure.
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  • 103
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    Journal of thermal analysis and calorimetry 53 (1998), S. 263-267 
    ISSN: 1572-8943
    Keywords: kinetics ; molybdenum sulphide ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper reports on the results attained in the determination of the mechanism of oxidation of molybdenum sulphide under non-isothermal conditions in an air atmosphere. The mechanism of the process was determined by simultaneous DTA-TG-DTG, and the kinetic parameters of the reactions involved were obtained according to the methods of Kissinger and Ozawa.
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  • 104
    ISSN: 1572-8943
    Keywords: DSC ; infrared spectrometry ; oxidation ; polyethylenes ; thermal analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of pure and recycled polyethylene samples was studied by thermal analysis (DTA-TG-DSC): presence of two exothermic peaks and mass loss. The thermo-oxidation products, containing C-O and C=O links, were identified by IR spectrometry and GC-MS spectrometry. The oxidation is easier from low to high density polyethylene.
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  • 105
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    Journal of thermal analysis and calorimetry 57 (1999), S. 473-486 
    ISSN: 1572-8943
    Keywords: cumene ; oxidation ; polymerization ; quinone-amine inhibitors ; solution microcalorimetry ; styrene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The application of solution microcalorimetry was demonstrated on two model examples – inhibited oxidation of cumene and radical polymerization of styrene. From the experimental dependences of the rate of heat release on time, the rate constants k 7 of the interaction of an inhibitor with radicals of substrate (RO 2 . or R.) in oxidation or in polymerization were determined for the set of inhibitors of N-aryl N-(2-quinone) amine series. It was shown that these compounds are weak inhibitors of oxidation of cumene and rather efficient inhibitor of polymerization of styrene.
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  • 106
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    Journal of thermal analysis and calorimetry 62 (2000), S. 575-578 
    ISSN: 1572-8943
    Keywords: active metal ; high-dispersed iron powder ; oxidation ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Two oxidation stages of electrolytic ultradispersed iron powder at the temperature range of 90–450°C have been stated. The contribution of increasing mass and evolving heat at the first oxidation stage due to changing Fe0 into Fe2O3 in the total oxidation effect is predominant. The thermal method of active metal determination in electrolytic iron powders has been developed. The coarse-grained reduced iron powder was not oxidized completely just to 900°C because of local sintering of big iron particles as a result of evolving heat at oxidation of high-dispersed iron particles.
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  • 107
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    Journal of thermal analysis and calorimetry 63 (2000), S. 507-515 
    ISSN: 1572-8943
    Keywords: boron carbide ; kinetic modelling ; oxidation ; water vapour
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation behaviour of a B4C based material was investigated in a dry atmosphere O2(20 vol.%)-CO2(5 vol.%)-He and also in the presence of moisture H2O (2.3 vol%) as boron oxide is very sensitive to water vapour. The mass changes of samples consisting of a chemical vapour deposit of B4C on silicon nitride substrates were continuously monitored in the range 500–1000°C during isothermal experiments of 20 h. The stability of boron oxide formed by oxidation of B4C was also studied in dry and wet atmospheres to explain the kinetic curves. In both atmospheres, oxidation is diffusion controlled at 700 and 800°C and enhanced by water vapour. At 900°C and higher temperatures, boron oxide volatilisation and consumption by reaction with water vapour modifies the properties of the oxide film and the material is no more protected. At 600°C, B4C oxidation is weak but the process remains diffusion controlled in dry conditions as boron oxide volatilisation is negligible. However, in the presence of water vapour, B2O3 consumption rate is significant and mass losses corresponding to this consumption and to the combustion of the excess carbon are observed.
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  • 108
    ISSN: 1572-8986
    Keywords: RF SiCl4 discharge ; mass spectrometry ; kinetics ; decomposition ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract Time-resolved mass spectrometry was used for analysis of the plasma reactions in radio frequency (RF) SiCl 4 and SiCl 4 −O 2 discharges as functions of starting partial pressure and electrical power. Molecular concentrations of the reactants and products from SiCl 4 alone and with O 2 were obtained from the mass spectra and used for plotting the kinetic curves. The SiCl 4 and O 2 consumption rates were calculated from the kinetic curves and compared with results of theoretical simulation of the reaction. Direct electron impact decomposition was found to be the main pathway for pure SiCl 4 conversion. On the contrary, the consumption of SiCl 4 in the SiCl 4 +O 2 mixtures was largely chemical. The experimental macrokinetics are in agreement with a model in which oxidation is caused by the atomic oxygen.
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  • 109
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    Plasma chemistry and plasma processing 19 (1999), S. 131-151 
    ISSN: 1572-8986
    Keywords: Styrene ; oxidation ; silent discharge ; plasma ; dielectric barrier
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract A silent discharge plasma reactor has been developed to study the oxidation of styrene vapor in argon/oxygen mixtures. A number of analytical techniques were employed to determine the destruction efficiency and to characterize the intermediate products. The destruction efficiency was measured as a function of initial styrene concentration, temperature, and energy density of the plasma. The formation of solid products was observed in most experiments. At low temperature (100°C), the solid deposit was polymeric in nature, while at high temperature (300°C) the solid appeared to be amorphous carbon. A combination of high temperature and high energy density resulted in high destruction efficiency and minimal production of solid films. The destruction efficiency vs. energy density is shown to be more complex than a simple model predicting exponential behavior. Several reasons for the discrepancy are suggested. The “e-folding” energy density for the destruction of styrene is compared to literature values for other organic compounds, measured using similar types of plasma reactors.
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  • 110
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    Plasma chemistry and plasma processing 19 (1999), S. 383-394 
    ISSN: 1572-8986
    Keywords: Nonthermal plasma ; benzene ; Al2O3 ; BaTiO3 ; oxidation ; absorption ; atmospheric pressure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract The combination of plasma discharge and adsorption was examined for oxidation of dilute benzene in air in a plasma reactor packed with a mixture of BaTiO 3 pellets and porous Al 2 O 3 pellets (i.e., an alumina hybrid reactor). The oxidative decomposition of benzene was enhanced by the benzene concentrating on the Al 2 O 3 pellets. Furthermore, there was a higher selectivity to CO 2 in the products from the hybrid than from a plasma reactor packed with BaTiO 3 pellets alone. The presence of the Al 2 O 3 pellets suppressed the formation of N 2 O.
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  • 111
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    Plasma chemistry and plasma processing 19 (1999), S. 421-443 
    ISSN: 1572-8986
    Keywords: Streamer corona ; NO x removal ; nonthermal plasma ; oxidation ; reduction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract In this paper, the NO-to-NO 2 conversion in various gaseous mixtures is experimentally investigated. Streamer coronas are produced with a dc-superimposed high-frequency ac power supply (10–60 kHz). According to NO x removal experiments in N 2 +NO x and N 2 +O 2 +NO x gaseous mixtures, it is supposed that the reverse reaction NO 2 +O→NO+O 2 may not only limit NO 2 production in N 2 +NO x mixtures, but also increase the energy cost for NO removal. Oxygen could significantly suppress reduction reactions and enhance oxidation processes. The reduction reactions, such as N+NO→N 2 +O, induce negligible NO removal provided the O 2 concentration is larger than 3.6%. With adding H 2 O into the reactor, the produced NO 2 per unit removed NO can be significantly reduced due to NO 2 oxidation. NH 3 injection could also significantly decrease the produced NO 2 via NH and NH 2 - related reduction reactions. Almost 100% of NO 2 can be removed in gaseous mixtures of N 2 +O 2 +H 2 O+NO 2 with negligible NO production.
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  • 112
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    Journal of sol gel science and technology 12 (1998), S. 35-48 
    ISSN: 1573-4846
    Keywords: yttrium acetate precursor ; particle coating ; oxidation ; corrosion ; Inconel
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract “Sol paint” that yields yttrium-based compounds was prepared by mixing four chemical ingredients, yttrium acetate tetrahydrate precursor, diethanolamine, isopropyl alcohol, and hydrochloric acid, and then applied as oxidation/corrosion resistant coatings for Inconel 625 substrates. Annealing the coatings at 500°C developed a coalescent microstructure of coarse particles consisting of amorphous yttrium carbonate as the major component and crystalline yttrium oxide (Y2O3) as the minor one. At 700°C, the yttrium carbonate was transformed into Y2O3 by decarbonation. Increasing the annealing temperature to 900°C led to the formation of the YCrO3 phase yielded by interaction between Y2O3 and the Cr2O3 which had arisen from the oxidation of the underlying Inconel; the YCrO3 phase created a particle coating with a densified microstructure. There were two key factors in mitigating the degree of oxidation of Inconel at 900°C in air: (1) an uptake of oxygen by Y2O3 in the coatings, and (2) a densified coating layer that suppresses the diffusion and permeation of oxygen through it. Furthermore, inhibiting the rate of NaCl-caused corrosion was not only due to the excellent coverage of particle coatings over the entire surfaces of the substrates, but also may be associated with a good adherence of the coatings to the substrates.
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  • 113
    ISSN: 1573-4889
    Keywords: ion implantation ; oxidation ; thermal ; stainless steel ; ion-beam analysis ; aluminum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract AISI-321 steel samples were implanted with Al ions (implantation-energy:40 keV; dose: 2×1017 ions/cm2). Thermal oxidationof the samples was performed at 450, 550, 600, and 650°C for periodsvarying from 1 to 6 days in air and in a corrosive CO2-containingenvironment. Nuclear Reaction Analysis (NRA) and Rutherford BackscatteringSpectrometry (RBS) were used to investigate the oxidized samples. Asignificant improvement of the oxidation resistance of the implantedmaterial in comparison to the nonimplanted material was observed. Thisespecially applies for samples oxidized at high temperatures. The aluminumdepth distribution determined by NRA [using the resonance at 992 keV of the27Al(p, γ )28Si nuclear reaction] and RBS,indicated no variation of the Al profile in the temperature region450–600°C, whereas at 650°C a slight Al diffusion wasobserved. Scanning electron microscopy (SEM–EDS) was applied to studythe surface morphology and the constitution of the oxide scale formed, aswell as to explain the influence of Al implantation on the oxidation behaviorof AISI-321 austenitic stainless steel.
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  • 114
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    Oxidation of metals 53 (2000), S. 467-479 
    ISSN: 1573-4889
    Keywords: Ni–5Cr–5Al ; oxidation ; magnetron sputtering ; nanocrystalline coating
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A NiO-forming Ni–5Cr–5Al (at.%) alloy has been developed anddeposited as a sputtered nanocrystalline coating. The oxide formation andoxidation behavior of this coating have been studied at 1000°C inair. The oxidation rate markedly decreased with time and the oxidationkinetics obeyed the fourth power law. Complex oxide scales, consisting ofNiO, NiAl2O4 and α-Al2O3,were formed during 200 hr oxidation. The outer oxide layer consisted of NiOand NiAl2O4 and an inner oxide layer ofα-Al2O3. The sputtered Ni–5Cr–5Alnanocrystalline coating showed good oxidation resistance due to theformation of an α-Al2O3 inner layer andexcellent adhesion of the complex oxide scales.
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  • 115
    ISSN: 1573-4889
    Keywords: ion plating ; steel ; TiAlN coating ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract To improve the high-temperature oxidation resistance of STD61 steels used ashot dies or cutting tools, Ti0.3Al0.2N0.5films were deposited on STD61 steel substrates by arc-ion plating. Thedeposited film consisted of Ti3Al2N2 andTi2N phases. The oxidation characteristics were studied attemperatures ranging from 700 to 900°C in air. The deposited STD61steels displayed excellent oxidation resistance up to 800°C, butexhibited large weight gains and breakaway oxidation at 900°C. Theoxidation products were primarily Fe2O3, TiO, TiO2,and α-Al2O3, the relative amount of each oxidebeing dependent on the oxidation condition. Among various oxides, TiO2and α-Al2O3 were the major oxides at 800°Cfor at least up to 16 hr. However, at a higher temperature or a longeroxidation period, the significant outward diffusion of iron from thesubstrate resulted in the formation of iron oxides, together with otheroxides of Ti and Al.
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  • 116
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    Oxidation of metals 54 (2000), S. 155-162 
    ISSN: 1573-4889
    Keywords: Ni–8Cr–3.5Al ; nanocrystallization ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Magnetron-sputter deposition was used to produce a Ni–8Cr–3.5Al(wt.%) nanocrystalline coating on substrates of the same alloy. Theoxidation behavior of the cast Ni–8Cr–3.5Al alloy and itssputtered coating were investigated at 1000°C in air. Complex,layered-oxide scales composed of Cr2O3 outer layer,mixed spinel NiAl2O4 and NiCr2O4middle layer, and α-Al2O3 inner layer were formedon the Ni–8Cr–3.5Al nanocrystalline coating during 200-hroxidation, whereas Cr2O3, with some NiCr2O4external layer with internal Al2O3, formed on the castalloy. Because of the formation of this α-Al2O3inner layer on the coating, the sputtered Ni–8Cr–3.5Al coatingshowed better oxidation resistance than the cast alloy. The effect ofnanocrystallization on oxide formation is discussed. It was indicated thatthe formation of this α-Al2O3 inner layer was closely related to therapid diffusion of Al through grain boundaries in the nanocrystallinecoating and the relatively high Cr content in Ni–8Cr–3.5Al.
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  • 117
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    Oxidation of metals 54 (2000), S. 189-209 
    ISSN: 1573-4889
    Keywords: oxidation ; β-FeAlCr ; coatings ; magnetron sputter-deposition ; ridge-type oxide ; Al2O3 phase transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract β-FeAl coatings containing various Cr contents of 6.5–45 wt.%were produced with a closed-field, unbalanced magnetron sputter (CFUMS)deposition technique. Cyclic oxidation tests at 1100°C in air for100 1-hr cycles and isothermal exposures at 1000°C in pure O2 for100 hr were carried out with the coatings and an as-cast FeAlspecimen. All of the coatings showed good scale-spallation resistanceduring cyclic oxidation and the coating with 6.5 wt.% Cr exhibited thelowest oxidation rates in both cyclic and isothermal oxidationexposures. After oxidation, fine-grain ridge-type oxide scales formed onthe coatings, while the oxide scale formed on the cast FeAl showed alarge quantity of θ-Al2O3 blades and large interfacial voids on thebase–alloy surface. The transformation from θ to α-Al2O3was accelerated due to the presence of Cr in the coatings. The fasttransformation considerably reduced oxidation rates, suppressed fastoutward Al diffusion for the growth of a θ-Al2O3 scale, and preventedthe formation of interfacial voids that played a major role in causing thescale spallation.
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  • 118
    ISSN: 1573-4889
    Keywords: plasma spraying ; chromium steel ; oxidation ; Fe–Cr spinel oxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract During plasma spraying of metals in air, rapid-oxidation reactions occur, inmost cases. In oxidation products of Cr-rich steels, Fe–Cr spineloxide is often found as a dominant oxide phase. A thermodynamic analysisof a system composed of Fe–13%Cr alloy and water vapor or air showedthat the oxidation product in a wide range of high temperatures isFe3-wCrwO4 (w〉2). This tetragonallydistorted spinel oxide is not stable at room temperature. Water vapor andair were considered as limits of the gaseous-phase composition inatmospheric spraying by a water-stabilized plasma gun, where the compositionof the plasma plume is modified by air entrainment. The equilibriumcalculations enabled determination of the effects of temperature andgas-to-solid ratio on w. To show the existence of chromium-rich,tetragonally distorted spinel oxide experimentally, a typical productresulting from oxidation of 13%Cr–steel particles during their flightin the plasma plume was studied after rapid solidific ation. This was madepossible by trapping and quenching the flying particles in liquid nitrogenat a distance from the plasma-gun nozzle corresponding to thenozzle–substrate distance in conventional plasma spraying. The resultsobtained by X-ray diffraction, Mössbauer spectroscopy, and X-rayfluorescence analysis showed that this oxide, in which w≈2.4, constitutedthe dominant phase in the oxidation product.
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  • 119
    ISSN: 1573-4889
    Keywords: dilute alloys ; oxidation ; Wagner-Hauffe rule
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Concerning the parabolic oxidation of alloys with a low content of a different valence element, we show that the Wagner-Hauffe valence approach contains some inaccuracies. This paper is devoted to the growth of an oxide MO with metal excess or oxygen deficit. The analytical processing consists in solving the differential equation connecting the point defect flux to the oxygen pressure. This equation has been solved analytically in the case where the foreign-element concentration is very high compared to that of the point defects in the pure oxide. On this assumption with a lower-valence dopant, as long as the oxide conductivity remains essentially electronic, the oxidation is limited only by the transport of ionic defects across the scale under the electric-potential gradient. Moreover, an increase of the dopant concentration may lead to an oxide exhibiting partial ionic conductivity. Consequently, the parabolic constant variations as a function of the dopant concentration is not monotonic, contrary to results published before. With a higher-valence dopant, the conductivity always remains electronic, and this result agrees with predictions based on the Wagner Hauffe approach, though the demonstrations are fundamentally different.
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  • 120
    ISSN: 1573-4889
    Keywords: oxidation ; copper ; Li-doped copper ; Cr-doped copper ; short-circuiting ; Mott's parabola ; Wagner's parabola
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The influence of shorting circuitry attachment between metal-oxide and oxideoxygen interfaces on the oxidation kinetics of copper, lithium-doped copper (Li: 400 ppm), and chromium-doped copper (Cr: 12 ppm) have been studied in dry air $$(P_{O_2 } = 21.27kPa)$$ in the temperature range of 523–1073 K. Oxide film or scale growth under short-circuiting as well as under normal oxidation conditions conforms to the parabolic rate law. The oxidation kinetics under short-circuiting resulted in decreased rates for Cu and Li-doped Cu up to a temperature of 773 K, while Cr-doped Cu exhibited an enhancement in rate compared to its normal oxidation in the same temperature range. However, above 873 K, all three systems under shorting circuitry attachment exhibited enhanced rates compared to their normal oxidation rates in conformity to the existing theoretical model. Use of additional resistances in series in the outer short-circuit Pt path have clearly established that below 773 K Mott's fieldinduced migration plays the most important role, while at elevated temperatures Wagner's electrochemical potential-gradient factor acts as the main driving force in the scale-growth process. The results have been interpreted on the basis of average defect concentration, the electrochemical potential gradient, electrical field gradient, and transport coefficient in the Cu2O layer.
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  • 121
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    Oxidation of metals 46 (1996), S. 109-127 
    ISSN: 1573-4889
    Keywords: oxidation ; Ni3Al base alloy ; chromium ; cobalt ; titanium
    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 Ni3Al+2.90 wt.% Cr, Ni3Al+3.35 wt% Co, and Ni3Al+2.99 wt.% Ti alloys was studied in 1 atm of air at 1000, 1100, and 1200°C. Isothermal tests revealed parabolic kinetics for all three alloys at all temperatures. Cyclic oxidation for 28 two-hour cycles produced little spallation at 1000°C, but caused partial spallation at 1100°C. Especially, at 1200°C severe spallation in all three alloys was observed. Although additions of Cr, Co, or Ti to Ni3Al alloys slightly increased the isothermal-oxidation resistance, the additions tended to decrease the cyclic-oxidation resistance. The major difference in the oxidation of the three alloys compared with the oxidation of pure Ni3Al alloys was the existence of small α-Al2O3 particles in the middle of the α-Al2O3 scale and the formation of irregularly shaped Kirkendall voids at the alloy-scale interface.
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  • 122
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    Oxidation of metals 47 (1997), S. 381-410 
    ISSN: 1573-4889
    Keywords: Ni-Base superalloys ; Astroloy ; Waspaloy ; Udimet 720 ; oxidation ; chromia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Several commercially available Ni-base superalloys were exposed isothermally in air at temperatures between 750° and 1000°C and also under cyclic conditions at 1000°C. The kinetics of oxidation were determined and the scales were analyzed by electron microscopy and X-ray diffraction. Thin adherent chromia-rich scales formed on the alloys at 750°C after 1000 hr. Although Waspaloy showed the lowest weight gain in this test, it also showed the deepest internal corrosion due to oxidation of the grain-boundary carbides. At temperatures up to 1000°C the external scales were also chromia-rich but there was greater internal corrosion. Titanium in the alloys oxidized, diffusing through the chromia scale to form faceted rutile (TiO2) grains at the surface as well as forming TiO2 and TiN internally. The amount of rutile at the oxide surface increased with temperature and alloy Ti concentration. Alumina formed as discrete internal oxides below the chromia scale, although Astroloy when oxidized isothermally at 1000°C developed a semicontinuous internal layer of alumina due to its higher Al content. Under cyclic conditions Astroloy formed a thicker, less-protective scale of transition oxides probably due to its lower Cr content.
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  • 123
    ISSN: 1573-4889
    Keywords: oxidation ; Incoloy 909 ; superalloy ; scale ; high temperature ; kinetics
    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 of an Fe-38Ni-13Co-4.7Nb-1.5Ti-0.4Si superalloy (Incoloy 909 type alloy), was investigated at temperatures between 1000 K and 1400 K in Ar-(1, 10%)H20 atmosphere using metallographic, electron probe microanalysis, and X-ray diffraction techniques. The oxide scales consist of an external scale and an internal scale which has an intergranular scale (above 1200 K) and an intergranular scale. The oxide phases in each scale are identified asα-Fe2,O3 (below 1200 K) or FeO (above 1300 K) and CoO · Fe2O3 and FeO · Nb2O5, respectively. The morphologies, the oxide phases and the oxidation rates do not depend on the partial pressure of H2O in the range between one and ten percent in Ar gas. The rate constants for the intergranular-scale formation in this alloy are about one-tenth as large as those in Fe-36%Ni alloy reported previously. At all the temperatures the scales grow according to a parabolic rate law and the apparent activation energies for the processes are estimated.
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  • 124
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    Oxidation of metals 47 (1997), S. 445-464 
    ISSN: 1573-4889
    Keywords: oxidation ; Fe-Cr-Al alloy ; water vapor ; ESCA ; RHEED
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Fe-21.5 wt. %Cr-5.6 wt. %Al oxidation, at 1000°C, in dry or wet oxygen shows that steam has an influence on the oxide-scale growth mechanism. Steam modifies the kinetics of early-stage oxidation. In dry oxygen, an initial fast linear regime is observed during one hour. Under wet conditions, weight-gain curves follow the same parabolic regime over the entire oxidation test. The scale structure strongly depends on the presence of steam in the gaseous environment. With dry oxygen, the scale is composed mainly ofα-Al2O3 after the initial formation ofγ-Al2O3 identified by ESCA and RHEED. The kinetics transient stage corresponds to the necessary time for the internal part of the initialγ-Al2O3 scale to transform into a continuousα-Al2O3 diffusion barrier. Under wet oxygen conditions, transient oxides are identified as (Mg, Fe) (Cr, Al)2O4, MgAl2O4 (orthorhombic), Al2O3 (hexagonal), these oxides transform into MgAl2O4 (cubic), Cr3O4, Fe2O3,α-Al2O3, with time. When water vapor does not change drastically oxidation kinetics, the induced presence of iron and chromium in the oxide scale could be responsible for weakening the protectiveness of alumina scales.
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    Oxidation of metals 47 (1997), S. 507-524 
    ISSN: 1573-4889
    Keywords: alloys ; high temperature ; 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 The initial transient high-temperature oxidation stage for binary alloys forming the most-stable oxide has been examined by means of a numerical procedure based on the finite-difference method. At variance with previous models, the present treatment takes into account the effect of the rate of the reaction at the scale/gas interface over the corrosion kinetics. The calculations concerning the transient stage are developed either using the general parabolic rate law to represent the overall scaling kinetics or using the rate law of the reaction at the scale/gas interface as a boundary condition without imposing any particular rate law to the overall process. A correct analysis of the oxidation behavior of binary alloys during the transient stage must take into account the kinetics effect of the rate of the surface reaction. The concentration of the most-reactive element at the alloy/scale interface changes regularly with time, decreasing gradually from the initial bulk value to its final steady-state value. The present results are in good agreement with those obtained by means of an approximate analytical model developed previously.
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  • 126
    ISSN: 1573-4889
    Keywords: high temperatures ; 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 The transient state in the oxidation of solid solutions of a most-noble componentA in a most-reactive componentB (beta phase) for binaryA-B alloys presenting a limited reciprocal solubility of the two metals has been examined assuming that theirB content is sufficient for the exclusive growth of externalBO scales. Above a criticalB content of the alloy theBO scales may grow directly on the surface of the beta phase, while below this limit they can only form over a layer ofB-depleted solid solution ofB inA (alpha phase), which appears after a critical time. An approximate analytical expression for the profile of concentration ofB in the alloy has been adopted to calculate the flux ofB in the metal. Moreover, the effect of the reaction between the gas and the external oxide surface has been taken into account using a procedure developed by Wagner for the oxidation of pure metals. The corrosion kinetics as well as all the parameters involved, such as the concentration ofB at the alloy-scale interface, have been calculated as functions of the corrosion time. The results show that, as time proceeds, the instantaneous parabolic rate constant increases and the concentration ofB at the alloy-scale interface decreases, both tending gradually to their corresponding steady-state values. It is also predicted that if the rate of transformation of the beta phase in the alpha phase after the alloy reaches the composition of equilibrium at the interface with the oxide is lower than the corresponding rate of displacement of the alloy surface due to scale growth, the corrosion of beta phase alloys may eventually lead to the formation of two phase mixtures of alpha phase andBO which are expected to grow at much larger rates than in the presence of a uniform continuous alpha layer.
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  • 127
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    Oxidation of metals 48 (1997), S. 1-39 
    ISSN: 1573-4889
    Keywords: Ni-base ODS superalloys ; oxidation ; initial stages of oxidation ; alumina ; chromia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Mechanically-alloyed Ni-base ODS superalloys currently receive attention for application in future gas turbines because they exhibit outstanding mechanical properties at high temperatures. They also protect themselves against oxidation by forming chromia and/or alumina scales. However, little attention has been given so far to the initial stages of oxidation of Ni-base ODS superalloys, containing Cr as well as Al in considerable amounts. In the current work, oxidation at 1150°C was studied for different holding times up to 200 hr for the commercial materials MA6000 and PM3030 which contain. Al in increasing amounts. MA 754, a chromia former, was investigated as a reference. It was shown that for the potential alumina formers MA6000 and PM3030 the continuity and therefore protectiveness of the secondary Al2O3 at later stages is indeed determined by the initial stages of oxidation.
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  • 128
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    Oxidation of metals 48 (1997), S. 129-141 
    ISSN: 1573-4889
    Keywords: decarburization ; nickel ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A commercial-grade nickel containing small amounts of carbon, manganese, and silicon was exposed to air for periods up to 288 hr at 1050°C to study the effect of oxidation on the formation of oxides of these impurity elements. Exposure of nickel to air led to decarburization. The maximum amount of decarburization occurred during the initial period of air exposure and the loss in carbon was more in the metal with a smaller section size. Decarburization in the metal produced voids in the oxide scale due to the formation of CO2 gas. It has been shown further that CO and/or CO2 gas bubbles, which form in high purity nickel on grain boundaries during exposure to air at elevated temperatures, cannot exist in commercial-grade nickel where manganese is present as an impurity. Instead, oxides of manganese form in the grain boundaries as well as in the matrix. This is because manganese oxide is more stable than CO or CO2 gas.
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  • 129
    ISSN: 1573-4889
    Keywords: oxidation ; kinetics ; iron ; iron-nitride
    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 of α-Fe and ɛ-Fe2N1−z at 573 K and 673 K in O2 at 1 atm was investigated by thermogravimetrical analysis, X-ray diffraction, light-optical microscopy, scanning electron microscopy and electron probe X-ray microanalysis. Upon oxidation at 573 K and 673 K, on α-Fe initially α-Fe2O3 develops, whereas on ɛ-Fe2N1−z initially Fe3O4 develops. In an early stage of oxidation the oxidation rate of ɛ-Fe2N1−z appears to be much larger than of α-Fe. This can be attributed largely to an effective surface area available for oxygen uptake, which is much larger for ɛ-Fe2N1−z than for α-Fe due to the porous structure of ɛ-Fe2N1−z as prepared by gaseous nitriding of iron. The development of a magnetite layer in-between the hematite layer and the α-Fe substrate, at a later stage of oxidation, enhances layer-growth kinetics. After 100 min oxidation at 673 K the (parabolic) oxidation rates for α-Fe and ɛ-Fe2N1−z become about equal, indicating that on both substrates the oxide growth is controlled by the same rate limiting step which is attributed to short-circuit diffusion of iron cations. Oxidizing ɛ-Fe2N1−z increases the nitrogen concentration in the remaining ɛ-iron nitride, because the outward flux of iron cations, necessary for oxide growth, leads to an accumulation of nitrogen atoms left behind.
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  • 130
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    Oxidation of metals 48 (1997), S. 201-214 
    ISSN: 1573-4889
    Keywords: titanium-aluminum alloys ; niobium ; intermetallics ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In a recent study, CO2 has been reported to enhance the oxidation rate of binary titanium-aluminum alloys. The detrimental effect of CO2 was not, however, observed in a ternary alloy containing niobium. In this paper, possible explanations for these observations are examined. First, results from the literature regarding the effects of niobium in improving the resistance of titanium-aluminum alloys are briefly reviewed. Second, a thermodynamic analysis which offers a possible explanation for the beneficial effect of niobium in eliminating the CO2-enhanced oxidation of titanium-aluminum alloys is presented.
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  • 131
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    Oxidation of metals 48 (1997), S. 215-224 
    ISSN: 1573-4889
    Keywords: nanocrystallization ; oxidation ; mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Many mechanisms for the effect of reactive elements on the selective oxidation and scale adhesion of alloys have been proposed. However, nanocrystallization (or microcrystallization) has recently been found to have almost the same effect as that of reactive elements. This note reviews the effect of nanocrystallization on the selective oxidation and adhesion of Al2O3 scale with particular reference to the author's own results.
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  • 132
    ISSN: 1573-4889
    Keywords: oxidation ; titanium ; rutile ; scale ; high temperature ; kinetics
    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 pure titanium has been investigated in the temperature range of 1000 K to 1300 K in CO2 or Ar-10%CO2. Optical microscopy, electron probe microanalyses, and X-ray measurements on the oxide scales formed during oxidation indicate that their structures are nearly independent of temperature and the corrosion atmosphere. The scales consisted of two layers, an external one and an internal one, having a rutile (TiO2) structure. The parabolic rate law was confirmed for growth of the external scale and the permeation depth of oxygen in titanium with apparent activation energies of 266 and 226 kJ/mol, respectively. The rate-determining diffusion species in the oxidation processes are discussed.
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  • 133
    ISSN: 1573-4889
    Keywords: zirconium ; X-ray diffraction ; oxidation ; phase analysis ; texture
    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 of zirconium at high temperature (T〉 400°C) leads to reaction products of two allotropic oxide (ZrO2 monoclinic and ZrO2 tetragonal). The distribution and proportion of these two phases were studied as a function of time and space by X-ray diffraction techniques. Quantitative analyses are possible after some corrections, and we demonstrate the presence of a phase gradient in the oxide scale. The interest of this nondestructive method is then discussed.
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  • 134
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    Oxidation of metals 48 (1997), S. 357-380 
    ISSN: 1573-4889
    Keywords: chromium ; copper ; binary alloys ; two-phase alloys ; oxidation ; high temperatures
    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 in air of three two phase Cu-Cr alloys with nominal Cr contents of 25, 50, and 75 wt. % was studied at 700–900°C. The alloys corroded nearly parabolically, except at 900°C, when the corrosion rates decreased with time more rapidly than predicted by the parabolic rate law. The corrosion rate decreased for higher Cr contents in the alloy under constant temperature and generally increased with temperature for the same alloy composition. The scales were complex and consisted in most cases of an outermost copper oxide layer free from chromium and an inner layer composed of a matrix of copper oxide or of the double oxide Cu2Cr2O4, often containing particles of chromium metal surrounded by chromia and then by the double oxide. Metallic copper was also frequently mixed with chromia. Cr-rich regions tended to form continuous chromia layers at the base of the scale, especially at the highest temperature. No chromium depletion was observed in the alloy.
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  • 135
    ISSN: 1573-4889
    Keywords: iron ; oxidation ; CeO2 coating ; in situ ; growth stress ; residual stress ; texture ; X ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In situ XRD stress determinations have been performed during oxidation of pure iron (p(O2=2 × 10−3 Pa,T=800°C)). The compressive stress, initially present in the substrate due to surface preparation, is completely released at 400°C. Under the test conditions, the in situ compressive-stress level determined in the FeO scale during oxidation is not strongly dependent upon the presence of a ceria coating. On blank and coated specimens, the compressive stress varies from −400 ± 80 MPa to −150 ± 100 MPa during 30 hr oxidation. The decrease is quicker at the beginning of the test performed on blank specimens. Epitaxial relationships between the wüstite scale and iron (under low-pressure starting conditions) caused thein situ compressive stress in the oxide scale to be two times greater compared to the usual test conditions. This indicates that epitaxial relationships can be a source of stress in an oxide scale that ceria coatings may lower compressive stresses.
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  • 136
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    Oxidation of metals 48 (1997), S. 527-551 
    ISSN: 1573-4889
    Keywords: chloridation ; oxidation ; Fe-Cr alloys ; Ni-Cr alloys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The chloridation-oxidation behavior of Fe-Cr (0–25 wt. %Cr) and Ni-Cr (0–20 wt.%Cr) alloys was studied at 800°C in three different H2-HCl-H2O(ν) environments. In a low-HCI and low-H2O(ν) environment, where Cr2O3 is thermodynamically stable, the corrosion resistance of the Fe-Cr alloys increased with increasing Cr content in the alloys. In a high-HCl and high-H2O(ν) environment, where FeCr2O4 is stable and CrCl2 is metastable, the corrosion resistance of the Fe-Cr alloys depended similarly on the Cr content. Low-Cr-Fe-Cr alloys exhibited large weight losses, while Fe-Cr alloys with higher than 19 wt. %Cr showed good corrosion resistance. In an environment of high-HCl in the absence of H2O(ν), the evaporative corrosion rate was fast and limited by gas phase diffusion, and independent of the Cr content in the Fe-Cr alloys. Ni and Ni-Cr alloys generally showed good corrosion resistance in the environments of high H2O(ν) because of the low NiCl2 vapor pressure and formation of a protective Cr2O3 scale. However, in the environment of high HCl in the absence of H2O(ν), selective formation and evaporation of CrCl2 occur, which results in Cr depletion and networks of voids for even a high-Cr Ni-Cr alloy.
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    Oxidation of metals 48 (1997), S. 553-596 
    ISSN: 1573-4889
    Keywords: chloridation ; oxidation ; HCl ; high-temperature alloys ; high-temperature corrosion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Chloridation-oxidation studies of nine commercial high-temperature alloys were carried out at 800°C in three different H2-HCl-H2O(ν) environments: (A) both low HCl and H2O(ν) partial pressures, where either Cr2O3 or FeCr2O4 is stable, (B) both high HCl and H2O(ν) partial pressures, where FeCrO4 is stable and CrCl2 is metastable, and (C) high HCl partial pressure in the absence of H2O(ν), where either CrCl2 or Cr2O3 is stable. Although alloy 600 has the lowest Cr content of these nine alloys, it showed excellent corrosion resistance in all three environments because of its high Ni content. Alloy 304, with the lowest Ni content of the nine alloys, exhibited poor corrosion resistance in the environment C, fair resistance in the environment B and good resistance in the environment A. Alloy 800 showed very good resistance in Environment A, and fair corrosion resistance in Environment B; however, it suffered linear weight-loss kinetics when exposed to Environment C The alloys 617, 214, HR-160, X, 230 and 86 have good corrosion resistance in Environments A and B because of their relatively high contents of oxide-scale-forming elements Cr and/or Al. In Environment C, chlorine dramatically decreased the adhesion of the scale on the surface, and aluminum in alloys 617 and 214 hardly showed its usual beneficial effect in combating corrosion, nor does silicon in alloy HR-160. Different corrosion mechanisms are proposed for the alloys in the different environments.
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    Molecular and cellular biochemistry 194 (1999), S. 257-263 
    ISSN: 1573-4919
    Keywords: glycation ; oxidation ; collagen ; diabetes ; free radicals
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract The present investigation was carried out to understand the effect of metal catalyzed oxidation on glycation and crosslinking of collagen. Tail tendons obtained from rats weighing 200-225 g were incubated with glucose (250 mM) and increasing concentrations of copper ions (5, 25, 50 and 100 μM) under physiological conditions of temperature and pH. Early glycation, crosslinking and late glycation (fluorescence) of collagen samples were analyzed periodically. Early glycation was estimated by phenol sulfuric acid method, and the crosslinking was assessed by pepsin and cyanogen bromide digestion. A concentrationdependent effect of metal ions on the rate of glycation and crosslinking of collagen was observed. Tendon collagen incubated with glucose and 100 μM copper ions showed 80% reduction in pepsin digestion within seven days, indicating extensive crosslinking, whereas collagen incubated with glucose alone for the same period showed only 7% reduction. The presence of metal ions in the incubation medium accelerated the development of Maillard reaction fluorescence on collagen, and the increase was dependent on the concentration of metal ions used. The metal chelator Diethylene triamine penta-acetate significantly prevented the increase in collagen crosslinking by glucose and copper ions. Free radical scavengers benzoate and mannitol effectively prevented the increased crosslinking and browning of collagen by glucose. The results indicate that the metal catalyzed oxidation reactions play a major role in the crosslinking of collagen by glucose. It is also suggested that the prevention of increased oxidative stress in diabetes may prevent the accelerated advanced glycation and crosslinking of collagen.
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    Molecular and cellular biochemistry 206 (2000), S. 151-157 
    ISSN: 1573-4919
    Keywords: cardiac function ; diabetes ; ischemia ; oxidation ; propionyl-L-carnitine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Previous studies have shown that propionyl-L-carnitine (PLC) can exert cardiac antiischemic effects in models of diabetes. In the nonischemic diabetic rat heart, PLC improves ventricular function secondary to stimulation in the oxidation of glucose and palmitate. Whether this increase in the oxidation of these substrates can explain the beneficial effects of PLC in the ischemic reperfused diabetic rat heart has yet to be determined. Diabetes was induced in male Sprague-Dawley rats by an intravenous injection of streptozotocin (60 mg/kg). Treatment was initiated by supplementing the drinking water with propionyl-L-carnitine at the concentration of 1 g/L. After a 6-week treatment period, exogenous substrate oxidation and recovery of mechanical function following ischemia were determined in isolated working hearts. In aerobically perfused diabetic hearts, compared with those of controls, rates of glucose oxidation were lower, but those of palmitate oxidation were similar. Diabetes was also characterized by a pronounced decrease in heart function. Following treatment with by propionyl-L-carnitine, however, there was a marked increase in rates at which glucose and palmitate were oxidized by diabetic hearts and a significant improvement in heart performance. Postischemic recovery of function in diabetic hearts was also improved with PLC. This improvement in contractile function was accompanied by an increase in both glucose and palmitate oxidation. Our findings show that postischemic diabetic rat heart can be improved following chronic PLC treatment. This beneficial effect of propionyl-L-carnitine can be explained, in part, by an improvement in the oxidation of glucose and palmitate.
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    Journal of materials synthesis and processing 8 (2000), S. 359-363 
    ISSN: 1573-4870
    Keywords: Mechanical activation ; brown coal ; electrophoretic mobility ; oxidation ; humic acids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract This paper presents a study of the influence of mechanochemical activation of coal on the process of formation and degradation of humic acids. The increasing period of mechanical activation of coal causes an increase in hydrophility, electrophoretic mobility, and of electrokinetic potential of surface layers as a result of acidic carboxyl and phenolic OH groups. The effective activation requires a short period of grinding. The increased time of activation causes the secondary processes of grain agglomeration and degradation of humic acids.
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  • 141
    ISSN: 1573-4889
    Keywords: oxidation ; segregation ; impurities ; CeO2-coated Fe-20Cr
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The interfacial segregation of sulphur and carbon during the oxidation in 1 torr O2 at 1173 K of Fe-20Cr alloy, which was either free of Ce, alloyed with 0.078 wt.% Ce, or sputter-coated with a 4 nm-thick CeO2 layer, was studied using polyatomic SIMS. Oxidation periods were up to 19 hr. During oxidation, sulphur and carbon accumulated at the alloy-oxide interface region of both uncoated and coated alloys. The amount of segregated sulphur did not vary appreciably with time, whereas carbon increased with time. The total amount of segregants was similar for both uncoated and coated alloys, although the scales formed on the sputter-coated alloy maintained adhesion and were about 10 times thinner than those on the uncoated alloys.
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  • 142
    ISSN: 1573-4889
    Keywords: Incoloy 800H ; oxidation ; sulphidation ; ion implantation ; CER
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Coatings, obtained by preoxidation of Incoloy 800H at low PO2 show good sulphidation resistance due to the higher chromia content in the oxide scale. Yttrium-ion implantation of Incoloy 800H has also a beneficial effect on sulphidation, if preoxidation is applied. The reason for this is presumably the segregation of yttrium to grain boundaries of the oxide. Furthermore, the oxidation kinetics of Incoloy 800H are independent of the partial pressure of the oxygen. Mechanical testing of the preformed oxide scale/substrate combinations in air at 600°C by means of constant-extension-rate experiments shows that preoxidation at low partial pressures of oxygen leads to earlier scalecracking.
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  • 143
    ISSN: 1573-4889
    Keywords: oxidation ; sulphur ; manganese ; silicium ; precipitate ; cracks
    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 of presulphidized Ni-Cr alloys has been studied by taking into account the influence of the two distinct oxidation mechanisms described in part I of this article. Sulphur enters the Cr2O3 scale (in Ni-34Cr alloys) mainly as S2− species, which at high temperatures increases the V‴Cr content, and hence the oxidation kinetics. Sulphur is randomly distributed in the scale, except at the inner oxide-alloy interface, where intergranular microsulphides are analyzed in the oxide-scale zone. In the case of NiO, NiCr2O4, Cr2O3 oxide multilayers (in a Ni-20Cr alloy), sulphur in the S2− state is distributed in the oxide layers or at Si-precipitate interfaces. Such a distribution leads to crack formation, especially during cooling.
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    Oxidation of metals 33 (1990), S. 301-308 
    ISSN: 1573-4889
    Keywords: Pb-In alloys ; oxidation ; oxide-inversion layer ; Auger analysis
    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 of several single-phase Pb-In alloys has been studied in air at room temperature using AES (Auger electron spectroscopy) combined with sputter-depth profiling. Alloy samples with indium composition between 3 and 64 at.% In, which were prepared using a microtome, were oxidized in air. The oxidation of alloys with low In contents was found to be the same as that of Pb-2.9 at.% Sn.1 Increasing the bulk composition of In increased the ratio of oxidized In to oxidized Pb in the oxide mixture, although Pb oxide was observed even on the surface of the oxide for samples up to 64 at.% In. The oxidation behavior of Pb-In alloys can be explained in terms of preferential oxidation of In due to its much greater affinity for oxygen than Pb.
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    Oxidation of metals 34 (1990), S. 47-70 
    ISSN: 1573-4889
    Keywords: erosion ; oxidation ; angle of incidence ; nickel ; cobalt
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The combined erosion-oxidation of cobalt and nickel at 600 and 780°C over a range of particle-impact angles has been studied by using weight change vs. time measurements and extensive morphological and microstructural characterization of exposed specimens. The oxidation process has been found to affect the angular dependence of the degradation rates. The effect is especially significant at low-impact angles where ripples and flakes are developed upon the surfaces of specimens.
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    Oxidation of metals 34 (1990), S. 465-472 
    ISSN: 1573-4889
    Keywords: Al-Mg alloys ; oxidation ; MgO layers ; growth mechanism ; oxide morphology
    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 of Al-5Mg alloy has been studied at 550°C in dry air. Morphological details of the MgO layers which develop on this alloy during hightemperature oxidation have been studied by scanning electron microscopy (SEM). A localized detachment of the protective, adherent MgO layer was found, which is caused by voids formed by vacancy condensation at the metal-oxide interface. The source of these vacancies was the outward diffusion of Mg through the oxide layer. Continuing growth of these voids was responsible for cracking of oxide ridges and nodules, as well as the growth of new MgO having a “cauliflower” morphology. A model describing the process of the outward diffusion is given.
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    Oxidation of metals 35 (1991), S. 333-348 
    ISSN: 1573-4889
    Keywords: oxidation ; multiphase alloys ; stereology ; diffusion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A nonsteady-state diffusional analysis has been applied to the oxidation of binary multiphase alloys. In addition to the solubility of the solute element in the continuous solid-solution phase, the volume fraction and the size of the second-phase particles have been found to be crucial for the exclusive formation of the solute oxide. By solving the diffusion equations, the oxidation behavior of a multiphase alloy has been quantitatively related to a microstructure parameter, P L ,which is a function of both the volume fraction and shape of the second phase. Moreover, the effectiveness of alloying for alloys with differently shaped second-phase particles on the oxidation of multiphase alloys has been discussed.
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    Oxidation of metals 36 (1991), S. 113-141 
    ISSN: 1573-4889
    Keywords: oxidation ; aluminide intermetallics ; niobium-aluminum-chromium alloys ; reactive element effect ; aluminum oxide scales
    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 of NbAl3 with additions of Cr and Y was studied to determine the mechanisms of the beneficial effects of these elements upon oxidation. Cr additions to the binary Nb Al3 alloy of up to 6.8 at. % reduced the scale growth rates and promoted α-Al2O3 formation over much longer times relative to binary NbAl3. A major effect of Cr is to form a layer of AlNbCr at the metal/ scale interface, which is inherently more oxidation-resistant than the matrix alloy in the long term. Yttrium additions to a Cr-containing alloy improved the scale growth rate and adherence, and changed the scale micro structure to mimic that of a typical protective Al2O3 scale.
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    Oxidation of metals 36 (1991), S. 157-174 
    ISSN: 1573-4889
    Keywords: bixbyite ; iron-chromium-manganese alloys ; spinel ; oxidation
    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 of nine ternary iron-chromium-manganese alloys was studied at 900°C in an oxygen partial pressure of 26.7 kPa. The manganese concentration was set at 2, 6, and 10 wt. %, and chromium at 5, 12, and 20 wt. %. The scales formed on the low-chromium alloys consisted of (Mn,Fe)2O3, α-Fe2O3, and Fe3O4. These alloys all exhibited internal oxidation and scale detachment upon cooling. The scales formed on the higher-chromium alloys were complicated by nodule formation. Initially, these scales had an outer layer of MnCr2O4 with Cr2O3 underneath, adjacent to the alloy. With the passage of time, however, nodules formed, and the overall reaction rate increased. This tendency was more marked at higher manganese contents. Although these alloys contained a high chromium content, the product chromia scale usually contained manganese. It was concluded that the presence of manganese in iron-chromium alloys had an adverse effect on the oxidation resistance over a wide range of chromium levels.
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  • 150
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    Oxidation of metals 36 (1991), S. 265-280 
    ISSN: 1573-4889
    Keywords: mild steel protection ; aluminum alkyls ; aluminizing ; oxidation ; microbalance ; deposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The deposition of Al on 1010 steel from mixtures of trimethyl (TMA) and triethyl (TEA) aluminum alkyls in argon and hydrogen was studied. Unlike earlier work with SiH4/H2 no aluminum diffusion onto the steel was observed even when the samples were heated to 800°C. Coatings obtained with TEA at temperatures between 300–400°C resulted in overlays of elemental Al or Al oxide after exposure to ambient conditions. No deposition was obtained at temperatures higher than 400°C in a hot-wall reactor due to rapid decomposi tion of TEA on the walls of the reactor. Deposition with TMA at temperatures between 400–800°C resulted in overlays of Al carbide. For deposition at tem peratures higher than 500°C, a cold-wall reactor was used. The Al overlay coatings resulting from TMA were dense, homogeneous, and adhered well to the steel. Both kinds of coatings provided oxidation protection to the steel in air at 800°C. The performance of the coatings produced with TMA was superior to the coatings produced with TEA and similar to the performance of an Alonized steel.
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  • 151
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    Oxidation of metals 36 (1991), S. 465-474 
    ISSN: 1573-4889
    Keywords: Pb-In alloy ; oxidation ; logarithmic and parabolic kinetics ; short-circuit diffusion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The solid-state oxidation kinetics of a Pb-64 at. % In (50 wt. %) single-phase alloy were studied from room temperature to 150°C using an AES (Auger Electron Spectroscopy) depth profiling technique. The general oxidation behavior of this alloy is different from that of a Pb-3 at.% In alloy but similar to that of a Pb-30 at.% In alloy. The oxide formed on this alloy is almost pure In oxide (In2O3) with the possible existence of some In suboxide near the oxide/alloy interface. At room temperature, oxidation of the alloy follows a direct logarithmic law, and the results can be described by the model proposed previously by Zhang, Chang, and Marcotte. At temperatures higher than 75° C, rapid oxidation occurred initially followed by a slower parabolic oxidation at longer time. These data were described quantitatively by the model which assumes the existence of short-circuit diffusion in addition to lattice diffusion in the oxide as proposed by Smeltzer, Haering, and Kirkaldy. The effects of alloy composition on the oxidation kinetics of (Pb, In) alloy are also examined by comparing the data for Pb-3, 30, and 64 at. % In alloys.
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  • 152
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    Oxidation of metals 37 (1992), S. 167-187 
    ISSN: 1573-4889
    Keywords: H2-H2S-H2O ; sulfidation ; NbO2 ; oxidation ; CoNb3S6
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The corrosion of Co-Nb alloys containing up to 30 wt.% Nb in H2-H2S-H2O gas mixtures was studied over the temperature range of 600–800°C. The gas composition falls in the stability region of cobalt sulfide and Nb2O5 in the phase diagrams of the Co-O-S and Nb-O-S systems at all temperatures studied. Duplex scales, consisting of an outer layer of cobalt sulfide and a complex, heterophasic inner layer, were formed at all temperatures studied. In addition to cobalt sulfide and CoNb3S6, a small amount of NbO2 was found in the inner layer. The reason for the formation of NbO2 over that of Nb2O5 in the scale is that the outer sulfide scale lowers the oxygen activity within the scale into the NbO2-stability region. Two-stage kinetics were observed for all alloys, including an initial irregular stage usually followed by a steady-state parabolic stage. The steady-state parabolic rate constants decreased with increasing amounts of Nb, except for Co-20Nb corroded at 700°C. Nearly identical kinetics were observed for Co-20Nb corroded at 600°C and 700°C. The presence of NbO2 particles leads only to a limited decrease of the available cross-section area for the outward-diffusing metal ions. The activation energies for all alloys are similar and are in agreement with those obtained in a study of the sulfidation of the same alloys. The primary corrosion mechanism involves an outward Co transport.
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    Oxidation of metals 37 (1992), S. 217-252 
    ISSN: 1573-4889
    Keywords: mixed gas ; Nb2O5 ; NiNb3S6 ; NiNb2S4 ; multi-layered scales ; oxidation ; sulfidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The corrosion behavior of Ni-Nb alloys containing up to 40 wt.% Nb was studied over the temperature range of 550–800°C in a mixed H2/H2O/H2S gas. The scales formed on all alloys were multilayered. The outer scale was single-phase Ni3S2, while the structure and constitution of the inner scale depended on alloy composition and reaction conditions. Internal oxidation has been found in Ni-20Nb and Ni-30Nb, external oxidation has been observed on Ni-34Nb. Platinum markers were located at the interface between the outer scale and inner scale. The decrease in corrosion rate with increasing Nb content may be attributed to the presence of increasing amounts of Ni-Nb double sulfides as well as to the presence of Nb2O5 in the inner region of the scale.
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  • 154
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    Oxidation of metals 38 (1992), S. 45-72 
    ISSN: 1573-4889
    Keywords: intermetallic-matrix composites ; oxidation ; NiAl ; fiber/matrix interfaces
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The 1200°C and 1300°C isothermal and cyclic oxidation behavior of Al2O3 continuous fiber (Saphikon™)-reinforced/ NiAl composites were studied. Oxidation resulted in formation of Al2O3 external scales in a similar manner as scales formed on monolithic NiAl. The isothermal oxidation of an Al2O3/NiAl composite resulted in oxidation of the matrix along the fiber/matrix interface near the fiber ends. This oxide acted as a wedge between the fiber and matrix, and, under cyclic oxidation conditions, led to further oxidation along the fiber lengths and eventual cracking of the composite. The oxidation behavior of composites in which the Al2O3 fibers were sputter coated with nickel prior to processing was much more severe. This was attributed to open channels around the fibers which formed during processing most likely as a result of the diffusion of the nickel coating into the matrix.
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  • 155
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    Oxidation of metals 38 (1992), S. 89-98 
    ISSN: 1573-4889
    Keywords: kinetics ; oxidation ; zirconium hydride
    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 kinetics of zirconium-hydride powders were studied in the temperature range of 298–1378 in air at atmospheric pressure. TG, DTA, DSC, x-ray analysis, and scanning electron microscopy were used. The results obtained are in accordance with the proposed pseudo-parabolic model of zirconium-hydride oxidation. This model includes the initial linear mode of oxide growth with oxygen diffusion through a non-solid film of ZrO2 of variable depth and a stationary diffusion process followed by oxide sintering. It has been established that the activation energy of the limiting stage of oxidation (238.3 kJ/mol) coincides with the activation energy of oxygen self-diffusion in monocline ZrO2.
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    Oxidation of metals 38 (1992), S. 267-287 
    ISSN: 1573-4889
    Keywords: oxidation ; electrons ; electrolyte ; ionic conduction ; electric field
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The imposition of a dc voltage across an oxide-ion-conducting solid electrolyte, upon which a gradient in the chemical potential of neutral oxygen (O, O2) is maintained, causes coupled gradients in the electrochemical potentials of oxygen ions and electrons. The concept of balancing these gradients to provide oxidation protection at high temperatures is discussed. Experimental results show a significant reduction in the oxidation of a zircaloy substrate under an applied electric field near the open-circuit potential. The current densities required are small enough to allow the use of electrically-conducting-ceramic electrodes.
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    Oxidation of metals 39 (1993), S. 197-209 
    ISSN: 1573-4889
    Keywords: oxidation ; binary alloys ; two-phase alloys
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The corrosion behavior of binary, two-phase alloys is considered in which the matrix contains mostly the less-noble metal that forms a fast-growing oxide, while the second phase is rich in a component that forms a more stable but slowly-growing oxide. It is assumed that the second phase exists as a dispersion of isolated, rod-like particles. It is further assumed that both phases form external films with no internal oxidation. It is shown that the oxidation behavior of this type of alloy depends on both the oxidation time and the size of the second-phase particles. In particular, for short oxidation times and large second-phase particles the matrix will oxidize faster than the dispersed phase, so that the dispersed particles will be only partly corroded or even incorporated into the matrix-oxide scale as unoxidized islands, forming an irregular alloy-scale interface. On the contrary, for long times and small particle sizes the two phases will tend to oxidize at approximately the same rate, leading to the formation of regular alloy-scale interfaces. The time for the transition between the two corrosion regimes depends not only on the ratio between the rate constants for the growth of the two oxides but also on the size of the dispersed-phase particles, smaller sizes producing shorter transition times. Eventually, under favorable conditions the formation of the fast-growing oxide may even stop, leading to the formation of a protective layer of the most-stable oxide.
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    Oxidation of metals 38 (1992), S. 299-307 
    ISSN: 1573-4889
    Keywords: microcrystal ; sputtering ; oxidation ; superalloy
    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 of sputtered and cast superalloy K38G specimens was studied. The sputtered alloy was microcrystalline, with an average grain size 〈0.1 μm. The mass gains of the sputtered alloy were much less than those of the cast alloy at 800, 900, and 1000°C up to 500 hr, and were even less than those of pack aluminide on the cast alloy. K38G is a chromia-forming cast nickel-base superalloy, so the oxide scale formed on it is composed of Cr2O3, TiO2, Al2O3, and a spinel. The oxide scale formed on the sputtered alloy was Al2O3. This scale is thin, compact, and adherent. This result implied that micro crystallization reduced the critical aluminum content necessary to form alumina on the surface of this superalloy. No oxide spoliation, as typically observed for cast of aluminized alloys, occurred on the sputtered superalloy. The reduction of the critical aluminum content for the formation of alumina and the improvement of the spoliation resistance may be attributed to the microcrystalline structure formed during sputtering. The numerous grain boundaries favor outward aluminum grain-boundary diffusion, provide increased nucleation sites, and reduced stresses in the oxide scales.
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    Oxidation of metals 41 (1994), S. 343-364 
    ISSN: 1573-4889
    Keywords: oxidation ; alumina scales ; adherence ; cavities
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Several features of the microstructure and the adherence of alumina scales formed on Fe−Cr−Al and Fe−Cr−Al−Y single- and polycrystalline alloys after oxidation at 1000°C were examined. The convolutions of the scale and especially of the scale/alloy interface are thought to be the major reason of poor spallation resistance of scales on the yttrium-free alloy. The flat oxide scale on the even interface of the yttrium-doped alloy, on the contrary, exhibits excellent adherence upon cooling. Interfacial cavities observed on the Fe−Cr−Al alloy result from the scale undulation under compressive growth stresses. The shape and the number of cavities depend on the initial surface orientation and most probably reflect a balance between the interfacial energy of convoluted substrate in contact with the oxide layer and the energy of separated surfaces.
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    Oxidation of metals 44 (1995), S. 265-308 
    ISSN: 1573-4889
    Keywords: oxidation ; corrosion ; high temperatures ; erosion ; wear
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract There are several engineering systems which require materials of construction to tolerate elevated temperatures, and aggressive environments of one kind or another; and where, furthermore, the performance of the system is limited by the materials capability. This paper reviews a number of these systems, drawn principally from the electric power industry, and describes both the current approaches to improving the materials capability, and potential directions for research and development for the future. Particular emphasis is given to cases where the problems related to oxidation and high-temperature corrosion are of major importance.
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    Oxidation of metals 44 (1995), S. 339-374 
    ISSN: 1573-4889
    Keywords: analytical techniques ; Fe, Cr, Fe−Cr alloys, Ni, Al, β-NiAl ; oxidation ; transport processes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract This paper considers the application of analytical techniques (particularly AES, SIMS, RHEED, laser Raman, Mössbauer, TEM, EELS) to high-temperature oxidation studies. Specific systems reviewed include NiO on Ni, oxides on Fe, Cr and their alloys, and Al2O3 on Al and β-NiAl. The often complementary information provided by the various techniques leads to a better understanding of oxide growth mechanisms on an atomic sale, interfacial segregation phenomena, and the role of reactive elements in modifying transport processes in oxides.
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    Oxidation of metals 44 (1995), S. 239-264 
    ISSN: 1573-4889
    Keywords: oxidation ; carburization ; sulfidation ; scaling ; internal precipitation ; diffusion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Scaling reactions between pure metals and multiple oxidant gases are reviewed briefly. It is recognized that elemental oxidant activities are usually so low that the actual reactant species are heteronuclear molecules such as SO2, CO2, etc. The formation of duplex, sulfide-oxide scales on iron and manganese, even when sulfide is unstable with respect to oxide, is attributed to direct reaction with SO2. The persistence of the metastable sulfide is due to its preservation by the rapidly growing scale. The reaction of pure chromium with a number of mixed gases is also discussed. The continued formation of carbides and nitrides beneath an external Cr2O3 scale layer indicates that the latter material is permeable to gas species. Interaction among different gas species is observed, and is attributed to selective adsorption on internal surfaces within the chromium oxide. New work on the reaction of alloys with mixed gases is reported. Several austenitic heat-resistant alloys were exposed at 1000°C to gases containing one, two or all of the oxidants carbon, sulfur and oxygen. Gases containing two or more oxidants produced multiple zones of internal precipitation. The precipitates were chromium-rich oxides, sulfides and carbides arranged in order of thermodynamic stability: oxides beneath the external scale, carbides deepest within the alloys and sulfides in an intermediate zone overlapping the oxide zone. Each precipitate zone widened according to parabolic kinetics. This finding confirms the as yet untested prediction made by J. L. Meijering in 1971. However, the rate at which a particular zone grows changes according to presence of other oxidants. Interactions between the oxidants can be large and reaction rates are currently not predictable.
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    Oxidation of metals 53 (2000), S. 427-449 
    ISSN: 1573-4889
    Keywords: sulfidation ; carburization ; oxidation ; high-temperature corrosion ; commerical alloys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A sulfidation/carburization study of seven commercial heat-resistant alloyswas carried out at 900°C in a H2–25 vol.%CH4–14.8N2–4CO–0.6CO2–0.6H2Satmosphere. The equilibrium partial pressures for oxygen (O2) andsulfur (S2) were 1.1×10−22 and 4.1×10−8 atm,respectively, and the carbon activity for this system was unity. The time ofexposure was 500 hr. Relatively thick, mixed sulfide scales were formed onall of the alloys tested. In addition, internal carburization occurred inall of the alloys. Using metal loss (i.e., the reduction in samplethickness) plus internal attack (internal sulfidation plus internalcarburization) as a performance criterion, an alloy with a nominalcomposition of Ni–29 wt.% Co–28Cr–2.75Si performed thebest, showing 0.71 mm of attack. An alloy with a nominal composition ofFe–20 wt.% Ni–25Cr performed the worst, being totally consumedby the test (〉3.18 mm of attack). Alloys containing relatively highamounts of silicon (〉2.5%) showed a dramatic increase in theirsulfidation resistance compared to the other alloys containing lowersilicon contents. The amount of iron present within a given material playeda dominant role in the carburization attack that occurred, with as expected,high-iron alloys showing significant internal carburization because of ahigh solubility and diffusivity of carbon in the matrix. The importance ofthe various alloying elements with respect to sulfidation and carburizationresistance is discussed.
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  • 164
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    Keywords: oxidation ; chromia ; alumina ; thin oxide films ; reactive element
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In order to study the effects on oxidation behavior of changing thecomposition of oxide scales without changing the composition of theunderlying alloys, thin films, which contained various amounts of Y2O3,Cr2O3, or Al2O3 have been deposited on Fe–25%Cr andFe–25%Cr–5%Al prior to oxidation. There were major differencesbetween the (Fe–25%Cr)–(Cr2O3–Y2O3) and(Fe–25%Cr–5%Al)–(Al2O3–Y2O3) systems. A film ofCr2O3 on Fe–25%Cr reduced the oxidation rate and Cr2O3–Y2O3films reduced it still further. A film of Al2O3 onFe–25%Cr–5%Al reduced the rate considerably, butAl2O3–Y2O3 films exhibited rates that were greater than those forAl2O3 alone. A film, which consisted entirely of Y2O3, greatly decreasedthe oxidation rate of Fe–25%Cr, but increased that ofFe–25%Cr–5%Al. The changes in oxidation rate produced byY2O3 in the (Fe–25%Cr)–(Cr2O3–Y2O3) system weremuch greater than those produced in the(Fe–25%Cr–5%Al)–(Al2O3–Y2O3) system. As far asoxidation rate is concerned, the optimum amount of Y2O3 in the(Fe–25%Cr)–(Cr2O3–Y2O3) system was found to begreater than or equal to 40% and less than 100%; in theFe–25%Cr–5%Al)–(Al2O3–Y2O3) systemit was approximately 10%. In thermal-cycling tests, the resultsfor the (Fe–25%Cr)–(Cr2O3–Y2O3) system followedthe same pattern as that for the isothermal tests; a film of Y2O3reduced the oxidation rate and a film of Cr2O3–33%Y2O3reduced it still further.
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  • 165
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    Keywords: Fe–Cr–Al alloy ; oxidation ; molybdenum ; breakaway oxidation ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Thin foils of Fe–20Cr–5Al alloys are susceptible to breakawayoxidation once the aluminum content of the substrate has fallen below somecritical value. The combined addition of 0.1 wt.% lanthanum and 0, 1, or 2wt% molybdenum has a beneficial effect on the high-temperature oxidation ofsuch foils. Lanthanum has the well-known reactive-element effect on adhesionof the protective alumina scale, thereby increasing the time to onset ofbreakaway oxidation, while, for alloys containing molybdenum, breakawayoxide spreads relatively slowly over the specimen in comparison to alloysthat contain no molybdenum. In particular, molybdenum-containing alloys areable to develop a protective Cr2O3 layer at the breakawayoxide–substrate interface. Conversely, molybdenum-free alloys form aninternal-oxide zone in the substrate adjacent to this interface, rather thana Cr2O3 layer, so breakaway oxide spreads rapidly. A martensitic phase isobserved in the substrate adjacent to the breakaway oxide formed on Fe–20Cr–5Al–La specimens, which means that theα-phase has transferred to the γ -phase at the temperature ofthe oxidation test (1150°C). Conversely, α-phase is retained inthe molybdenum-containing alloy, even after breakaway takes place, sincemolybdenum, which is a strong ferrite former, is enriched in the alloyadjacent to areas of breakaway oxide. The diffusion rate of chromium isslower in the γ than in the α-phase so a continuouschromium-rich oxide layer, which is effective in inhibiting breakawayoxide from spreading, cannot be established at the breakawayoxide–substrate interface for the molybdenum-free alloys.
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    Oxidation of metals 54 (2000), S. 63-71 
    ISSN: 1573-4889
    Keywords: microstructure ; Inconel 625 ; oxidation ; deformation substructure ; deformation twins ; energy-dispersive spectroscopy (EDS) ; internal oxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The high-temperature, isothermal-oxidation behavior of a superalloy was studied in the as-rolled and deformed conditions. The microstructural changes occurring during the oxidation of samples were examined using optical, scanning electron microscopy (SEM), fine-probe EDS microanalysis, and X-ray diffraction techniques. The topography of the oxide layers formed in the as-rolled and cold-deformed specimens exposed at various temperatures and time intervals is also examined. The kinetics and microstructural results are presented for the comparative study of the structural changes occurring during high-temperature oxidation. It was found that a Cr2O3 external layer was adherent and uniform on the rolled specimens in comparison to the scattered and preferential oxide developed on the deformed specimens. The latter can be attributed to the concurrent dynamic changes occurring in the deformed substructure that subsequently lead to breaking and spallation of the oxide.
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    Oxidation of metals 54 (2000), S. 121-138 
    ISSN: 1573-4889
    Keywords: titanium aluminides ; oxidation ; oxygen-affected zone ; alpha case ; TEM
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The isothermal oxidation behavior of binary Ti–25 at.% Al was studiedat 1073, 1173, and 1273 K in air and oxygen with emphasis on themicrostructure of the subsurface zone underneath the external oxidescale. Thermogravimetric analysis, acoustic-emission (AE) analysis, lightmicroscopy, scanning electron microscopy (SEM), atomic force microscopy(AFM), and cross-sectional transmission electron microscopy (TEM) werecarried out. Three layers could be identified in the subsurface regionconsisting of an internal oxidation zone of α-Al2O3,and α-Ti, a ternary phase with the empirical formulaTi–21Al–15O (at.%), and an oxygen penetration zone consisting ofα2-Ti3Al(O).
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    Oxidation of metals 54 (2000), S. 445-456 
    ISSN: 1573-4889
    Keywords: quasicrystals ; aluminides ; oxidation ; nodules
    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 of a quasicrystal with the nominal compositionAl63Cu25Fe12 was studied around 800°Cin environmental and synthetic air by means of thermogravimetric analysis,electron microscopy, and analytical electron spectroscopy. In an earlyoxidation stage, γ-Al2O3 formed with an orientational relationship tothe quasicrystal. At the oxide–metal interface, γ-Al2O3transformed into large hexagonal shaped α-Al2O3grains. The change in surface morphology indicated that at theoxide–gas interface γ-Al2O3 continued togrow as Θ-Al2O3. Locally the metastable aluminalayer was transformed thoroughly into α-Al2O3,which then continued to grow with a nodular morphology. On top of the oxidenodules, several at.% of Cu2+ were detected.
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    Oxidation of metals 45 (1996), S. 153-181 
    ISSN: 1573-4889
    Keywords: oxidation ; 18O diffusion ; nickel ; stress effects on diffusion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract This study deals with the influence of various mechanical loadings (fatigue, creep, creep-fatigue) on oxygen diffusion in a particular system, oxidizing nickel. A distinction between the behavior of the oxide layer and underlying nickel was noted during the first step of oxidation at 550°C, in PO 2=1 atm. Mechanical loading causes a decrease of the oxygen mobility through the oxide scale (factor of 103). The oxide thicknesses on nickel undergoing mechanical loadings are different than for an unloaded sample, due to distinct contributions of the oxygen and nickel fluxes in the growing oxide. In the substrate, the ingress of oxygen becomes easier with a constant tensile load (creep). The intergranular-oxygen diffusion coefficient, Di, is increased by a factor of 102 with respect to other samples. In creep, oxygen diffusion takes place along grain boundaries of a structure with smaller grains than in unstrained Ni. A short fatigue period during creep-fatigue decreases the sensitivity of nickel to intergranular-oxygen diffusion.
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    Molecular and cellular biochemistry 112 (1992), S. 35-44 
    ISSN: 1573-4919
    Keywords: lactoperoxidase ; 5,7-dihydroxytryptamine ; oxidation ; peroxidation ; superoxide dismutase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Spectral data provide the first evidence that lactoperoxidase, a model enzyme for most mammalian peroxidases, catalyzed the one-electron oxidation and/or peroxidation of 5,7-dihydroxytryptamine. This process correlates with the production of superoxide radicals as is evident from the observed inhibitory effect of superoxide dismutase on product formation. 5,7-Dihydroxytryptamine is a classical peroxidase-oxidase substrate acting as a one-electron donor for enzyme compounds I, II and III. The one-electron peroxidatic oxidation of this serotonergic neurotoxin, responsible for the selective degeneration of central (5-hydroxytryptamine) neurons, is a fast process requiring measurement on the ms time scale. Attention is drawn to the biochemical and toxicological implications, because this fast reaction results in formation of known cell damaging species: free radicals, superoxide radicals and quinoidal products probably involved in the toxic action of 5,7-dihydroxytryptamine.
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  • 171
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    Molecular and cellular biochemistry 95 (1990), S. 177-182 
    ISSN: 1573-4919
    Keywords: periodate ; oxidation ; membrane ; cells ; interleukin-1
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Interleukin-1 (IL-1) production by periodic acid (H5IO6)-oxidized human peripheral blood mononuclear (PBMN) cells was assessed by the thymocyte co-mitogenesis assay. Maximum IL-1 levels (∼ 1.2 U/ml) in the conditioned media of PBMN cells were registered within the first 24 hrs post-oxidation, whereas no IL-1 was detected in the media from 24 hrs control cultures. Thymocyte proliferation, driven by periodic acid-induced IL-1, was abolished by an antibody to IL-1alpha and IL-1β. Quantitative analysis of IL-1-containing medium by radioimmunoassay (RIA) indicated that IL-1β comprised about 80% of total IL-1. Partial characterization of H5IO6-induced IL-1β indicated that it was identical to IL-1 produced by lipopolysaccharide-stimulated macrophages. It is concluded that oxidation of human PBMN cells by H5IO6 triggers synthesis and release of IL-1, most of which was in its IL-1β form.
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  • 172
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    Journal of materials synthesis and processing 6 (1998), S. 191-195 
    ISSN: 1573-4870
    Keywords: Transmission electron microscopy observation ; interfacial microstructure ; oxidation ; ZrC ; cubic ZrO2 ; amorphous carbon film
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Microstructure at the interface of ZrC and ZrO2 formed by oxidation of a single crystal of ZrC with 100 faces at 600°C at an oxygen pressure of 2 kPa was observed by high-resolution transmission electron microscopy and scanning electron microscopy. The ZrO2 scale was shown to consist of two subscales, zones 1 and 2. The interfacial area in zone 1 was composed of regular lattice fringes corresponding to the 111, 200, and 220 lattices of cubic ZrO2 (c-ZrO2) crystallites 2 to 10 nm in size and an amorphous phase. The growth of crystallites occurred in zone 2, which visualized the interface of zones 1 and 2. Black thin films reminiscent of zone 1 were successfully separated, which were composed of amorphous carbon in which c-ZrO2 particles 2 to 20 nm in size were included.
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  • 173
    ISSN: 1573-4889
    Keywords: oxidation ; carbon ; manganese ; nickel ; silicon ; Ni-Cr alloys
    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 Ni-Cr alloys (34 and 20 wt.% Cr) was investigated between 850 and 1200°C in oxygen for a maximum duration of about 70 hr. The oxide-growth mechanism is a diffusion process controlled by either outward diffusion of chromium in Cr2O3 (Ni-34Cr alloy) or by an increase in grain size (Ni-20Cr alloy). In the case of the Ni-34Cr alloy, low values of chromium diffusion were found for the growth of Cr2O3 by taking into account the general equation of Wagner. The influence of impurities (Si, C, Mn, Ni) diffusing from the underlying alloy is analyzed because of their doping effect in the outer oxide scales.
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  • 174
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    Oxidation of metals 34 (1990), S. 23-45 
    ISSN: 1573-4889
    Keywords: erosion ; oxidation ; high-temperature corrosion ; interactions ; nickel ; cobalt
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The combined erosion-oxidation of nickel, cobalt, and the oxides of these metals have been studied at 780°C in air to examine two regimes of interactionnamely, a regime of erosion-enhanced oxidation during which an oxide scale of constant thickness covers metal specimens, and a regime of oxidation-affected erosion that is characterized by a composite surface layer of metal, oxide, and erodent. In the case of cobalt, these two regimes have been documented and the transition from one regime to another described. For the range of conditions examined, only the oxidation-affected erosion regime was observed for nickel due to its lower oxidation rate compared to cobalt.
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  • 175
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    Oxidation of metals 34 (1990), S. 217-228 
    ISSN: 1573-4889
    Keywords: pack Cementation ; titanium aluminides ; activator ; diffusion ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The practical application of titanium aluminide metal-matrix composites (MMCs) at high temperatures requires suitable surface coatings to provide the needed oxidation resistance. Without a coating, the titanium aluminide alloys suffered from rapid oxidation attack at elevated temperatures, particularly under thermal cyclic conditions. The pack-cementation coating process was utilized to aluminize the surface region of a Ti3Al-base alloy to TiAl3, the most oxidation-resistant phase. With the existence of an adherent conversion coating, a thin protective alumina scale formed on the outer surface, and a significant improvement in the corrosion resistance was observed. Excellent coating efficiency and geometric flexibility were demonstrated in this study by the pack-cementation technique. Further development of the cementation process will focus on the elimination of surface cracking in the coating.
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  • 176
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    Oxidation of metals 34 (1990), S. 229-258 
    ISSN: 1573-4889
    Keywords: nickel ; oxidation ; oxygen tracer ; SIMS ; duplex scale
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The effect of oxidation conditions on the penetration of oxygen into growing nickel oxide scales has been examined using oxygen isotope tracers and SIMS analysis. Depth profiles and cross-section images of oxide scales show that the proportion of oxygen penetration is increased as the temperature is reduced. At 600°C, the amount of oxygen tracer transported to the scale-metal interface is considerable, approaching that observed for a conventional “duplex” microstructure. The formation of healing oxide along numerous fissures through the oxide is directly observed in SIMS images. These fissures seem to coincide with grain boundaries in the preexisting oxide. As the oxidation temperature is increased, the oxygen transport becomes less uniform, some regions of the scale showing little or no transport. Reduction in the oxygen pressure reduces the amount of oxygen penetrating the scale.
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    Oxidation of metals 34 (1990), S. 323-333 
    ISSN: 1573-4889
    Keywords: Al-Mg alloys ; oxidation ; high-temperature mechanisms
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Surface-analysis techniques (x-ray photoelectron spectroscopy and Auger electron spectroscopy) and electron microscopy (SEM and TEM) have been used to study the mechanism of steady-state high-temperature oxidation of Al-Mg alloys. Two high-purity alloys containing 0.4 and 2.0 wt.% Mg were heat-treated in dry air at 550°C up to 90 hr. It was found that the oxide layer was composed of MgO and spinel (MgAl2O4), the major constituent being MgO. The molar concentration of MgO decreased with increasing depth, while that of spinel increased. The rate-controlling mechanism for the growth of the oxide layer in the Al-0.4Mg alloy was the solid-state diffusion of Mg in the MgO-spinel constituents. For alloys of higher-magnesium content, the growth of the oxide layer was controlled by solid-state diffusion of Mg through the adherent protective oxide areas and by the transport of Mg vapor across voids formed between the alloy substrate and the oxide layer.
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    Oxidation of metals 33 (1990), S. 1-17 
    ISSN: 1573-4889
    Keywords: Ni-Cr-Al alloys ; alloy microstructure ; oxidation ; refractory-metal additions
    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 at 1023 and 1123 K in air has been followed for several Ni-Cr-Al ternary alloys and with small additions of refractory elements Nb, Mo, and Ta. Prior to testing, the alloys were characterized by microscopic and microanalytic methods. Microstructural observations have shown that the formation of oxide layers depends on the original microstructure. Discontinuous thermogravimetric tests were used to relate the behavior of different chromium, aluminum, and refractory-element additions, and eventually to service conditions in similar environments in which general oxidation takes place. The addition of refractory elements generally impaired the oxidation resistance.
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  • 179
    ISSN: 1573-4889
    Keywords: Alloy 800H ; sulphidation ; oxidation ; sol/gel method ; cerium ; reactive elements ; ceramic coatings ; thermogravimetric experiments
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The corrosion protection of oxide scales formed by electrophoretic deposition in a cerium-containing sol on Alloy 800H, a 32Ni-20Cr steel, followed by firing in air at 1123 K was studied in oxidizing and mixed oxidizing/sulphidizing environments at elevated temperatures. In particular, the influence of type of sol solvent, sol concentration, and thickness of deposited layer on the protection were studied. An optimized treatment was deduced which led to a significant improvement in corrosion behavior in oxidizing/sulphidizing environments.
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  • 180
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    Oxidation of metals 33 (1990), S. 309-320 
    ISSN: 1573-4889
    Keywords: manganese steels ; aluminum coatings ; oxidation ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Austenitic Mn-Al alloys (20–32 W/O Mn, 7–10 Al, 2–3 Si, 1C) were found to have satisfactory oxidation resistance up to 950°C under isothermal conditions in air. Surface enrichment of aluminum is a necessary condition for obtaining an almost pure alumina scale for uses at higher temperatures. Four different Mn-steels were Al-coated by the Capuano electroplating process. In all the steels there was an increase in the hot-oxidation resistance. The best results were obtained with steels containing both Al and Si, and this for temperatures up to 1100°C. No spalling was noticed during rapid cooling of the test pieces. Silicon was found to act as a diffusion barrier to outward iron diffusion. It appears that there is formation of a pure, thin film of alumina from the matrix which interacts with the aluminum diffusing from the superimposed, coating for the formation of good bonds.
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    Oxidation of metals 36 (1991), S. 281-315 
    ISSN: 1573-4889
    Keywords: Fe-Cr-Ni alloys ; rapid solidification processing ; oxidation ; spallation ; silica ; sulfur
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Austenitic Fe-18Cr-20Ni-1.5Mn alloys containing 0, 0.6, and 1.5 wt.% Si were produced both by conventional and rapid solidification processing. The isothermal and cyclic oxidation resistance of the alloys were studied at 900°C in pure O2 to elucidate the role of alloy microstructure and Si content on oxidation properties. The conventionally-processed, large-grained alloy that contained no silicon formed Fe-rich nodules during oxidation. The nodule formation was effectively eliminated by either reducing the alloy grain size by rapid solidification or by adding Si to the alloy. The lowest weight gains were achieved when a continuous silica layer formed between the alloy and the external chromia scale. The formation of the continuous silica layer required a ombination of fine alloy grain size and high Si content. The presence of S in the alloy was found to be detrimental to oxide scale adherence when the silica layer was continuous.
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  • 182
    ISSN: 1573-4889
    Keywords: aluminum-lithium alloys ; oxidation ; oxide nucleation ; lateral oxide growth ; secondary ion mass spectrometry ; scanning ion microprobe
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The high-temperature oxidation behavior of binary Al-Li alloys has been characterized by scanning electron microscopy and secondary ion mass spectrometry in order to understand the mechanism of rapid oxidation in these alloys and to correlate the oxide morphology to its microchemistry. The oxide scale developed on polished specimens during short exposures in air at 530°C shows characteristic nodules that usually nucleate at grain boundaries. Examination of the alloy surface after removal of the oxide layer shows that the initial growth of the oxide nodules occurs laterally in addition to thickening normal to the oxide/alloy interface. Microchemical analysis of the oxide film with a scanning ion microprobe reveals a thick Li-oxide layer at the oxide/gas interface indicating preferential oxidation of Li at the free surface; the rest of the oxide film is composed of both Al- and Li-rich oxides, probably Li2O and LiAlO2 The presence of trace impurities (K, Na, F, and Cl) in the oxide scale was also detected. A microstructural model for the development of the oxide film in the Al-Li system is presented on the basis of both morphological and microanalytical data obtained in this study; this new model is compared with existing models.
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    Oxidation of metals 36 (1991), S. 439-464 
    ISSN: 1573-4889
    Keywords: V-A1 alloy ; Cr and Ti additions ; oxidation ; kinetics ; V2O5 ; Al2O3
    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 in air of pure vanadium, V-30Al, V-30Al-10Cr, and V-30Al-10Ti (weight percent) was investigated over the temperature range of 700–1000° C. The oxidation of pure vanadium was characterized by linear kinetics due to the formation of liquid V2O5 which dripped from the sample. The oxidation behavior of the alloys was characterized by linear and parabolic kinetics which combined to give an overall time dependence of 0.6–0.8. An empirical relationship of the form: ΔW/A=Bt + Ct1/2 + D was found to fit the data well, with the linear contribution suspected to be from V2O5 formation for V-30Al and V-30Al-10Cr, and a semi-liquid mixture of V2O5 and Al2O3 for V-30Al-10Ti. The parabolic term is presumed related to the formation of a solid mixture of V2O5 and Al2O3 for V-30Al and V-30Al-10Cr, and TiO2 for V-30Al-10Ti The addition of aluminum was found to reduce the oxidation rate of vanadium, but not to the extent predicted by the theory of competing oxide phases proposed by Wang, Gleeson, and Douglass. This was attributed to the formation of a liquid-oxide phase in the initial stages of exposure from which the alloys could not recover. Ternary additions of chromium and titanium were found to decrease the oxidation rate further, with chromium being the most effective. The oxide scales of the alloys were found to be highly porous at 900° C and 1000° C, due to the high vapor pressure of V2O5 above 800° C.
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    Oxidation of metals 36 (1991), S. 491-491 
    ISSN: 1573-4889
    Keywords: oxidation ; adhesion ; sulfur ; growth mechanisms ; grain boundaries ; chromia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A TEM and STEM examination has been carried out of cross-sectioned specimens of convoluted chromia scale formed by oxidizing chromium at 950° C. Sulfur was detected at the oxide/metal interface and the oxide grain boundaries (apart from low-angle grain boundaries), but not within the oxide grains. These results are consistent with the “sulfur effect” theory.
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  • 185
    ISSN: 1573-4889
    Keywords: non-isothermal ; oxidation ; Al2O3+Cr2O3 coatings ; Fe, Fe-Cr alloys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The non-isothermal oxidation behavior of electrolytic-grade iron and Fe-Cr alloys in dry air has been studied using linear heating rates of 6 K/min, 10 K/ min, and 15 K/min up to a final temperature of 1273–1473 K. Some of the iron and iron-chromium alloy samples were given a surface treatment by dipping them in an aqueous solution containing both Cr and Al ions before their oxidation studies. This pretreatment has resulted in improved oxidation resistance and scale adherence as depicted by no scale rupture even after a second thermal cycle. Mass changes were recorded gravimetrically, and scales have been characterized by SEM, EPMA, and x-ray diffraction analyses.
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    Oxidation of metals 37 (1992), S. 111-124 
    ISSN: 1573-4889
    Keywords: oxidation ; titanium aluminide ; oxidation kinetics ; oxidation products
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Static oxidation kinetics of Ti-25Al-10Nb-3V-1Mo (atomic percent) were investigated in air over the temperature range of 650–1000°C using thermogravimetric analysis. The oxidation kinetics were complex at all exposure temperatures and displayed up to two distinct stages of parabolic oxidation. Breakaway oxidation occurred after long exposure times at high temperatures. Oxidation products were determined using x-ray diffraction techniques, electron microprobe analysis, and energy dispersive x-ray analysis. Oxide scale morphology was examined using scanning electron microscopy of the surfaces and cross-sections of oxidation specimens. The oxides during the parabolic stages were compact and multilayered, consisting primarily of TiO2 doped with Nb, a top layer of Al2O3 and a thin bottom layer of TiN. The transition between the first and second parabolic stage is linked to the formation of a TiAl layer at the oxide-metal interface. Porosity also formed in the TiO2 layer during the second stage, causing degradation of the oxide and breakaway oxidation.
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  • 187
    ISSN: 1573-4889
    Keywords: molybdenum ; molybdenum trioxide ; oxidation ; oriented growth ; growth mechanism
    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 of polycrystalline Mo plates and of Mo(100), Mo(110), and Mo(111) single-crystal plates in pure oxygen at 8 × 104 and 2.7 × 103 Pa, at 743–1023 K leads to the growth of orthorhombic MoO3 only, as shown by X-ray diffraction and SEM observations. The stable oxides MoO2 and Mo4O11 were not identified. At each side of the molybdenum plate, the oxide scale is a stacking of MoO3 crystals with their [100] axes oriented normal to the surface of the initial Mo plate. The MoO3 crystals are very thick in the [010] direction, compared with the well-known shape of the MoO3 crystals grown from the vapor phase. Two main factors determine the oriented growth of MoO3 crystals from Mo oxidation. A growth mechanism involving a structural rearrangement of the Mo atoms at the reactional interface and oxygen diffusion through the oxide is proposed.
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  • 188
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    Oxidation of metals 36 (1991), S. 57-80 
    ISSN: 1573-4889
    Keywords: Fe-Cr-Al ; oxidation ; aluminum oxide ; air ; exhaust gas
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Fe-20Cr-5Al alloy foils are used in automotive catalytic converters. This work examines oxidation behavior of four production-processed alloy foils in both air and synthetic exhaust gas environments. Oxidation tests were performed between 750° C and 1150° C for times to 96 hrs. Weight gain results in both atmospheres were similar, an indication that the same mechanism controls oxidation in both environments. At high temperatures (〉-950° C) both atmospheres produce weight gains consistent with α-alumina growth. Activation energies of 323 kJ/gmole and 271 kJ/gmole were calculated for oxidation in air and synthetic exhaust gas, respectively. At lower temperatures (〈-850° C), accelerated weight gains can occur from growth of transition alumina. Despite similar weight gain results, the two atmospheres produce different oxide morphologies: at 950° C and above, air produces a rounded, porous oxide while synthetic exhaust produces a more compact, angular oxide. Unexpectedly, oxide spalling occurred on foils oxidized in synthetic exhaust at 1050° C and above.
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    Oxidation of metals 36 (1991), S. 395-407 
    ISSN: 1573-4889
    Keywords: nickel-base alloys ; oxidation ; Sulfidation ; hot-corrosion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The effect of preoxidation in H2/H2O and in dry H2 on the sulfidation resistance of Ni-20Cr-Al alloys with 2, 3.5, and 5 wt.% Al has been investigated. The samples were sulfidized 4 hr in H2/5% H2S at 750, 800, and 850° C. Best results were obtained for the Ni-20Cr-5Al alloy pretreated for 100 hr at 1000°C in dry H2. The sulfidation reaction in H2/5% H2S was retarded strongly by this treatment for a period of 4 hr at 850°C and of 15 hr at 750°C. Although less pronounced, preoxidation of alloys with lower Al contents or pretreatment in H2/H2O show positive effects as well.
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    Oxidation of metals 36 (1991), S. 475-490 
    ISSN: 1573-4889
    Keywords: oxidation ; mechanism ; Ti-Al alloys ; Ti-Si alloys ; nickel-based alloys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Thermodynamic calculations are performed to estimate isothermal sections of Ti-Al-O, Ti-Si-O, and Ni-Al-O phase diagrams. Very small aluminum levels (〈10−10 at. %) are needed to stabilize alumina on Ni-Al alloys. However, much higher aluminum (≳50%) and silicon (≳40%) levels are needed to stabilize alumina and silica on Ti-Al and Ti-Si alloys, respectively. These calculations suggest that the mechanism of formation of the protective oxide films on titanium-based alloys is radically different from that on nickel-based alloys. The aluminum levels needed to form a continuous film of alumina on nickel-based alloys are dominated by kinetic factors. On the other hand, thermodynamic factors appear to dominate the alloy compositions needed to form protective films of alumina and silica on titanium-based alloys. Further work is needed to evaluate any possible role of kinetic factors.
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    Oxidation of metals 37 (1992), S. 23-37 
    ISSN: 1573-4889
    Keywords: aluminum-lithium alloys ; oxidation ; second-phase particles ; secondary ion mass spectrometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Oxidation behavior of Al-Li alloys, containing a high volume fraction of Ferich second-phase particles, was studied at 530°C and 200°C. Morphological studies showed enhanced growth of Li-rich oxides in the vicinity of the insoluble second-phase particles. Microanalytical depth profiling of the oxide layer with a high resolution scanning ion microprobe indicated rapid diffusion and subsequent oxidation of Li at the free surface. Examination of the alloy surface after removal of the oxide layer suggested that the initial oxide growth occurred in the lateral direction. Secondary ion image depth profiling of the alloy surface after oxide removal revealed Li segregation to the alloy/second-phase interface, supplying Li for accelerated oxidation. A microstructural model of the oxidation process in this case is presented.
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  • 192
    ISSN: 1573-4889
    Keywords: Fe-Cr-Al ; oxidation ; air ; exhaust gas ; aluminum oxide ; oxide adherence ; reactive elements
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract This work evaluated the adherence of oxide grown in air and synthetic exhaust gas on Fe-20Cr-5Al alloys containing strong sulfide-forming elements: Ca, Mg, Y, Ce, La, Ti, and Zr. Results support the theory that reactive elements provide good oxide adherence on alumina-forming materials primarily by tying up sulfur as stable Sulfides; however, other influences on adherence were found. Highly volatile elements, such as Ca and Mg, lose their sulfur-controlling ability by diffusing out of the matrix and into the growing oxide scale. Zirconium results in the growth of an extensive network of oxide pegs into the substrate which improves adherence. Titanium segregates to the alumina scale and acts as a sink for S in the matrix. In synthetic exhaust gas (N2+CO2+H2O), local oxide spalling was observed and was shown to be caused by H2O in the atmosphere. The added benefits of Ti and Zr, i.e., forming oxide pegs and sinks for S, improve adherence in this environment.
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    Oxidation of metals 39 (1993), S. 69-91 
    ISSN: 1573-4889
    Keywords: oxidation ; titanium nitride ; ceramic-matrix composites ; rutile ; oxide layers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The mechanism and kinetics of high-temperature (up to 1500°C) oxidation of pressureless-sintered TiN and hot-pressed silicon nitride-TiN, alumina-TiN, aluminum nitride-TiN, and AlON-TiN ceramic composites were studied in air under isothermal and nonisothermal conditions. Analysis of the oxidation products revealed the formation of rutile in the temperature range from 600 to 1000°C. An interaction of TiO2 with the matrix and/or its oxidation products was observed at higher temperatures. The oxidation of TiN-containing composites shows different behavior depending on the temperature. The presence of fine isolated inclusions of TiN (〈30 mass %) in the silicon-nitride matrix does not change the mass gain during oxidation or increases it only slightly, as compared with a TiN-free material. For materials containing a continuous skeleton of TiN (〉30 mass %) a noticeable increase of the oxidation rate was observed.
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    Oxidation of metals 39 (1993), S. 155-165 
    ISSN: 1573-4889
    Keywords: oxidation ; sulfidation ; nickel alloys ; stresses
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Two alloys, Ni-20Cr and Ni-15Cr-8Fe, as wire specimens, were exposed to sulfur dioxide between 325 and 800°C, with applied external stresses (mode I). Their mechanical properties have been investigated, and the variation of their radius has been precised by conductivity measurements. For the Ni-20Cr alloy, below 550°C, the failure process combines cracking and corrosion: Cr2S3 crystals formed at the tip of the cracks facilitate their propagation. Above 550°C, no barrier effect is observed, and intergranular corrosion takes place. For the Ni-15Cr-8Fe alloy, mode-I stresses bolster intergranular corrosion.
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    Oxidation of metals 39 (1993), S. 211-220 
    ISSN: 1573-4889
    Keywords: oxidation ; sulfidation ; nickel alloys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Two nickel-base alloys, Ni-20Cr and Ni-15Cr-8Fe, in the form of wire specimens, have been exposed to 100 mbar of sulfur dioxide between 550 and 850°C. For Ni-20Cr, an outer Cr2O3 layer formed only at the beginning of the reaction, but very quickly Ni3S2 grew preferentially at the exterior by outward diffusion of nickel. The reaction rate is regulated by an external interfacial process. A barrier effect was noted near 645°C associated with the formation of NiCr2O4; a new acceleration takes place above 680°C. The external growth of Ni3S2 is attributed to the low radius of curvature of the samples. For Ni-15Cr-8Fe, the reaction mechanism is rather similar, except that no barrier effect occurred. A protective Cr2O3 layer formed above 800°C in both cases.
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  • 196
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    Oxidation of metals 39 (1993), S. 231-261 
    ISSN: 1573-4889
    Keywords: oxidation ; single-crystal superalloys ; coating ; reactive-element effect
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Several commercial single-crystal superalloys (CMSX-2, CMSX-3, CMSX-4, CMSX-6, SRR 99) and some laboratory versions of one of them (CMSX-4) with various Y-additions were investigated concerning their oxidation resistance in air at temperatures between 800 and 1200°C. The investigations also included two materials (CMSX-6, SRR 99) with an RT-22 coating. Weight change was recorded for times of up to 1000 hr (in some cases up to 1600 hr). Oxidized coatings and substrates were characterized by metallography, SEM, and microprobe analysis. Most of the alloys showed good oxidation resistance up to 1000°C, while there was complete spalling during cooling after oxidation at 1150°C and 1200°C for the uncoated and Y-free alloys. Coated alloys were superior, however the best behavior was shown by a laboratory version of CMSX-4 containing between 10 and 60 ppm Y. Interdiffusion at 1000°C is tolerable for the coated alloys, but there was extremely rapid degradation of the coating by interdiffusion at 1200°C.
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  • 197
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    Oxidation of metals 40 (1993), S. 5-20 
    ISSN: 1573-4889
    Keywords: sheet resistance ; resistivity ; oxidation ; tantalum nitride ; thin films
    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 of reactively-sputtered, tantalum—nitride thin films has been studied between 473 and 773 K in air. Films with thicknesses that correspond to sheet resistances of 43, 75, and 150 Ω/□ were evaluated in this study. X-ray diffraction revealed that the films and the oxidation products were amorphous. The oxidation products were characterized with AES and XPS. The oxidation process was monitored by measuring the change in sheet resistance with time. Sheet resistance measurements were performed with a four-point probe. The oxidation kinetics can be represented by the equation ΔR/R n =k′t. ΔR/R is sheet resistance change in %, t is time, and k′ is the rate constant. The oxidation kinetics, for the thickest film, were parabolic above about 598 K, and approximately quartic below this temperature. The 75 Ω/□ films deviated from parabolic kinetics below 603 K, and approached approximate cubic kinetics at 498 K. However, the data were forced to fit parabolic kinetics with good correlation. For the thinnest film, no deviation from parabolic kinetics was observed. The rate constants obeyed the Arrhenius relation. An activation energy of 147 kJ/mole (1.52eV) was calculated, for the thickest film, during parabolic kinetics. This value is approximately equal to the activation energy obtained during quartic kinetics. A model that explains the deviation from parabolic to quartic oxidation kinetics at lower temperatures is presented. In this model, the change in resistance as a function of time was due to simultaneous change in film resistivity, as a result of oxygen dissolution into the film, and oxide-scale growth. The temperature at which this deviation occurs should be a function of film thickness.
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  • 198
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    Oxidation of metals 40 (1993), S. 109-118 
    ISSN: 1573-4889
    Keywords: oxidation ; gaseous diffusion ; hafnium carbide ; hafnia ; porosity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A counter-current gaseous diffusion model is presented to describe the oxidation of hafnium carbide between 1200 and 1530°C. The model separates the porous hafnia scale into two gas diffusion regions separated by a flame front, where O 2 and CO react to form CO 2.In the outer region, O 2 and CO 2 counter-diffuse; in the inner region, CO 2 and CO counter-diffuse. The concentration gradients of each gaseous specie in the pores of the hafnia are determined and the rate of oxidation is calculated. A porosity of 2% and a pore radius of 0.01 μm are representative of the values observed in hafnia during the early stages of HfC oxidation. These values lead to predictions of parabolic rate constants that are close to those measured by thermogravimetric analysis. In addition, the predicted and measured parabolic rate constants are shown to have the same dependence upon temperature and oxygen partial pressure.
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  • 199
    ISSN: 1573-4889
    Keywords: single crystal ; superalloy ; oxidation ; microstructure ; grain size ; cast and forged alloys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Oxidation studies have been carried out on NiCrAl-base alloys in air and air containing 1% sulphur dioxide at 1000°C. The alloys used were in the cast, forged and single-crystalline form. There was considerable difference in the oxidation behavior of the as-cast alloy and that of forged alloy, when the environment contained sulphur dioxide. In the absence of the latter, the behavior of the two alloys was not very different. The oxidation behavior of the single crystals was also very similar to that of the cast and forged alloys, when the atmosphere was oxidizing. A few single-crystalline alloys, however, underwent catastrophic oxidation when about 1% sulphur dioxide gas was present, in a manner similar to that of the cast alloy. Oxidation tests at 1000°C as well as detailed scale analysis indicated that the different microstructure, especially large difference in grain size was probably the main reason for the large difference in their oxidation behavior.
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  • 200
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    Oxidation of metals 40 (1993), S. 421-432 
    ISSN: 1573-4889
    Keywords: oxidation ; chromium ; water ; oxygen ; SIMS
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The initial oxidation of pure, polycrystalline-chromium metal with gas mixtures of oxygen-labeled water, H2 18O, and oxygen,16O2, at temperatures 300–730 K has been studied in situ with secondary ion mass spectrometry, SIMS. The fraction of O in secondary ion species: CrO+, Cr2O+, CrOH+, Cr2OH+, CrOH2 +, and Cr2OH2 + originating from water and oxygen was found. The reaction of water and oxygen in the oxygen/water gas mixture with Cr is then revealed. The dissociation of water in its reaction with Cr in such a gas mixture was analyzed. Oxide growth on cleaned Cr surfaces during the reaction with H2O, O2 and H2O/O2 gas was also studied in situ with X-ray photoelectron spectroscopy, XPS. A correlation between a chemical shift in XPS and the OH content in the oxide is discussed.
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