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  • 1
    Digitale Medien
    Digitale Medien
    Springer
    Journal of polymers and the environment 3 (1995), S. 199-203 
    ISSN: 1572-8900
    Schlagwort(e): Chemiluminescence ; oxidation ; stability ; acrylonitrile-butadiene-styrene
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Energietechnik , Maschinenbau
    Notizen: Abstract The thermal oxidative stability of various formulations based on emulsion-grade ABS was studied by the chemiluminescence technique. Emulsion products were found to be essentially less stable than ionic mass polymerization resins. Among the antioxidants studied, Santonox R is clearly more efficient than Irganox 1076 and Irganox 3114, and its superiority is reflected primarily in improved induction period values. The introduction of Tinuvin 770 and Tinuvin 328 UV stabilizers into emulsion resins does not change the durability of the products. In mixtures where both Irganox 1076 and UV stabilizers are present, a certain antagonistic effect was noted at high UV stabilizer concentrations.
    Materialart: Digitale Medien
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  • 2
    ISSN: 1572-8765
    Schlagwort(e): carbonado ; diamond ; oxidation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation of carbonado type synthesized polycrystalline diamonds produced from graphite together with catalytic Ni-Mo alloy doped with TiB2 and BNcub was investigated. It was found that the addition of these boron compounds increases the oxidation resistance of the carbonado type synthesized polycrystalline diamonds. The oxidation mechanism acting on the carbonado type synthesized polycrystalline diamonds and the role of boron compounds in increasing the resistance to the oxygen reaction are discussed.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    Springer
    Plasma chemistry and plasma processing 6 (1986), S. 27-38 
    ISSN: 1572-8986
    Schlagwort(e): AC discharge ; discharge chemistry ; hydrogen cyanide ; cyanogen ; chemiluminescence ; oxidation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Technik allgemein
    Notizen: Abstract The AC high-voltage discharge-induced decomposition chemistry of trace levels of hydrogen cyanide in helium has been studied. In the absence of oxygen only low levels of molecular nitrogen were evolved. With oxygen added, the principal products were CO, CO2, and N2. No significant concentrations of NO or N2O were observed. The response of a commercial NOx analyzer to HCN and C2N2, in the NOx mode, was determined to be linear through three decades in concentration. The oxidation chemistry of HCN and C2N2 in the stainless steel converter of the analyzer was studied as a function of the amount of added oxygen.
    Materialart: Digitale Medien
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  • 4
    ISSN: 1572-8986
    Schlagwort(e): RF SiCl4 discharge ; mass spectrometry ; kinetics ; decomposition ; oxidation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Technik allgemein
    Notizen: 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.
    Materialart: Digitale Medien
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  • 5
    Digitale Medien
    Digitale Medien
    Springer
    Plasma chemistry and plasma processing 19 (1999), S. 131-151 
    ISSN: 1572-8986
    Schlagwort(e): Styrene ; oxidation ; silent discharge ; plasma ; dielectric barrier
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Technik allgemein
    Notizen: 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.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    Springer
    Plasma chemistry and plasma processing 19 (1999), S. 383-394 
    ISSN: 1572-8986
    Schlagwort(e): Nonthermal plasma ; benzene ; Al2O3 ; BaTiO3 ; oxidation ; absorption ; atmospheric pressure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Technik allgemein
    Notizen: 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.
    Materialart: Digitale Medien
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  • 7
    Digitale Medien
    Digitale Medien
    Springer
    Plasma chemistry and plasma processing 19 (1999), S. 421-443 
    ISSN: 1572-8986
    Schlagwort(e): Streamer corona ; NO x removal ; nonthermal plasma ; oxidation ; reduction
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Technik allgemein
    Notizen: 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.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 28 (1987), S. 195-211 
    ISSN: 1573-4889
    Schlagwort(e): Uranium ; corrosion ; oxidation ; liquid metal
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The reactions of water vapor and oxygen with liquid uranium were studied by modulated molecular-beam mass spectrometric methods. Equivalent pressures of the reactant fluxes on the surface ranged from 6×10 −6 to 2×10−4 torr. Temperatures up to 1570 K were investigated. The metal surface was kept clean during reaction by mechanical removal of the oxide formed with a tungsten needle. For the clean liquid uranium surface, a water reaction probability of ∼0.4 was deduced both from measurement of the reaction-product hydrogen signal and by the temperature dependence of the scattered reactant signal. Based solely on the latter measure, a reaction probability of 0.6 was estimated for oxygen. The reaction probabilities on the clean surface were temperatureindependent. They decreased as the coverage of the surface by islands of oxide increased and, for water, appeared to approach a value of 0.08 for a surface completely covered with an oxide estimated to be 500 Å thick. Bombardment of the surface during reaction with argon ions produced an increase in the reactivity on solid uranium but had a negligible effect on the reaction probability for the liquid.
    Materialart: Digitale Medien
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  • 9
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 28 (1987), S. 353-389 
    ISSN: 1573-4889
    Schlagwort(e): Grain growth ; nickel oxide ; high temperature ; oxidation ; nickel
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract In systems such as the oxidation of nickel, in which grain-boundary diffusion in the oxide can control the rate of oxidation, understanding of the factors governing the grain structure is of importance. High-purity mechanically polished polycrystalline nickel was oxidized at 700°C, 800°C, and 1000°C for times up to 20 hr in 1 atm O2. The scale microstructures were examined by parallel and transverse cross section transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Texture coefficients were found by X-ray diffraction (XRD). Each grain in the transverse section grain boundary networks was systematically analyzed for width parallel to the Ni-NiO interface and perpendicular length, for boundary radius of curvature and for number of sides. The variation of these parameters with depth in the scale was examined. In particular, grains were increasingly columnar (i.e., with ratio of grain length to width 〉1) at higher temperatures and longer times. Columnar grain boundaries tended to be fairly static; the columnar grain width was less than the rate controlling grain size predicted from the oxidation rate. The mean boundary curvature per grain provided a guide to the tendency for grain growth, except in the region of the Ni-NiO interface, where the boundaries were thought to be pinned.
    Materialart: Digitale Medien
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  • 10
    ISSN: 1573-4889
    Schlagwort(e): dilute alloys ; oxidation ; Wagner-Hauffe rule
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 11
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; copper ; Li-doped copper ; Cr-doped copper ; short-circuiting ; Mott's parabola ; Wagner's parabola
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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.
    Materialart: Digitale Medien
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  • 12
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 46 (1996), S. 109-127 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; Ni3Al base alloy ; chromium ; cobalt ; titanium
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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.
    Materialart: Digitale Medien
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  • 13
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 47 (1997), S. 381-410 
    ISSN: 1573-4889
    Schlagwort(e): Ni-Base superalloys ; Astroloy ; Waspaloy ; Udimet 720 ; oxidation ; chromia
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 14
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; Incoloy 909 ; superalloy ; scale ; high temperature ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 15
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 47 (1997), S. 445-464 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; Fe-Cr-Al alloy ; water vapor ; ESCA ; RHEED
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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.
    Materialart: Digitale Medien
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  • 16
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 47 (1997), S. 507-524 
    ISSN: 1573-4889
    Schlagwort(e): alloys ; high temperature ; oxidation ; transient state
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 17
    ISSN: 1573-4889
    Schlagwort(e): high temperatures ; oxidation ; transient state
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 18
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 48 (1997), S. 1-39 
    ISSN: 1573-4889
    Schlagwort(e): Ni-base ODS superalloys ; oxidation ; initial stages of oxidation ; alumina ; chromia
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 19
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 48 (1997), S. 129-141 
    ISSN: 1573-4889
    Schlagwort(e): decarburization ; nickel ; oxidation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 20
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; kinetics ; iron ; iron-nitride
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 21
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 48 (1997), S. 201-214 
    ISSN: 1573-4889
    Schlagwort(e): titanium-aluminum alloys ; niobium ; intermetallics ; oxidation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 22
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 48 (1997), S. 215-224 
    ISSN: 1573-4889
    Schlagwort(e): nanocrystallization ; oxidation ; mechanism
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 23
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 48 (1997), S. 289-302 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; titanium ; rutile ; scale ; high temperature ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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.
    Materialart: Digitale Medien
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  • 24
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 48 (1997), S. 329-345 
    ISSN: 1573-4889
    Schlagwort(e): zirconium ; X-ray diffraction ; oxidation ; phase analysis ; texture
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 25
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 48 (1997), S. 357-380 
    ISSN: 1573-4889
    Schlagwort(e): chromium ; copper ; binary alloys ; two-phase alloys ; oxidation ; high temperatures
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 26
    ISSN: 1573-4889
    Schlagwort(e): iron ; oxidation ; CeO2 coating ; in situ ; growth stress ; residual stress ; texture ; X ray diffraction
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 27
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 48 (1997), S. 527-551 
    ISSN: 1573-4889
    Schlagwort(e): chloridation ; oxidation ; Fe-Cr alloys ; Ni-Cr alloys
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 28
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 48 (1997), S. 553-596 
    ISSN: 1573-4889
    Schlagwort(e): chloridation ; oxidation ; HCl ; high-temperature alloys ; high-temperature corrosion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 29
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 24 (1985), S. 133-148 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; nickel ; yttrium
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation of Ni, Ni-0.1 wt.% Y, and Ni-0.3 wt.% Y alloys was carried out in the temperature range 500–900°C at pO 2= 1 atm.
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  • 30
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 24 (1985), S. 177-197 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; short-circuit diffusion ; nickel ; chromium ; binary Ni-Cr alloys
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The evidence for short-circuit diffusion during the oxidation of nickel, chromium, and nickel-chromium alloys is reviewed. On the basis of experimental evidence for the Ni/NiO and Cr/Cr2O3 systems, inferences are made about the role of short-circuit diffusion through the oxide scales forming on the binary nickel-chromium alloys. The review highlights the importance of scale microstructure in governing oxidation rates.
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  • 31
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 26 (1986), S. 139-155 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; Co-Cr-Ti alloys ; kinetics ; scale morphology
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Cobalt-based alloys containing 3,5,10,15, and 20% Cr with 1 and 3% Ti were oxidized at 1000°C in slowly flowing oxygen gas. In general, titanium additions decreased the oxidation rate with the most pronounced effect being observed at the 10% Cr level. Titanium accelerated the formation of Cr2O3 layers at the metal-oxide interface. Faceted CrxTiyOz spinel particles were found at the metal-oxide interface which varied in composition according to microprobe results. There was no evidence of spalling on the Co-Cr-Ti alloys studied in contrast to the severe spalling normally encountered in Ni-Cr-Ti alloys. Distinct morphological differences existed on the outer CoO layer of the 1% Ti alloys in comparison to the O and 3% Ti alloys.
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  • 32
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 26 (1986), S. 305-314 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; metals ; high temperatures ; oxidation theory ; oxidation kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract A theoretical study on the high-temperature oxidation of thick oxide films grown under a time-dependent gas partial pressure is reported. The diffusion across the film is assumed to be the rate-limiting step of the overall reaction, and Wagner's hypotheses were used as the starting point for our reasoning. A general formulation for the oxidation under no time constant gas pressure, in terms of a time-dependent answer function is given. The effect of an external electric field on the reaction rate is also reported when a constant current density,J, is applied to the oxide scale. If the oxide is a good electronic conductor atJ=0 andt ≫ τ, we found that the reaction rate assumes formally the well-known Wagner's expression of the rate constant but with a gas partial pressure at oxide/gas interface which is a time function. If the oxide is a good ionic or electronic conductor, the effect due to an external electric field,J ≠ 0, on the reaction rate is the same as predicted by the Wagner's theory.
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  • 33
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 26 (1986), S. 201-212 
    ISSN: 1573-4889
    Schlagwort(e): chromium ; NaCl ; chloride ; oxidation ; hot corrosion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract This paper describes new phenomena about chloride-induced accelerated oxidation of chromium. Thermal analysis was adopted to examine the oxidation, which was studied particularly in the case of NaCl. The presence of NaCl remarkably accelerates the oxidation of chromium. The process occurs below the melting point of NaCl, and the main reaction product is Cr2O3. In the accelerated oxidation NaCl plays a catalytic role because it is not consumed significantly in the process. DTA analysis reveals that the heat of reaction also accelerates the rate of oxidation, especially at an early stage of the reaction. The accelerated oxidation takes place similarly under the presence of chlorides other than NaCl, but the oxidation rate depends on the kind of salt. Therefore the Cl− anion plays an important role in the process, while the nature of the cation affects the rate of acceleration.
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  • 34
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 26 (1986), S. 231-252 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; titanium ; thermogravimetry ; microhardness ; modeling
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation kinetics of commercial purity Ti-A55 exposed to laboratory air in the 593–760°C temperature range were continuously monitored by thermogravimetric analysis. The oxide thickness was measured by microscopy and the substrate contamination was estimated from microhardness measurements. The microhardness depth profiles were converted to oxygen composition profiles using calibration data. The oxygen diffusion coefficient in alpha-Ti appears to be approximately concentration independent in the 1–10 at. % oxygen range. The combination of an “effective diffusion coefficient” and an “effective solubility” at the oxide-metal interface usefully describes the diffusion process over the entire composition range. A model for the total parabolic oxidation kinetics, accounting for the two individual components, oxide growth and solid solution formation, has been proposed. Diffusion coefficient for oxygen in TiO2 has been estimated as a function of temperature and is found to be about 50 times the value in alpha-Ti. The metallographically prepared cross-sections of the oxidized specimens revealed a “moving boundary” in the substrate, parallel to the oxide-metal interface. This boundary was associated with a specific oxygen level of 5.0±0.5 at.%. It occurred at a distance from the oxide-metal interface which was correlatable with temperature and time of exposure. The diffusion coefficient corresponding to the composition of this moving boundary is in excellent agreement with the effective diffusion coefficient for the substrate contamination.
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  • 35
    ISSN: 1573-4889
    Schlagwort(e): Raman microscopy ; Fe-Cr alloys ; oxidation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Raman microscopy has been used to study the nature and distribution of corrosion products formed on iron and iron-chromium alloys in air at high temperatures. Fe and Fe-Cr alloys containing 2, 5, 14, and 18% Cr were oxidized at 400, 600, and 850°C for 2 hr, in addition samples of each alloy were oxidized for 24 hr at 400°C to obtain thicker scales at this temperature. The corroded samples showed varying distributions of the oxides Fe2O3, Fe3O4, Cr2O3, and FeCr2O4. Fe2O3 and Fe3O4 were formed exclusively on the pure iron and the 2 and 5% chromium alloys at all temperatures and on the 14% chromium alloy at 400°C. The 14 and 18% Cr alloys formed scales containing Cr2O3 and FeCr2O4 at the higher temperatures (600 and 850°C). Examples of small regions of Fe2O3 being formed within Cr2O3-FeCr2O4 scales are suggested as possible indications of breakaway corrosion initiation sites.
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  • 36
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 27 (1987), S. 83-93 
    ISSN: 1573-4889
    Schlagwort(e): silicon carbide ; oxidation ; constructional ceramics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The process of high temperature oxidation of two silicon carbide based materials differing by methods of their production and properties has been studied up to 1500°C in air. The oxidation was performed under the isothermal conditions and at the programmed heat rate of 10° per minute. It was found that the oxidation resistance of the material was the function of the presence of extrinsic metals having close affinity for oxygen. It was also found that under heating up to 1500°C in air phase transitions occurred in the SiC surface layer.
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  • 37
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 26 (1986), S. 385-396 
    ISSN: 1573-4889
    Schlagwort(e): coatings ; oxidation ; rare earth addition ; dispersed oxides ; scale adhesion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Oxidation studies were conducted on plasma sprayed coatings of Ni-20Cr-12.5Al containing one of the following: 1% MgO, 1% La2O3, 1% Y2O3, and 0.8% Y. The alloy powders containing dispersed oxides were prepared by a variety of processes employing attrition and ball milling. The TEM characterization of the plasma sprayed deposits of Ni-20Cr-12.5Al-1Y2O3 indicated that the oxide particles ranged from almost pure aluminum oxide to various compounds of aluminum and yttrium oxide. In cyclic tests conducted at 1150 and 1225°C, the coating containing 1% Y2O3 appeared to provide the best oxidation resistance. The oxidation resistance appeared to be influenced by the size and distribution of the oxide particles.
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  • 38
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; adhesion ; growth-mechanisms ; impurities ; sulfur
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The “sulfur effect” theory proposes that elements such as sulfur segregate to the scale-metal interface, where they have a deleterious effect on scale-metal adhesion, and that reactive elements and dispersions of their oxides are beneficial because they prevent this segregation. Evidence in favor of this theory has been obtained by showing that the adhesion of the scale formed on chromium in 0.1 atm. oxygen at 950°C. is greatly improved if the chromium is annealed beforehand in hydrogen instead of in vacuo. It is shown that the theory can explain not only all the experimental observations regarding the beneficial effects of reactive elements and their oxides on scale-metal adhesion, but also their effects on scale growth-mechanisms.
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  • 39
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 26 (1986), S. 105-124 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; titanium ; thermogravimetry ; microhardness ; modeling ; mechanical properties ; space shuttle reentry
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Ti-6Al-2Sn-4Zr-2Mo titanium alloy is a candidate material for multiwall thermal protection system concepts for advanced space transportation system vehicles. The total oxidation kinetics for this alloy, exposed to laboratory air in the 593–760°C range, were monitored by thermogravimetric analysis. The oxide thickness was measured by microscopy and the substrate contamination was estimated from microhardness measurements. Tensile elongation was determined for selected foil specimens after exposure to simulated space shuttle reentry conditions. The variation of total weight gain with time was found to have two distinct parabolic stages separated by a transient region. This transient was due to a process which involved an increase in the parabolic growth rate constant for the oxide and a simultaneous increase in oxygen solubility at the oxide metal interface. The time dependent increase in oxygen solubility at the interface was from about 7 at. % in stage 1 to about 18 at. % in stage 2. The diffusion coefficient for oxygen in the alloy was determined as a function of temperature using the difference between the total weight gain in stage 1 and the corresponding weight gain due to oxide growth. A model for the total oxidation kinetics, accounting for the two individual components namely oxide growth and solid solution formation, is proposed. The activation energy for the diffusion of oxygen in the alpha-solid solution is shown to be roughly equal to the activation energy for the degradation of tensile elongation for the alloy in the foil gage condition.
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  • 40
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 26 (1986), S. 315-332 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; multilayer oxides ; oxidation kinetics theory ; diffusion mechanisms ; iron
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract A quantitative theory for the growth of three-layered oxide scales on pure metals that form MevO, MeδO, and MeɛO has been developed. The theoretical parabolic rate constants,K p (MevO),K p (MeδO), andK p (MeɛO), for the simultaneous growth of each oxide on metals are related to oxidation data of the overall rate constant,K p , and the oxide thickness ratios. These theoretical parabolic rate constants can also be calculated from diffusion data in each oxide, and the oxide thickness ratios can therefore be predicted. To verify the validity of the theory, it was applied to the oxidation of iron in air at temperatures of 800 to 1200° C. Good agreement was found between the theoretical parabolic rate constants calculated from oxidation data and from diffusion data for wustite and magnetite. However, to match with the rate constant calculated from oxidation data, additional information about short-circuit diffusion in hematite is required.
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  • 41
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 27 (1987), S. 21-36 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; steam ; Ni-base superalloy ; Al oxides ; Ti oxides
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The role of aluminum and titanium on the oxidation process of a nickel-base superalloy containing 18.89%Cr, 2.13%Al, and 2.41%Ti was investigated in steam at 800°C. A Cr2O3-rich scale was formed on the alloy surface. Aluminum formed only internal oxides below the Cr2O3-rich scale. On the other hand, titanium formed not only internal oxides but also oxides in the scale and the granular particles of TiO2 outside the scale. Agglomeration of the TiO2 particles also occurred. The oxidation behavior of aluminum and titanium was discussed from thermodynamic and kinetics aspects.
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  • 42
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 27 (1987), S. 37-55 
    ISSN: 1573-4889
    Schlagwort(e): laser treatment ; chromia scales ; oxidation ; nickel-chromium alloys ; laser glazing
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The influence of laser surface treatment on the isothermal oxidation of Ni-10%Cr and Ni-15%Cr at 1025°C in oxygen at 1 atm pressure has been studied. Particular emphasis has been placed on the progressive establishment of a Cr2O3 healing layer, which is facilitated by rapid-diffusion paths for chromium to the surface from the bulk alloy. For nonlaser treated alloys, such paths are alloy grain boundaries. A partial Cr2O3 layer forms initially in localized sites at, and immediately adjacent to, these boundaries and progresses into the alloy grains in a stepwise manner following lateral diffusion of chromium from the grain boundaries, thereby developing a contoured configuration. For Ni-15%Cr, there is sufficient chromium in the bulk alloy grains to sustain the eventual development of a self-healing layer parallel to the surface. For Ni-10%Cr, this is not the case and complete development of the healing layer results entirely from the stepwise progression from the grain boundaries. Establishment of the healing layer on laser-glazed surfaces is facilitated by additional rapid-diffusion paths, particularly retained alloy grain boundaries, retained alloy twins, a laser-induced microstructure and solidification artifacts (such as ripples). The relative importance of these features is discussed in relation to the oxidation behavior.
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  • 43
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 27 (1987), S. 95-102 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; acoustic emission technqiue ; copper
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The acoustic emission technique has been utilized as an alternative technique to thermogravimetry to study the anomalous behavior of copper metal oxidation at 500°C The present work demonstrates an excellent example of the application of this technique in detecting cracks in growing oxide films.
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  • 44
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    Digitale Medien
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    Oxidation of metals 29 (1988), S. 487-497 
    ISSN: 1573-4889
    Schlagwort(e): Alloy ; oxidation ; platinum ; palladium ; rhodium
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The surfaces of Pt-45Pd-10Rh foils oxidized over the range 875–1075 K in a 20% O2-Ar mixture at atmospheric pressure were examined by Auger electron, X-ray photoelectron, and Raman spectroscopy. The composition of the oxide formed on the surface was found to vary with temperature from predominantly PdO at 875 K to PdRhO2 at 1075 K. Only a few atomic percent Pt was observed, present in both the metallic and (apparently) +1 oxidation states at 875 K and in the metallic state at 1075 K. The formation of PdRhO2 (and no Rh2O3) at 1075 K was found to persist upon reoxidation following a low-temperature reduction cycle in which the increased Rh concentration on the surface was retained. An oxidation-induced Rh enrichment of the surface of the alloy foil beyond 50 at. % does not appear likely within the temperature/pressure regime investigated.
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  • 45
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 31 (1989), S. 71-89 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; duplex NiO scale ; segregation ; 18O tracer ; secondary ion-mass spectrometry
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The development of a duplex NiO scale microstructure on a Ni-0.1 wt.% Al alloy at 900°C has been examined, principally using secondary-ion mass spectrometry and analytical transmission electron microscopy. The18O-tracer distribution following sequential oxidation in18O2/18O2 showed that the inner NiO layer formed as a result of gaseous-oxygen penetration of the scale. The provision of pathways for oxygen transport as well as the role of Al, Si, and Ce segregation at oxide grain boundaries in influencing the growth rate and spallation behavior of the scale are discussed.
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  • 46
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 31 (1989), S. 431-452 
    ISSN: 1573-4889
    Schlagwort(e): aluminides ; oxidation ; TEM cross sections
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Cross sections of oxide scale/(Ni-Al) intermetallics were prepared by a new method and studied using primarily transmission electron microscopy (TEM). The cross sections were prepared by encasing an oxidized metal specimen sandwich in a low-melting-temperature zinc alloy. Observations of oxidized zirconium-doped β-NiAl cross sections revealed crystallographic voids beneath an adherent Al2O3 scale. The oxide-metal interface was incoherent, but a high dislocation density in the metal near the interface suggested that a large tensile stress was induced by the attached oxide scale. A duplex Al2O3-NiAl2O4 scale formed on zirconium-doped and zirconium/boron-doped γ′-Ni3Al alloys. Additional results are presented involving oxidation mechanisms and oxide-metal interface structures.
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  • 47
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 32 (1989), S. 317-335 
    ISSN: 1573-4889
    Schlagwort(e): 316L austenitic stainless steel ; porosity ; various additions in stainless steel ; oxidation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation behavior of sintered 316L austenitic stainless steel-Y2O3 composites and the effect of various additions, such as copper (up to 3 wt.%), bronze (up to 3 wt.%), phosphorus (up to 2 wt.%), and silicon (up to 5 wt.%) have been studied at 550°C inflowing oxygen at one atmosphere pressure for a maximum period of 9 hr. Among all the alloys studied, 316L-1% P showed excellent oxidation resistance. Under the general conditions, Cr2O3 is always the preferred protective scale. In general, Y2O3-containing composites showed greater oxidation as compared to 316L with other additions.
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  • 48
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 32 (1989), S. 295-316 
    ISSN: 1573-4889
    Schlagwort(e): Fe-base superalloy ; oxidation ; corrosion in water vapor ; creep rupture strength in water vapor
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation kinetics and creep behavior of Incoloy 800 were studied in air and in water vapor charged with oxygen. Oxidation kinetics were determined by thermogravimetry. The creep behavior of samples tested in air and in H2O∶O2=1∶1 atmospheres was investigated by electron microscopic techniques. The oxidation rate of samples tested in air was governed by a p-conducting chromia interlayer. Depending upon water vapor pressure, chromia became n-conductive. As a consequence, a continuous rate-governing silica interlayer formed. The oxygen activity in the alloy was established by the dissociative pressure of the respective diffusion-rate-governing oxide scale. The stability of the dispersion-hardening Ti(C, N) particulates within the alloy was affected by the respective oxygen activity. In the samples tested in air, partial oxidation of the particulates due to enhanced oxygen activity caused a loss of coherency with the matrix. As a result, the deformation behavior during creep was changed to planar-slip mode, bringing about loss of creep resistance and ductility.
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  • 49
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 44 (1995), S. 265-308 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; corrosion ; high temperatures ; erosion ; wear
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 50
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 44 (1995), S. 339-374 
    ISSN: 1573-4889
    Schlagwort(e): analytical techniques ; Fe, Cr, Fe−Cr alloys, Ni, Al, β-NiAl ; oxidation ; transport processes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 51
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 44 (1995), S. 239-264 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; carburization ; sulfidation ; scaling ; internal precipitation ; diffusion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 52
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 45 (1996), S. 153-181 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; 18O diffusion ; nickel ; stress effects on diffusion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 53
    Digitale Medien
    Digitale Medien
    Springer
    Journal of materials synthesis and processing 6 (1998), S. 191-195 
    ISSN: 1573-4870
    Schlagwort(e): Transmission electron microscopy observation ; interfacial microstructure ; oxidation ; ZrC ; cubic ZrO2 ; amorphous carbon film
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 54
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 23 (1985), S. 17-33 
    ISSN: 1573-4889
    Schlagwort(e): Cold work ; oxidation ; spinel ; 21/4 Cr-1 Mo steel
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The effect of cold work on the oxidation rate of 21/4 Cr-1 Mo steel in pure oxygen at 1 atm pressure at temperatures ranging from 400 to 950
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  • 55
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 24 (1985), S. 233-263 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; carbide dispersion ; iron-base alloys ; decarburization ; thermodynamic stability ; oxidation resistance
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation behavior of Fe-5M-C alloys (where M is Si, Ti, V, Nb, Ta, Cr, W, or Ni, and C is 0, 0.1, 0.4, 0.8 or 1.2 wt.%) has been studied in the temperature range of 600–850°C in one atmospheric pressure of oxygen. Except for Si-containing alloys, all the alloys exhibited a parabolic rate law during oxidation, and the oxidation rate increased with increasing carbon content. The deviations from the above generalization can be explained on the basis of either phase composition of the alloy matrix at the oxidation temperature or carbon losses incurred during oxidation. Alloys rich in carbide phases have much lower oxidation rates than alloys containing solid-solution phases. This has been attributed to the decrease in mobility of carbon in iron-base alloys in the presence of a carbide-formin addition. The disruption of the oxide scales, which is the result of decarburization, also influences the oxidation behavior of iron-base alloys. At the 1.2% C level, the parabolic rate constant, Kp, follows the order: $$Fe - 5Cr 〉 Fe 〉 Fe - 5Ni 〉 Fe - 5Ti 〉 Fe - 5Ta 〉 Fe - 5Nb 〉 Fe - 5V 〉 Fe - 5W$$ The order is approximately similar to the increasing free energy sequence for the oxidation of carbides to oxides in Fe-5M-C alloys.
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  • 56
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 24 (1985), S. 331-350 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; initial stages ; reactive element addition ; oxide grain growth
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Structural Fe-Cr-Ni alloys rely upon a thermally formed, protective, surface oxide scale to prevent rapid corrosive degradation. The protective capacity of the surface scale may be strongly influenced by the alloy composition, with minor additions of reactive elements playing an important role in the initial stages of scale formation. The influence of an addition of Zr on initial scale growth on an Fe-Cr-Ni alloy has been investigated in situ utilizing an environmental cell incorporated into a high-voltage electron microscope. Oxidation experiments were conducted on a pure ternary Fe-Cr-Ni alloy and one containing 6 wt.% Zr for durations up to 1800 s. At 500°C in a low oxygen-partialpressure environment, a continuous surface oxide layer formed more quickly on the Zr-free alloy than on the Zr-modified alloy. Also, on the Zr-modified alloy, the scale was richer in Cr, and the rate of increase in oxide grain size was also greater.
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  • 57
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 23 (1985), S. 77-106 
    ISSN: 1573-4889
    Schlagwort(e): cobalt-chromium ; oxidation ; internal oxidation ; annealing
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The influence of an initial preinternal oxidation treatment in Co/CoO on the subsequent oxidation behavior of a series of dilute Co-Cr alloys (containing 0–1.5 wt. % Cr) in 105 and 103 Pa oxygen at 1473–1623 Khas been investigated. Particular emphasis has been placed on determining the solubility and mobility of Cr3+ ions in CoO. Use has been made of subsequent annealing in argon $$(p_{O_2 } - 10^{ - 1} {\text{ }}Pa)$$ .
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  • 58
    ISSN: 1573-4889
    Schlagwort(e): grain boundary diffusion ; nickel oxide ; oxidation ; active element
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract NiO scales were formed on pure Ni and Ni-0.1 wt.% Y alloy by oxidation in pure O2 at 1200°C, and the grain boundary self-diffusion coefficients of Ni in the dense region of the scale were measured by the tracer-sectioning technique. The volume diffusion coefficient was also measured in the alloy scale. The grain boundary and volume diffusion coefficients and the grain boundary width were found to be the same for the two materials within the experimental uncertainty.
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  • 59
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; Y2O3 ; dispersoid ; 80Ni-20Cr ; nucleation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Specimens of a 80Ni-20Cr type alloy, with and without Y2O3 dispersoid particles, were oxidized at 1000°C in H2/H2O mixtures where the partial pressure of oxygen (P O 2) was varied between 103 and 1024 atm. Oxide particles nucleated homogeneously on both alloys, and preferential nucleation on dispersoid particles at the surface was not observed. Continuous Cr2O3 films formed slightly faster at aP O 2 of 10−21 atm on the alloy containing the dispersoid, but the difference was negligible at higher pressures. Oxidation atP O 2=10-19 and 10−21 atm involved both the formation of Cr2O3 and the evaporation of chromium. Thin films of α-Al2O3 were observed on both alloys after oxidation atP O 2.
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  • 60
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 25 (1986), S. 83-92 
    ISSN: 1573-4889
    Schlagwort(e): NaCl vapor ; Ni-Cr alloys ; oxidation ; scales
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Ni-Cr alloys are known for their resistance to high temperature oxidation. The kinetics of scale formation and the nature of the scale in these alloys are affected by NaCl liquid or vapor. There have been a few investigations dealing with the influence of NaCl on long-time exposure. But the nature of reaction at short times can provide information on the initiation of such attack. In this investigation, Ni-Cr alloys with Cr varying from 0 to 25 wt% were exposed to NaCl vapor at 850°C for a few minutes. The surface chemistry of these alloys along with the unattached ones was analyzed by Auger electron spectroscopy. The nature of scale and the distribution of chlorine was found to vary with the Cr content in the alloys, which has a direct bearing on the rate of oxidation of these alloys in NaCl vapor.
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  • 61
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 29 (1988), S. 75-102 
    ISSN: 1573-4889
    Schlagwort(e): Ni-Cr-Al Alloys ; oxidation ; diffusional transport ; breakaway oxidation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The cyclic oxidation behavior of several cast γ+β, Ni-Cr-Al(Y, Zr) alloys and one LPPS γ+β, Ni-Co-Cr-Al(Y) alloy was examined (γ, fcc; β, NiAl structure). Cyclic oxidation was performed by cycling between 1200°C and approximately 70°C. Oxide morphologies and microstructural changes during cyclic oxidation were noted. Recession of the high-Al β phase was nonparabolic with time. Kirkendall porosity resulting from diffusional transport within the alloy was observed in the near-surface γ-phase layer of one alloy. Concentration profiles for Ni, Cr, and Al were measured in the γ-phase layer after various cyclic oxidation exposures. It was observed that cyclic oxidation results in a decreasing Al concentration at the oxide-metal interface due to a high demand for Al (a high rate of Al consumption) associated with oxide scale cracking and spalling. In addition, diffusion paths plotted on the ternary phase diagram shifted to higher Ni concentrations with increasing cyclic oxidation exposures. The alloy with the highest rate of Al consumption, and highest Al content, underwent breakaway oxidation after 500 1-hr cycles at 1200°C. Breakaway oxidation occurred when the Al concentration at the oxide-metal interface approached zero. The relationship between the Al transport in the alloy and breakaway oxidation is discussed.
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  • 62
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 29 (1988), S. 225-238 
    ISSN: 1573-4889
    Schlagwort(e): Nickel ; SO2 ; oxidation ; sulfidation ; diffusion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The reaction of nickel with SO2 has been studied. The composition and morphology of the scale formed in sulfur dioxide (1.013×105 Pa) at 600°C and the transport phenomena occurring in the growing scale have been investigated. The experimental methods consisted of metallography, scanning electron microscopy, and electron microprobe analysis. The transport phenomena have been studied by the marker method and with the use of a35S radioisotope. The scale was composed of a NiO and Ni3S2 mixture and grew by the outward diffusion of nickel and inward transport of SO2 molecules through the discontinuities of the scale. It has been shown that outward transport of sulfur originating from grains of sulfide occurs.
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  • 63
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 27 (1987), S. 103-120 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; iron ; aluminum ; silicon
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract This paper reports an investigation into reducing the Cr concentration in commercial-grade stainless steels while maintaining oxidation protection at elevated temperatures. Aluminum and Si were added as partial substitute alloy elements to enhance the reduced operation protection resulting from Cr concentration reduced by approximately 50 pct of that found in stainless steels. The goal of this study was to determine the oxidation mechanism of such an Fe, Al-Si alloy: Fe-8Cr-14Ni-1Al-3.5Si-1Mn. During the initial oxidation period the protection resulted from a thin film of Al2O3 over an Fe and Cr spinel. Long-term oxidation protection resulted from the gradual formation of a Cr sesquioxide (Cr2O2) inner oxide layer. Eventually an outer oxide layer formed that was a mixed composition spinel of Cr and Mn (MnO · Cr2O3). The Al2O3, which was part of the original protective layer flaked off early in the oxide testing, and the aluminum oxide that formed later appeared as an internal oxide precipitate.
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  • 64
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 30 (1988), S. 259-266 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; adhesion ; growth mechanisms ; sulfur ; impurities ; segregation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The results of studies involving both alumina and chromia formers have demonstrated that segregation of low levels of indigenous impurity elements commonly found in metals and alloys can segregate to the scale-metal interface. Such segregation markedly affects protective-oxide-scale adherence to produce scale exfoliation. The most important element to cause exfoliation effects is sulfur, which is not uncommonly present in metals and alloys to levels of ∼50 ppm. The reduction of such sulfur to the 1–2 ppm range strongly increases oxide scale adherence without requiring additions of “active” elements, such as yttrium. The results of experiments that led to this conclusion are reiterated.
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  • 65
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 30 (1988), S. 329-343 
    ISSN: 1573-4889
    Schlagwort(e): Fe-S-O ; Co-S-O ; oxidation ; sulfidation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The equilibrium oxygen potentials of the two-phase equilibria Fe3O4/Fe1−xS, Co1−xS/Co3S4, Co3S4/CoS2, Co1−xS/CoO, and CoO/CoSO4 were measured as a function of temperature. A solid-state emf technique using calcia-stabilized zirconia (CSZ) solid electrolyte was used. These equilibria were studied atP SO2≃1 atm; the equilibrium Co1−xS/CoO was also studied atP SO2≃0.1 atm. Two emf cell designs were used for the measurements atP SO2≃1 atm andP SO2≃1 and 0.1 atm, respectively. The homogeneity range of FeS in equilibrium with Fe3O4 and that of Co1−xS in equilibrium with CoO at ∼ 1073 K andP SO2≃1 atm were measured by electron microprobe analysis.
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  • 66
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 30 (1988), S. 267-269 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; adhesion ; impurities ; sulfur
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Materialart: Digitale Medien
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  • 67
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 32 (1989), S. 433-447 
    ISSN: 1573-4889
    Schlagwort(e): chromium ; oxidation ; scale failure ; scale morphology
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation kinetics of chromium at 900°C are independent of the oxygen partial pressure. Although this observation gives evidence for a defect mechanism where chromium interstitials account for the chromium transport in the oxide scale, the experimental phenomena do not support one single model. The occurrence of oxide whiskers and oxide ridges are explained by the energy of activation for the breakup of the oxidant molecule. Large oxide pegs are formed at metal multiple-grain junctions after scale breakdown.
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  • 68
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 43 (1995), S. 157-172 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; NiAl ; ion implantation ; TEM
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The influence of Y-ion implantation on the oxidation of β-NiAl single crystals has been investigated using SEM, TEM, and STEM. Y ions having an energy of 70 keV were implanted with a concentration of 5×1016 ions/cm2. The oxidation experiments were performed in air at 1223 K. Y-ion implantation resulted in a 45-nm disordered layer. Oxidation of Y-implanted β-NiAl leads to the formation of a fine-grain layer, consisting of γ-Al2O3 containing Y and a θ-Al2O3 layer. After further oxidation the metastable Al2O3 transformed into α-Al2O3, which started at the metal-oxide interface. Y-Al-garnet (YAG) particles were observed and Y segregation to α-Al2O3 grain boundaries has been detected.
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  • 69
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 43 (1995), S. 217-236 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; reactive-element effects ; electrodeposition ; Y2O3 ; oxide film
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Thin Y2O3 films were deposited by the electrochemical deposition-pyrolysis process on Fe−25Cr and Fe−25Cr−10Al alloys. The influence of the films on the oxidation behavior of the alloys was studied at 850°C and 1000°C. The results showed that Y2O3 films remarkably decreased the oxidation rate of Cr2O3-forming alloys and spallation of the scales, but they did not decrease the oxidation rate of the Al2O3-forming alloys, although they do reduce the spallation of Al2O3 scales. Y2O3 films remarkably change the morphology of the scales on both alloys, depending on the oxidation temperatures. These results show that the reactive-element effects of Y2O3 films on the Cr2O3 formers and Al2O3 formers are different.
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  • 70
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 43 (1995), S. 185-215 
    ISSN: 1573-4889
    Schlagwort(e): copper ; oxidation ; direct current ; uninterrupted mode ; interrupted mode
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Oxidation kinetics of copper in the temperature range of 973–1173 K atP O 2=21.27 kPa exhibit enhancement and deceleration in the rates with changing polarity compared to normal oxidation under interrupted mode of directcurrent application. These conditions are achieved by connecting the oxidizing copper covered with an initially formed thin oxide film to the positive and negative terminal of a dc source, respectively. However, the influence of direction of the current is found to be opposite under uninterrupted mode of impressed current flow in the same temperature range. The effect of short-circuiting the metal to the outer oxide/air interface on the reaction kinetics is also reported. The rate of oxide-scale growth under normal condition, and two different modes of current applications as well as with shorting circuitry attachment conform to the parabolic growth law. The results pertaining to the two different modes of impressed current have been discussed considering both the phenomena of electrolysis of the oxide electrolyte and the polarization at the two phase boundaries. The enhancement and the reduction in rates under uninterrupted impressed current conditions are explained on the basis of increased and decreased average defect concentrations, respectively, within the oxide layer. The acceleration and deceleration in the rates under interrupted mode of current flow have been explained in the light of sustenance of a steeper and flatter electrochemical-potential gradient of defects, respectively, across the growing-oxide layer. The possible different responses of the metal/oxide and oxide/air interfaces to the impressed current brought into play by two different modes of current application, have enabled to display a better insight on the mechanistic aspects of scale growth under the influence of an externally applied current.
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  • 71
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 43 (1995), S. 237-261 
    ISSN: 1573-4889
    Schlagwort(e): manganese ; oxidation ; ceria ; coating ; air ; low oxygen pressure ; high temperature ; manganosite ; transport mechanism ; iron ; CeFeO3 structure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The kinetics, scale composition, and growth mechanism of ceria-coated and blank specimens of manganese oxidation in air were examined. The scale growth obeys the parabolic rate law at 700°C for all specimens. Lower parabolic rate constants for coated specimens are attributed to the presence of a CeO2 external scale. It constitutes a limiting factor of the oxygen activity at the gas-oxide interface. This lower-oxygen activity leads to a less-metal-deficient state of the scale. Due to this, the inner-MnO scale becomes more adherent to the substrate. Preheating at 700°C, in hydrogen (PO 2=10−24 atm), was performed in order to be placed in the MnO stability domain and try to introduce cerium in the manganese-oxide scale. This pretreatment promotes macroscopic bonding in the layer formed during subsequent oxidation in air. It ensures a better scale adherence. A new diffusional-transport mechanism in manganosite is proposed in accordance with all experimental observations of the literature and with the cerium-manganese-oxygen system studied in the present work. This model considers the high Mn3+ stability in octahedral sites of the MnO oxygen ion body. Low-oxygen partial pressure conditions permit the formation of an adherent inner-MnO scale on coated specimens. A CeO2 scale formed above the MnO scale; MnO is present as a minor component in this scale and it is located mainly at the internal interface. The difficulties in forming the cerium-orthomanganite are attributed to the very high stability of MnO related to this wide range of nonstoichiometry and to the low manganese diffusivity through the cerium-containing scale.
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  • 72
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; chromium coating ; laser ; oxygen diffusion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation of a chromium PVD coating on pure iron by a continuous 5-kW CO2 laser beam in pure oxygen at 700°C for 20 min was compared with classical furnace oxidation. Laser oxidation induces faster oxidation kinetics, especially at the beginning of oxidation, without modifying the oxide nature (Cr2O3) and morphology. Oxygen-isotopic-exchange tests show that oxygen grain-boundary diffusion does not depend on the oxidation conditions, at least after 12 min oxidation. The effec of the laser treatment is discussed with respect to oxide nucleation, metastable-oxide formation, and oxide-formation-entropy evolution. The oxidation kinetics follow a parabolic law, and the oxide-growth mechanism was attributed to countercurrent oxygen and chromium diffusion along grain boundaries. Oxygen diffusion occurred by oxygen interstitials. The oxidation constant calculated from grain-boundary diffusion in the chromia scale is smaller than the experimental oxidation constant, suggesting the presence of particular short circuits (e.g., microcracks).
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  • 73
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    Oxidation of metals 43 (1995), S. 317-328 
    ISSN: 1573-4889
    Schlagwort(e): microcrystalline ; rehealing ; oxide scales ; superalloys ; coating ; oxidation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The rehealing ability of the protective oxide scales formed on a microcrystalline coating of the Ni-base superalloy K38G has been studied. The results indicated that the oxide scales on the coating may be rehealed when the original scales are destroyed, and the coating still has excellent resistance against high-temperature oxidation. When the original Al2O3 oxide scales spall, mixed-oxide scales of both (Al, Cr)2O3 and TiO2 can form on the surface. The mixed scales are very protective and adherent.
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  • 74
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    Oxidation of metals 43 (1995), S. 263-277 
    ISSN: 1573-4889
    Schlagwort(e): Fe−Cr−Ni alloy ; oxidation ; silica ; spallation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract In order to determine the effect of alloy grain size on the oxidation properties of silica-coated austenitic Fe-18Cr-20Ni stainless steel, both coarse-grain (100-μm grain size) and fine-grain (5-μm grain size) forms of the alloy were produced. A 1-μm-thick vitreous silica coating was deposited by chemicalvapor deposition on the alloys, which were subjected to isothermal and cyclic oxidation in air at 900°C. The coarse-grain alloys underwent widespread oxidation below the silica coating, leading to extensive coating spallation. This was attributed to the inability of the alloy to supply a sufficient outward flux of chromium to prevent oxygen penetration through microcracks in the silica coating. Due to an abundance of chromium available at the surface of the finegrain alloy, chromia formed in the microcracks within the silica layer. As a result, the silica-coated, fine-grain alloy demonstrated superior oxidation resistance and excellent adhesion of the coating.
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  • 75
    ISSN: 1573-4889
    Schlagwort(e): Ni−Cr−Al−Ti−Si bond-coating alloy ; phase stability ; oxidation ; interdiffusion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract A novel, low-expansion experimental Ni−Cr−Al−Ti−Si bond-coating alloy was investigated in the as-cast state concerning its phase stability, oxidation resistance in air, and interdiffusion with single-crystal IN-100 at 900, 1000, and 1100°C. Isothermal oxidative thermogravimetry was employed up to 500 hr. Interdiffusion was compared to a commercial Ni−Co−Cr−Al−Y alloy on IN-100. Oxidized Ni−Cr−Al−Ti−Si specimens and diffusion couples were characterized by metallography, SEM, EDX, XRD, and XRF. The Ni−Cr−Al−Ti−Si alloy provides good oxidation resistance in air at least up to 1000°C. The alloy is an alumina former. Due to its coarse microstructure, other oxides (e.g., rutile) may form and considerably dominate the oxidation behavior. The kinetics of oxidation were correlated with temperature, formation of phases, and morphology of oxides. Interdiffusion fluxes between Ni−Cr−Al−Ti−Si and IN-100 were mainly directed to the superalloy. They were faster than in Ni−Co−Cr−Al−Y/IN-100 diffusion couples.
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  • 76
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    Oxidation of metals 43 (1995), S. 379-394 
    ISSN: 1573-4889
    Schlagwort(e): two-phase alloys ; oxidation ; scale structure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The main possible modes of the high-temperature corrosion of binary two-phase alloys by a single oxidant under gas-phase pressures sufficient to corrode only the most-reactive alloy component are examined to compare their behavior with that of single-phase alloys. In the absence of important diffusion processes of the metal components in the alloy, the scale structures expected are different from those typical of single-phase alloys. Moreover, when diffusion in the alloy becomes important, these systems may develop an outer single-phase layer depleted in the most-reactive component, which may lead to different possible scale structures. The conditions for the transition between the various oxidation modes as well as the effect of the various parameters of kinetic, thermodynamic, and structural nature over the corrosion behavior of two-phase alloys are also examined.
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  • 77
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; reactive-element effect ; reactive-element oxysulfide ; reactive-element oxide ; reactive-element orthochromite
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Nickel-base alloys of nominal composition Ni-25 Wt.% Cr-(0-0.6 Wt.%) RE (RE=Y, La, and Ce) were prepared by conventional arc-melting Ni, Cr, and Y metal. The microstructure of the alloys was characterized by using electron diffraction and X-ray energy dispersive spectroscopy (XEDS) to determine the structure, morphology, and distribution of second-phase particles. Selected alloys were oxidized at 900°C and 1000°C in 1-atm air, and the resultant oxide scales were characterized using the same analytical techniques. The experimentally determined electron-diffraction data were compared with a JCPDF-EDD database, and several compounds were matched. The observed phases were RE oxysulfide, cerium orthochromite-CeCrO3, yttria-Y2O3, yttrium orthochromite-YCrO3, and Ni5Y. The significance of these observations is discussed with respect to the current level of knowledge on the role of sulfur in the reactive-element effect. The ability of the reactive elements to getter sulfur is examined with respect to the thermodynamic stability of the oxysulfide species.
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  • 78
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    Oxidation of metals 43 (1995), S. 395-409 
    ISSN: 1573-4889
    Schlagwort(e): microcrystalline film ; TiAl intermetallic compound ; oxidation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation behavior of a cast TiAl intermetallic compound and its sputtered microcrystalline film was investigated at 700–900°C in static air. At 700°C, both the cast alloy and its sputtered microcrystalline film exhibited excellent oxidation resistance. No scale spallation was observed. However, at 800–900°C, the oxidation kinetics for the cast TiAl alloy followed approximately a linear rate law, which indicates that it has poor oxidation resistance over this temperature range. The poor oxidation resistance of TiAl was due to the formation of an Al2O3+TiO2 scale which spalled extensively during cooling. Nevertheless, the sputtered, TiAl-microcrystalline film exhibited very good oxidation resistance. The oxidation kinetics followed approximately the parabolic rate law at all temperatures. Although the composition of the scales was the same as that of scales formed on the cast alloy, the scales formed on the sputtered microcrystalline-TiAl film are adherent strongly to the substrate. No scale spallation was found at 700–850°C, while a small amount of spallation was observed only at 900°C. This indicates that microcrystallization can improve the oxidation resistance of the TiAl alloy.
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  • 79
    Digitale Medien
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    Oxidation of metals 43 (1995), S. 509-526 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; kinetics ; tantalum ; oxide ; suboxide ; impurities ; diffusion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The kinetics, structural aspects, and phase morphologies were studied for tantalum oxidation in air from 600 to 1000°C for samples of different purity (99.15%, 99.76%, and 99.95% Ta). Regardless of purity, tantalum oxidation in the temperature range of 600–800°C as a rule is governed by a linear rate law. From 900 to 1000°C the initial-stage oxidation is governed by the parabolic rate law, which changes to the linear rate law with time. TGA, XRD, SEM, and AES methods were used. The, effect of purity on tantalum oxidation was shown to be determined by the mechanism of intermediate-oxide formation. They are TaO z (Ta2O) at 600–800°C and TaO at 900–1000°C. The final product of oxidation was β-Ta2O5.
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  • 80
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 43 (1995), S. 527-542 
    ISSN: 1573-4889
    Schlagwort(e): Co−Nb alloys ; high temperature ; oxidation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation of two Co−Nb alloys containing 15 and 30 wt.% Nb has been studied at 600–800° C in H2−CO2 mixtures providing an oxygen pressure of 10−24 atm at 600°C and 10−20 atm at 700 and 800°C, below the dissociation pressure of cobalt oxide. At 600 and 700°C both alloys showed only a region of internal oxidation composed, of a mixture of alpha cobalt and of niobium oxides (NbO2 and Nb2O5) and at 700°C also the double oxide CoNb2O6, which formed from the Nb-rich Co3Nb phase. No Nb-depleted layer formed in the alloy at the interface with the region of internal oxidation at these temperatures. Upon oxidation at 800°C a transition between internal and external oxidation of niobium was observed, especially for Co−30Nb. This corrosion mode is associated with the development of a single-phase, Nb-depleted region at the surface of the alloy. The corrosion mechanism of these alloys is examined with special reference to the effect of the low solubility of niobium in cobalt and to the relation between the microstructures of the alloys and of the scales.
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  • 81
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    Oxidation of metals 44 (1995), S. 177-209 
    ISSN: 1573-4889
    Schlagwort(e): sulfidation ; oxidation ; common and refractory metals and alloys ; amorphous alloys
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The role of defect and transport properties of transition metal sulfides on the kinetics and mechanism of high-temperature sulfide corrosion of metals and alloys is discussed. It has been shown, that due to the very high concentration of defects in common metal sulfides, not only pure metals but also conventional high-temperature alloys (chromia and alumina formers) undergo very rapid degradation in highly sulfidizing environments. Refractory metals, on the other hand, are highly resistant to sulfide corrosion, their sulfidation rates being comparable with the oxidation rate of chromium. Pioneering work of Douglasset al. has shown that alloying of common metals by niobium or molybdenum, and in particular combined alloying by molybdenumand aluminum, dramatically decreases the sulfidation rate. A novel Fe−30Mo−9Al alloy has been proved to be highly resistant to sulfide corrosion, its sulfidation rate being comparable with that of pure molybdenum. Even better resistance to highly-sulfidizing environments show new amorphous Al−Mo and Al−Mo−Si alloys, these materials also being simultaneously oxidation resistant. Thus, new prospects have been created for the development of a new generation of coating materials, resistant to multicomponent sulfidizing-oxidizing atmospheres, often encountered in many branches of modern technology.
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  • 82
    ISSN: 1573-4889
    Schlagwort(e): binary alloys ; oxidation ; transient state ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The initial transient stage in the oxidation of binary alloys forming scales exclusively composed of the most stable oxide is examined by means of a simplified approach which avoids the numerical integration of the diffusion equation for the transport of the metal components in the alloy. At variance with previous solutions to this problem obtained by means of numerical methods, this treatment takes into account also the effect of the gas-scale reaction at the outer surface of the oxide. The concentration of the most-reactive component at the alloy surface changes gradually with time from the initial bulk value towards the corresponding steady-state value without involving any minimum, while the overall rate of the reaction presents a gradual transition from an initial nearly linear towards final parabolic behavior.
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  • 83
    Digitale Medien
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    Oxidation of metals 47 (1997), S. 247-258 
    ISSN: 1573-4889
    Schlagwort(e): Ni3Al-base alloy ; sputtering ; nanocrystalline coating ; oxidation ; scale adhesion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Isothermal and cyclic oxidation resistance at 1000°C in air were investigated for a cast Cr-containing Ni3Al-base alloy and its sputtered nanocrystalline coating. The results indicated that both the cast Ni3Al alloy and its sputtered coating exhibit excellent isothermal oxidation resistance as a result of the formation of Al2O3 scales. However, the cast alloy possesses very poor cyclic oxidation resistance because of the spallation of the initially formed Al2O3 scale during cooling and subsequent formation of NiO. On the contrary, the sputtered Ni3(AlCr) nanocrystalline coating exhibits very good cyclic oxidation resistance due to the significant improvement of the adhesion of Al2O3.
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  • 84
    Digitale Medien
    Digitale Medien
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    Interface science 3 (1995), S. 133-141 
    ISSN: 1573-2746
    Schlagwort(e): silicon ; Si/oxide interface ; oxidation ; Monte-Carlo ; thin-films
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Physik
    Notizen: Abstract Experiments have shown that the early stages of silicon oxidation proceed layer by layer, so that one layer is essentially complete before another develops. Other experiments show that the mechanism does not involve step growth, the most obvious mechanism. We use a new approach to modelling the growth to show that these two observations can be understood when there is a rate-determining step which depends strongly on the local oxide thickness. The rate in question might be the sticking probability, or the rate of incorporation of adsorbed oxygen species into the oxide network. Such mechanisms are possible when transport by an ionic species dominates, contrary to the situation for thicker films. Our modelling suggests the mechanisms are driven by the image interaction, as in earlier suggestions by Stoneham and Tasker, rather than an effect of the electric field central to the Mott-Cabrera mechanism.
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  • 85
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    Digitale Medien
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    Journal of materials synthesis and processing 6 (1998), S. 335-338 
    ISSN: 1573-4870
    Schlagwort(e): PbZrO3 ; oxidation ; nonstoichiometry
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract This paper reports the results of work function (WF) changes of undoped PbZrO3 during subsequent isothermal oxidation and reduction experiments at 500°C in the p(O2) range between 10 and 2.1 × 104 Pa. The results, obtained during three consecutive runs, indicate that heating at 500°C leads to continuous changes of surface properties resulting in a complex WF vs. time characteristic. The WF changes during the first oxidation are determined by a p(O2)-induced structural transition. The second oxidation results in two competitive processes, such as rapid increase of oxygen non-stoichiometry followed by a structural transition. Finally, the third oxidation is determined by changes of oxygen nonstoichiometry.
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  • 86
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    Digitale Medien
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    Journal of materials synthesis and processing 6 (1998), S. 373-377 
    ISSN: 1573-4870
    Schlagwort(e): Zirconia ; oxidation ; preparation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract This paper reports surface electrical properties of zirconia studied using work function measurements in the temperature range 297–1173 K during oxidation. It was found that surface preparation procedures, such as grinding and polishing, result in a change of its reactivity with oxygen. The effects produced by the preparation can be removed during thermal treatment at 1473 K.
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  • 87
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    Digitale Medien
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    Journal of materials synthesis and processing 6 (1998), S. 407-410 
    ISSN: 1573-4870
    Schlagwort(e): CaB6 ; oxidation ; weight gain ; calcium borate ; oxidation resistance
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation of CaB6 powders at high temperatures was investigated. The sample oxidized at 873 to 973 K for 25 hours exhibited weight gain with increasing oxidation temperature; the oxidation proceeded in accordance with the parabolic law during the initial oxidation stage. On the other hand, the weight gain of the sample oxidized at and above 1073 K for 4 h was approximately 80%; however even if the oxidation time was prolonged, an additional weight change did not occur. Based on the results of the X-ray diffraction analysis, calcium borate (CaB4O7) was present on the surface of the sample oxidized at 1073 K. The sample showed a good oxidation resistance at 1273 to 1373 K, because the surface film of calcium borate (CaB2O4) formed by oxidation acted as an oxidation resistant layer.
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  • 88
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 28 (1987), S. 73-98 
    ISSN: 1573-4889
    Schlagwort(e): chromium ; oxidation ; sulfidation ; mixed oxidants
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation of pure chromium in H2-H2O-H2S gas mixtures was studied as a function of gas composition at 900°C. Oxidation kinetics were measured using a thermogravimetric apparatus, and the oxidation products were characterized using scanning electron microscopy (SEM) and scanning transmission electron microscopy (STEM). Chromia scales formed when the H2O/H2S ratio was about 10 or greater. Scales that comprised a mixture of Cr2O3 and chromium sulfides formed when the H2O/H2S ratio was about 3, even though Cr2O3 was the thermodynamically stable phase under these conditions; i.e., a kinetic boundary exists for pure chromium in H2-H2O-H2S gas mixtures. The transition from chromia scale formation to the formation of scales containing both oxide and sulfide with a change in gas composition (decrease in the H2O/H2S ratio) is associated with an inhibition of the overgrowth of growing, metastable sulfide nuclei by the thermodynamically stable Cr2O2 phase. Presulfidation experiments confirmed that metastable chromium sulfide can continue to grow after H2O is added to the gas phase when the H2O/H2S ratio in the gas phase is less than a critical value at the temperature of interest.
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  • 89
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    Digitale Medien
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    Oxidation of metals 25 (1986), S. 217-234 
    ISSN: 1573-4889
    Schlagwort(e): nickel alloys ; oxidation ; sulfidation ; grain-boundary segregation ; corrosion mechanism
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The corrosion of nickel with alloy additions of Si, Fe, and/or Mn up to 4 wt% has been studied in SO 2+O2/SO3 at 700°C. All alloy additions greatly improve the corrosion resistance of nickel in oxygen-rich atmospheres (O2 with about 4% SO2); the best improvements are achieved with Si, Fe+Si, and Fe+Mn+Si additions. High-purity nickel corrodes rapidly under these conditions; the scale then consists of NiO+Ni3S2, and the sulfide forms a three-dimensional network along the grain boundaries of the NiO grains and serves as the diffusion path for rapid outward migration of nickel. From studies of the microstructure and distribution of the alloying elements in the protective scales, it is proposed that the alloying additions exert their beneficial effects by accumulating/segregating at the grain boundaries of NiO (e.g., as silicates) and thereby influence the wetting characteristics and disrupt the sulfide network.
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  • 90
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 25 (1986), S. 235-268 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; Mn2O3 ; spinels ; manganowustite ; mechanisms ; fusion reactors
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation in air of an austenitic Fe-Mn-Cr steel containing 17.8 Mn, 9.5 Cr, 1.0 Ni, 0.27 C, and 0.03 N was studied over the range 700–1000°C. Oxidation of surface-abraded samples at “low” temperatures, 700–750°C, resulted in only Mn 2O3 containing dissolved chromium, except at corners, where large nodules containing spinel and manganowustite formed. The Mn2O3 layer grew into the substrate forming a globular-type film. This growth mode was the result of slow interdiffusion in the alloy after the cold-worked surface layer had been recrystallized and/or consumed, as evidenced by the formation of a ferrite layer subjacent to the scale and by the instability of the planar interface. No internal oxidation was observed beneath the Mn2O3 film at either 700 or 750°C. Samples oxidized in the“high-temperature” region, 800–1000°C, exhibited vastly different behavior, forming thick stratified scales at long times (24 hr), the scales consisting of a very thin outer layer of Mn2O3 (with appreciable iron in solution), Fe-Mn spinel beneath the outer layer, and a thick inner layer of manganowustite and a chromium-containing spinel. No chromium was found in the outer two layers. A thin layer of nearly pure Fe2O3 formed between Mn2O3 and the outer spinel. Quasiparabolic kinetics were observed. The high-temperature rates were about 103 to 104 times greater than at low temperatures at the “transition” temperature. The rapid rates at high temperatures were attributed to manganowustite growth. However, oxidation of an electropolished sample at 750°C, from which the superficial cold-worked layer had been removed, formed scales similar to those observed at high temperatures at comparable rates. A difference by a factor of over 104 existed between the oxidation rate of the electropolished sample and the surface-abraded sample at 750°C. The much slower oxidation rate of the latter is attributed to greatly enchanced manganese diffusion through the high dislocation-density, cold-worked layer. Short-time tests at 800°C revealed an incubation period during which a thin protective layer of Mn2O3 formed. The incubation period corresponded to the recrystallization time of the cold-worked layer. Subsequently, nodular growth occurred which was associated with internal oxidation. The nodules, consisting of spinel and manganowustite, eventually linked up to form a thick, stratified scale. Comparison of the scale structures with calculated phase diagrams of composition versus oxygen activity (at constant temperature), showed that the protective films formed at low temperatures were due to kinetics factors, involving enhanced manganese diffusion through the cold-worked layer, rather than to thermodynamics. A model for the breakdown of protective films is proposed which involves internal oxidation.
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  • 91
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    Oxidation of metals 26 (1986), S. 125-138 
    ISSN: 1573-4889
    Schlagwort(e): hot corrosion ; oxidation ; aluminide coatings ; nickel ; nickel alloys
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Aluminide and chromaluminide diffusion coatings on nickel and a nickel-base superalloy, EI 867, were subjected to different corrosion tests consisting of oxidation under isothermal and thermal cycling conditions, and oxidation in the presence of fused sodium sulfate. It was found that chromium present in the surface layers of aluminide coatings has a beneficial effect on their resistance to oxidation and hot corrosion.
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  • 92
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 26 (1986), S. 45-76 
    ISSN: 1573-4889
    Schlagwort(e): Ni-base alloys ; oxidation ; influence of oxygen partial pressure at high temperatures ; kinetics and mechanisms of high temperature oxidation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation behavior of the Ni-base alloys IN 617, IN 713 LC, Ni20Cr, and Ni20Cr+Si has been investigated in the temperature range from 850°C to 1000°C in air and at low-oxygen partial pressure p(O2) (10−19 to 10−16 bar). With the exception of alloy IN 713 LC, the materials show no influence of p(O2) on the oxidation mechanisms and the kinetics. This result can be explained by the formation of a dense Cr2O3 layer, the growth rate of which is controlled by the Cr ion interstitial concentration in Cr2O3 at the phase boundary oxide/alloy and the mobility of Cr ions in Cr2O3. For the alloy IN 713 LC which develops a dense Al2O3 layer in air, a modified transition mechanism at low p(O2) leads to the formation of Cr2O3 at the surface and a strong internal oxidation of Al.
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  • 93
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    Oxidation of metals 27 (1987), S. 1-20 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; titanium ; silicon ; adherence ; titanium-silicon alloys
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation behavior of Ti-Si alloys (0.25, 0.5, and 1 Wt. % Si) was investigated between 550 and 700°C; in oxygen by continuous thermogravimetry for a maximum duration of about 500 hr and, in air by daily weighing for durations from a few hundred to several thousand hours. The kinetics results revealed that the presence of silicon leads to a decrease in oxidation rate which is more evident when the temperature is raised and the silicon content is increased. Morphological and structural examinations revealed that silicon modifies the internal architecture of oxide layers when compared with unalloyed titanium; in particular, reduced porosity in the layers is observed. Analysis showed that silicon is uniformly distributed in the oxide layer. However, while part of the silicon is in solid solution in the rutile, some is also precipitated as small crystals (φ 〈1 μm at 850°C) of SiO2, of cristobalite structure. The adherence of oxide layers to the metal substrate was measured after cooling of samples; the addition of silicon has been observed to modify, in a manner dependent on its content, the adherence of oxide layers.
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  • 94
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    Oxidation of metals 27 (1987), S. 315-332 
    ISSN: 1573-4889
    Schlagwort(e): chromium ; NaCl ; oxidation ; hot corrosion ; mechanism
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation rate of NaCl-coated chromium was measured over the temperature range of 823–1043 K. Although the melting point of NaCl is 1074 K, accelerated oxidation was observed at every temperature. Oxidation mass-gain curves were divided into two types. Type I involved only accelerated oxidation during the initial stage followed by the formation of a thin protective Cr2O3 film. Type II pertained to an acceleration over a long time, forming a thick and nonprotective Cr2O3film containing Na2CrO4. The former type of oxidation occurred at lower temperatures or with a small amount of NaCl, whereas the latter occurred at higher temperatures and with large amounts of NaCl. A comparison of these oxidation processes with those by CaCl2 or BaCl2, revealed two problems: (1) Why was the oxidation rate of chromium so high in the presence of NaCl?, and (2) Why did the high oxidation rate continue for such a long time?
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  • 95
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    Oxidation of metals 27 (1987), S. 301-314 
    ISSN: 1573-4889
    Schlagwort(e): diffusion mechanisms ; point defects ; oxidation ; NiO-V2O5
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract A model is proposed for the oxidation of metals including both bulk crystal lattice diffusion and short-circuit diffusion paths. Assuming local equilibrium between point defects in the bulk and in grain boundaries, we obtain an effective parabolic rate constant keff=kbulk [1+θ exp-(ΔH/RT],where ΔH is the enthalpy for the reaction between point defects in the bulk and in short circuits, θ is the fraction of the short-circuit area, and T is temperature. In the case of the high-temperature oxidation of nickel coated with a thin film of vanadium pentoxide, this model yields to a rate law with a critical oxygen pressure P c. The nickel vanadium oxide located in the short circuits of the growing oxide NiO is liquid below Pc, leading to a rapid short-circuit diffusion. Above this value, a vanadate precipitates and acts as diffusion blocks for migrating Ni ions.
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  • 96
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    Oxidation of metals 29 (1988), S. 153-167 
    ISSN: 1573-4889
    Schlagwort(e): zirconium ; oxidation ; parabolic kinetics ; linear kinetics ; cubic kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract A model is proposed to describe parabolic followed by linear oxidation kinetics of zirconium and zircaloy. The one-dimensional description presented here for parabolic kinetics considers the superficial oxide layer as formed by a succession of diffusion layers of crystalline oxide alternating with short-circuit paths for diffusion. Within this framework, the parabolic-linear transition can be viewed as the result of the rupture of the thin diffusion laters, leaving behind long channels connecting the oxidizing environment with the diffusion region adjacent to the oxide-metal interface. These channels represent easy paths for oxygen diffusion. This model unifies the description of parabolic oxidation of Zr with that of linear kinetics and can be also connected with the description of cubic oxidation kinetics. The latter can be thought of as the result of a recrystallization process where the oxidation rate diminishes more than during a parabolic regime as time progresses due to the growing influence of volume diffusion.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 97
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 29 (1988), S. 409-418 
    ISSN: 1573-4889
    Schlagwort(e): Microstructure ; oxidation ; chromium oxide
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Four commercially available Ni-Cr-based alloys used with porcelain enamels were studied. Major alloying elements were Al, Be, Si, B, Nb, and Mo. All alloys were multiphase. During heat treatments simulating enameling conditions, phase changes occurred in most alloys and were detected using hardness testing, differential thermal analysis (DTA), and microscopy. Oxidation of these alloys at 1000°Cfor 10 min produced an oxide layer consisting principally of chromium oxide, but the oxide morphology varied with each alloy depending on the alloy microstructure. Controlling alloy microstructure while keeping the overall composition unchanged may be a means of preventing wrinkled poorly adherent scales from forming.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 98
    ISSN: 1573-4889
    Schlagwort(e): Ni-base alloy IN 617 ; reactor helium ; oxidation ; carburization ; decarburization ; kinetics ; mechanisms
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Application of the technical nickel-base alloy IN 617 in the primary circuit of the high-temperature gas-cooled reactor is limited essentially by the chemical reactions with the impurities (CO, CO2, H2, CH4, H2O) in the helium coolant. The interactions of the alloy with the reactive impurities in different helium-base gases were investigated by thermogravimetry in a gas-tight microbalance and by simultaneous measurement of the changes in gas composition by a continuous sensitive mass spectrometric analysis. The results demonstrate that the set of six reaction equations deduced in part 1 can be applied to describe the corrosion of the alloy. The occurrence of the various reactions is determined essentially by temperature. For the case of a standardized helium gas (HHT-He), three temperature regions can be distinguished. Below a critical temperature (about 1105 K), the presence of CO can cause simultaneous oxidation and carburization. Above this temperature, this reaction does not reverse itself. Rather, oxidation by CO2 and H2O takes place that shows, after a transient period, the same kinetics observed in undiluted oxygen-containing gases. At temperatures above about 1205 K, decarburization of the alloy accompanied by the production of CO takes place, leading to severe destruction of the carbide microstructure and, therefore, limiting the applicability of the material.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 99
    ISSN: 1573-4889
    Schlagwort(e): constant-extension-rate tests ; Incoloy 800H ; sulfidation ; oxidation ; sol-gel method ; cerium ; ceramic coatings
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The mechanical properties of ceramic coatings containing cerium oxide, prepared by the sol-gel method and used to protect Incoloy 800H against aggressive environments, are reported. Deformation and cracking behavior in oxidizing and sulfidizing environments has been investigated by constant-extension-rate tests. Extension rates were between 9.3×10−6 and 3.7×10−7 sec−1 at 823 〈T〈973 K. Under these conditions, cerium oxide sol-gel-coated specimens do not show any failure at extensions of 1.0% or more, but in hydrogen, sulfide failure is found at lower extensions than in air.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 100
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 31 (1989), S. 305-323 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; sulfidation ; Fe-Cr-Ni alloys ; Nb addition ; Zn addition ; breakaway corrosion ; mixed-gas atmospheres
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Structural Fe-Cr-Ni alloys may be rapidly degraded in oxygen-sulfur mixed-gas environments at elevated temperatures unless protective oxide scales can be formed and maintained. The breakaway corrosion process was examined in model alloys of Fe-25wt.% Cr-20wt.% Ni with and without Nb and Zr additions. Oxide scales were preformed in S-free environments and subsequently exposed to oxygen-sulfur mixed-gas atmospheres. Preformed scales were found to delay the onset of breakaway corrosion. The beneficial effects of refractory metal additions were achieved via formation of a barrier layer at the Cr2O3 alloy interface.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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