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  • Engineering General
  • oxidation
  • 1985-1989  (2,541)
  • 1970-1974  (492)
  • 1950-1954
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 17 (1988), S. 581-599 
    ISSN: 1572-8927
    Keywords: Copper ; oxidation ; NaCl solutions ; ionic strength ; speciation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The rates of oxidation of Cu(I) in air saturated solutions was measured as a function of pH, temperature (5–45°C), and ionic strength (0.5 to 6m) in NaCl and NaCl−NaClO4 solutions. In pure NaCl solutions, the effect of pH is independent of ionic strength and temperature. The overall rate constant is given by logk=12.32+0.12(pH)−2064/T−3.69I1/2+ 0.73I The energy of activitation was 39±2 kJ-mol−1 and is independent of ionic strength. At a constant ionic strength (I=1, 3 and 6m) in NaCl−NaClO4 mixtures the Cl− dependence of the rates is attributed to the oxidation of the various forms of Cu(I) in the solution. The rate constants for the oxidation of the various species are found to be functions of ionic strength. At a constant ionic strength (I=1) in NaCl−NaClO4 solutions, the effect of temperature is independent of the chloride concentration. The effect of Mg2+ and HCO 3 − on the oxidation rate was determined as a function of chloride concentration (1 to 6m) at 25°C and pH=8. The addition of Mg2+ causes the rate to decrease and the addition of HCO 3 − causes the rate to increase. The possible causes of these effects are discussed. Empirical equations for the rate of oxidation of Cu(I) in Na-Mg-Cl-HCO3 solutions as a function of composition are used to make reliable estimates of the oxidation in seawater and Red Sea waters.
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  • 2
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    Journal of solution chemistry 18 (1989), S. 585-599 
    ISSN: 1572-8927
    Keywords: Fe(II) ; oxidation ; ionic strength ; NaCl ; NaClO4
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The rates of oxidation of Fe(II) in NaCl and NaClO 4 solutions were studied as a function of pH (6 to 9), temperature (5 to 25°C), and ionic strength (0 to 6m). The rates are second order with respect to [H+] or [OH−] and independent of ionic strength and temperature. The overall rate of the oxidation is given by $$d[Fe(II)]/dt = - k[Fe(II)][OH^ - ]^2 [O_2 ]$$ where [OH−]=K W * /[H+](K W * is the stoichiometric dissociation constant for water) and [O 2 ] is the molal concentration of the oxygen. The experimental results were fitted to equations of the form $$log{\text{ }}k = log{\text{ }}k_0 + {\rm A}\sqrt {\rm I} + {\rm A}\sqrt {\rm I} /T + CI$$ where log k0=21.56−1545/T, A=0.470, B=−646, and C=0.723 (σ=0.07) for NaCl; A=−1.638, B=0, and C=0.836 (σ=0.11) for NaClO 4 . The lower results in NaCl at higher ionic strengths are attributed to the formation of FeCl+ that has a slower rate of oxidation. The kinetic results giveβ FeCl = 1.2 ± 0.5, which is in reasonable agreement with literature data. Measurements of the effect of various ions on the rates were studied at constant ionic strength. The results were in the order HCO 3 − 〉Br−〉ClO 4 − 〉Cl−〉NO 3 − 〉SO 4 2− 〉B(OH) 4 − and were attributed to the relative strength of the interactions of Fe 2+ with these anions. The strong interactions of Fe 2+ with SO 4 2− and B(OH) 4 − were used to estimate the stability constants, logβ FeSO 4 = 1.8 ± 0.1 and logβ FeB(OH) 4 = 3.2 ± 0.1, which are in reasonable agreement with literature data.
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  • 3
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    Catalysis letters 3 (1989), S. 191-195 
    ISSN: 1572-879X
    Keywords: Iron ; zirconium ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Small α-iron particles with diameter less than 10 nm and enlarged lattice constant have been obtained by low temperature oxidation and reduction of an amorphous Fe91Zr9 alloy.In-situ X-ray diffraction has been used to study the transformation of the alloy at 300 °C which is far below the crystallization temperature. Scanning electron microscopy showed that the reacted sample consisted mainly of aggregates of small iron particles. This might offer a promising method for the effective preparation of heterogeneous catalysts.
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  • 4
    ISSN: 1436-5073
    Keywords: thionic compounds ; oxidation ; potassium permanganate ; nephelometric determination
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The indirect determination of thionic compounds by nephelometric determination of barium sulfate, formed after treatment of the compounds containing the group CS with potassium permanganate in neutral aqueous solutions, has been studied. Allylthiourea, thiourea, thioacetamide and thiosemicarbazide have been tested. The determination limit was 0.05 μg/ml and the RSD less than 10%.
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  • 5
    ISSN: 1436-5073
    Keywords: silicon carbide ; surface ; oxidation ; FT-IR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The surface of ultrafine silicon carbide powders, prepared by a laser-driven gas-phase reaction was studied as a self-supporting disk by FT infrared spectrometry. After evacuation silicon and carbon atoms located at the surface give rise tovSiH andvCH bands. When heating in oxygen, subtraction spectra showed features which could be strictly correlated with a progressive growth of a silica layer: SiH and CH bands were replaced by new bands characteristic of amorphous silica and the typical band of surface silanol groups on silica (3745 cm−1) simultaneously increased.
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  • 6
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    European journal of clinical pharmacology 7 (1974), S. 461-466 
    ISSN: 1432-1041
    Keywords: Acetanilide ; oxidation ; diphenylhydantoin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Acetanilide and diphenylhydantoin have a similar first stage biotransformation in that both are oxidized in the para position of the benzene ring incorporated in each of the two molecules. The elimination of acetanilide from the plasma was studied in thirty healthy volunteer subjects following a single oral dose of 50 mg per kg metabolically active mass (MAM = weight to the power of 0.7). Plasma clearance values varied from 12.4 to 25.11 per hour. A dose of 5 mg diphenylhydantoin sodium (DPH) per kg MAM was then given thrice daily for 13 days to the same volunteers. The steady state plasma concentrations of DPH varied from 3.4 to 19.6 µg per ml. Statistically significant correlation was demonstrated between plasma acetanilide clearance and DPH clearance (r=+0.4984). This finding suggests either a common enzyme acceptor or a common rate-limiting step in the metabolism of the two drugs. It is possible that the pharmacokinetics of other widely used drugs known to be oxidized, especially phenylbutazone, may also be correlated with the kinetics of acetanilide and of DPH. If this were so, then certain individuals might be at a relatively high risk (due to drug accumulation) of developing adverse effects from drugs metabolized mainly by oxidation, and certain other individuals who metabolize these compounds at a fast rate are likely not to derive therapeutic benefit. A single dose study with simple measurement of acetanilide pharmacokinetics could be used to identify these groups.
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  • 7
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    European journal of clinical pharmacology 35 (1988), S. 441-442 
    ISSN: 1432-1041
    Keywords: debrisoquine ; oxidation ; diurnal variation ; metabolic ratio ; oxidative phenotype
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary A study was performed to show whether debrisoquine phenotyping could be performed as an overnight procedure. Phenotyping of 33 normal volunteers was carried out during the day and night. A good correlation was observed between the day-and night-time metabolic ratios, although wide variation was observed in 3 subjects.
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  • 8
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    Plasma chemistry and plasma processing 6 (1986), S. 27-38 
    ISSN: 1572-8986
    Keywords: AC discharge ; discharge chemistry ; hydrogen cyanide ; cyanogen ; chemiluminescence ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract 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.
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  • 9
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    Oxidation of metals 28 (1987), S. 195-211 
    ISSN: 1573-4889
    Keywords: Uranium ; corrosion ; oxidation ; liquid metal
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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.
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  • 10
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    Oxidation of metals 28 (1987), S. 353-389 
    ISSN: 1573-4889
    Keywords: Grain growth ; nickel oxide ; high temperature ; oxidation ; nickel
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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.
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  • 11
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    Oxidation of metals 8 (1974), S. 393-407 
    ISSN: 1573-4889
    Keywords: cobalt alloys ; oxidation ; manganese
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Earlier studies have suggested that manganese might be attractive as an alternative fcc stabilizer to nickel in cobalt base alloys because of its beneficial effect on the sulfidation resistance. Because it has relatively high oxygen affinity, it seemed possible that it might modify the ability of the alloys to form a protective Cr 2O3 scale. Thus, a range of alloys having compositions close to the critical Co-20 Cr value have been investigated in the temperature range 900–1150° C for times up to 240 hr in air and oxygen. Similar, but less extensive studies, have been conducted on alloys containing iron or nickel. None of these elements has a significant effect on the oxidation behavior, or on the ability of the alloys to develop a protective Cr 2O3 layer. However, manganese has a significant adverse effect on the scale spallation, apparently because of its increasing the brittleness of the oxide, particularly the CoO.
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  • 12
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    Molecular and cellular biochemistry 88 (1989), S. 155-159 
    ISSN: 1573-4919
    Keywords: phospholipase A2 ; fatty acids ; oxidation ; suppression
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Summary Cis-unsaturated fatty acids, but not saturated fatty acids, inhibited phospholipase A2 activity (PLA2) in vitro, and may function as endogenous suppressors of lipolysis. To probe the possible role of lipid peroxidation in the regulation of myocardial lipid catabolism, a neutral-active and Ca2+-dependent PLA2 was extracted from rat heart and was partially purified by sulfopropyl cation exchange chromatography. Myocardial PLA, activity was inhibited in a dose-dependent manner by oleic, linoleic, linolenic, and arachidonic acids; the IC50 for arachidonic acid was approx 65 μM. Palmitic acid was not inhibitory. When arachidonic acid was incubated at 37°C, exposed to air, there was a time- and pH-dependent peroxidation of the arachidonic acid as monitored by turbidity, thiobarbituric acid reactivity, and thin layer chromatography. Peroxidation was increased as the pH was lowered from 7.5 to 4.5, and was accompanied by a decrease in PLA2 inhibitory potency. Thus, arachidonate incubated for 24 hours at pH's 4.5, 6.0 and 7.5 lost 84%, 32%, and 20% respectively, of its inhibitory potency. Therefore, in vitro acidosis promotes the oxidation of cis-unsaturated fatty acids and relieves their inhibitory or suppressive activity toward PLA2s. Increased lipid peroxidation of unesterified unsaturated fatty acids during acidosis may therefore promote lipolysis observed during myocardial ischemia and reperfusion injury.
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  • 13
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    Oxidation of metals 24 (1985), S. 133-148 
    ISSN: 1573-4889
    Keywords: oxidation ; nickel ; yttrium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of 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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  • 14
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    Oxidation of metals 24 (1985), S. 177-197 
    ISSN: 1573-4889
    Keywords: oxidation ; short-circuit diffusion ; nickel ; chromium ; binary Ni-Cr alloys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The 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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  • 15
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    Oxidation of metals 26 (1986), S. 139-155 
    ISSN: 1573-4889
    Keywords: oxidation ; Co-Cr-Ti alloys ; kinetics ; scale morphology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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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  • 16
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    Oxidation of metals 26 (1986), S. 305-314 
    ISSN: 1573-4889
    Keywords: oxidation ; metals ; high temperatures ; oxidation theory ; oxidation kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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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  • 17
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    Oxidation of metals 26 (1986), S. 201-212 
    ISSN: 1573-4889
    Keywords: chromium ; NaCl ; chloride ; oxidation ; hot corrosion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract 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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  • 18
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    Oxidation of metals 26 (1986), S. 231-252 
    ISSN: 1573-4889
    Keywords: oxidation ; titanium ; thermogravimetry ; microhardness ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation kinetics of 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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  • 19
    ISSN: 1573-4889
    Keywords: Raman microscopy ; Fe-Cr alloys ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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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  • 20
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    Oxidation of metals 27 (1987), S. 83-93 
    ISSN: 1573-4889
    Keywords: silicon carbide ; oxidation ; constructional ceramics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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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  • 21
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    Oxidation of metals 26 (1986), S. 385-396 
    ISSN: 1573-4889
    Keywords: coatings ; oxidation ; rare earth addition ; dispersed oxides ; scale adhesion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Oxidation studies 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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  • 22
    ISSN: 1573-4889
    Keywords: oxidation ; adhesion ; growth-mechanisms ; impurities ; sulfur
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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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  • 23
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    Oxidation of metals 26 (1986), S. 105-124 
    ISSN: 1573-4889
    Keywords: oxidation ; titanium ; thermogravimetry ; microhardness ; modeling ; mechanical properties ; space shuttle reentry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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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  • 24
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    Oxidation of metals 26 (1986), S. 315-332 
    ISSN: 1573-4889
    Keywords: oxidation ; multilayer oxides ; oxidation kinetics theory ; diffusion mechanisms ; iron
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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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  • 25
    ISSN: 1573-4889
    Keywords: oxidation ; steam ; Ni-base superalloy ; Al oxides ; Ti oxides
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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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  • 26
    ISSN: 1573-4889
    Keywords: laser treatment ; chromia scales ; oxidation ; nickel-chromium alloys ; laser glazing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The influence of 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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  • 27
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    Oxidation of metals 27 (1987), S. 95-102 
    ISSN: 1573-4889
    Keywords: oxidation ; acoustic emission technqiue ; copper
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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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  • 28
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    Oxidation of metals 29 (1988), S. 487-497 
    ISSN: 1573-4889
    Keywords: Alloy ; oxidation ; platinum ; palladium ; rhodium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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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  • 29
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    Oxidation of metals 31 (1989), S. 71-89 
    ISSN: 1573-4889
    Keywords: oxidation ; duplex NiO scale ; segregation ; 18O tracer ; secondary ion-mass spectrometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract 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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  • 30
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    Oxidation of metals 31 (1989), S. 431-452 
    ISSN: 1573-4889
    Keywords: aluminides ; oxidation ; TEM cross sections
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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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  • 31
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    Oxidation of metals 32 (1989), S. 317-335 
    ISSN: 1573-4889
    Keywords: 316L austenitic stainless steel ; porosity ; various additions in stainless steel ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation 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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  • 32
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    Oxidation of metals 32 (1989), S. 295-316 
    ISSN: 1573-4889
    Keywords: Fe-base superalloy ; oxidation ; corrosion in water vapor ; creep rupture strength in water vapor
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation kinetics 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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  • 33
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    Oxidation of metals 8 (1974), S. 379-391 
    ISSN: 1573-4889
    Keywords: oxidation ; sulfidation ; kinetics ; parabolic rate law
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The conditions necessary to determine the oxidation kinetics of metals and alloys are discussed quantitatively, and a new method of calculating the rational rate constants was suggested. It was shown that the size and the shape of a metal sample has an effect on the kinetics of oxidation. Further, it was established that the values of the parabolic rate constants of corrosion, calculated from the empirical Pilling and Bedworth equation, contain a serious systematic error, if changes in the metallic core surface area during the oxidation process are neglected.
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  • 34
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    Molecular and cellular biochemistry 82 (1988), S. 97-106 
    ISSN: 1573-4919
    Keywords: sheep red blood cells ; membrane thiols ; oxidation ; alkylation ; ouabain-resistant ; Cl-dependent ; K transport
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Summary The stimulatory effects of two thiol (SH) group oxidants, methylmethane thiosulfonate (MMTS) and diazene dicarboxylic acid bis [N,N-dimethylamide] (diamide), on the kinetics of ouabain-resistant (OR) K:Cl [co]-transport in low K (LK) sheep red blood cells were compared with the effects of alkylating agents, notably N-ethylmaleimide (NEM). At low concentrations, both MMTS and diamide stimulated K:CI [co]-transportv and with a latency period, as measured by OR zero-trans K efflux and OR uptake of external Rb, Rbo, as K congener in Cl and NO3 media. At high concentrations the effect of diamide saturated, and that of MMTS disappeared. The stimulatory effect of MMTS was partially reversed by the reducing agent dithiothreitol (DTT) known to fully restore the diamide-activated K flux (Lauf, J. Memb. Biol. 101:179–188, 1988). In diamide pre-equilibrated LK sheep red cells, the Km of K:Cl [co]-transport for external Cl, Clo, was 84.3 mM, and 18.7 mM for Rbo, with nearly identical Vmax values around 4 mmol Rb/L cells × h for K (Rb) fluxes in Cl and after correction for the small Cl-independent component. Zero net K (Rb) flux existed at Kc (cell K)/Rbo concentration ratios, [K]c/[Rb]c, of 0.8 i.e. when the electrochemical driving forces across the membrane were about equal. The measured K efflux/Rb influx ratios were almost twice those predicted from [K]c/[Rb]o and the Cl equilibrium potential suggesting that the diamide-stimulated K (Rb) flux may occur through non-diffusional, carrier-mediated transport. The effects of NEM and of A23187 plus/minus Ca or chelators on K: [co]Cl-transport (Lauf, Am. J. Physiol. 249:C271–278, 1985) consisted primarily of Vmax changes. Thus, all chemical interventions resulted in an increase of the number of actively transporting K:Cl [co]-transport units or an augmented turnover number per existing site.
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  • 35
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    Oxidation of metals 23 (1985), S. 17-33 
    ISSN: 1573-4889
    Keywords: Cold work ; oxidation ; spinel ; 21/4 Cr-1 Mo steel
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The effect of 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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  • 36
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    Oxidation of metals 24 (1985), S. 233-263 
    ISSN: 1573-4889
    Keywords: oxidation ; carbide dispersion ; iron-base alloys ; decarburization ; thermodynamic stability ; oxidation resistance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation behavior of 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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  • 37
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    Oxidation of metals 24 (1985), S. 331-350 
    ISSN: 1573-4889
    Keywords: oxidation ; initial stages ; reactive element addition ; oxide grain growth
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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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  • 38
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    Oxidation of metals 23 (1985), S. 77-106 
    ISSN: 1573-4889
    Keywords: cobalt-chromium ; oxidation ; internal oxidation ; annealing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The influence of 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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  • 39
    ISSN: 1573-4889
    Keywords: grain boundary diffusion ; nickel oxide ; oxidation ; active element
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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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  • 40
    ISSN: 1573-4889
    Keywords: oxidation ; Y2O3 ; dispersoid ; 80Ni-20Cr ; nucleation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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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  • 41
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    Oxidation of metals 25 (1986), S. 83-92 
    ISSN: 1573-4889
    Keywords: NaCl vapor ; Ni-Cr alloys ; oxidation ; scales
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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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  • 42
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    Oxidation of metals 29 (1988), S. 75-102 
    ISSN: 1573-4889
    Keywords: Ni-Cr-Al Alloys ; oxidation ; diffusional transport ; breakaway oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The 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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  • 43
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    Oxidation of metals 29 (1988), S. 225-238 
    ISSN: 1573-4889
    Keywords: Nickel ; SO2 ; oxidation ; sulfidation ; diffusion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The 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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  • 44
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    Oxidation of metals 27 (1987), S. 103-120 
    ISSN: 1573-4889
    Keywords: oxidation ; iron ; aluminum ; silicon
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract This paper 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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  • 45
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    Oxidation of metals 30 (1988), S. 259-266 
    ISSN: 1573-4889
    Keywords: oxidation ; adhesion ; growth mechanisms ; sulfur ; impurities ; segregation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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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  • 46
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    Oxidation of metals 30 (1988), S. 329-343 
    ISSN: 1573-4889
    Keywords: Fe-S-O ; Co-S-O ; oxidation ; sulfidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The 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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  • 47
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    Oxidation of metals 30 (1988), S. 267-269 
    ISSN: 1573-4889
    Keywords: oxidation ; adhesion ; impurities ; sulfur
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 48
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    Oxidation of metals 32 (1989), S. 433-447 
    ISSN: 1573-4889
    Keywords: chromium ; oxidation ; scale failure ; scale morphology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation 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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  • 49
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    Oxidation of metals 28 (1987), S. 73-98 
    ISSN: 1573-4889
    Keywords: chromium ; oxidation ; sulfidation ; mixed oxidants
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of 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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  • 50
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    Oxidation of metals 25 (1986), S. 217-234 
    ISSN: 1573-4889
    Keywords: nickel alloys ; oxidation ; sulfidation ; grain-boundary segregation ; corrosion mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The 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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    Oxidation of metals 25 (1986), S. 235-268 
    ISSN: 1573-4889
    Keywords: oxidation ; Mn2O3 ; spinels ; manganowustite ; mechanisms ; fusion reactors
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation in air of 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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    Oxidation of metals 26 (1986), S. 125-138 
    ISSN: 1573-4889
    Keywords: hot corrosion ; oxidation ; aluminide coatings ; nickel ; nickel alloys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract 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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  • 53
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    Oxidation of metals 26 (1986), S. 45-76 
    ISSN: 1573-4889
    Keywords: Ni-base alloys ; oxidation ; influence of oxygen partial pressure at high temperatures ; kinetics and mechanisms of high temperature oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation 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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    Oxidation of metals 27 (1987), S. 1-20 
    ISSN: 1573-4889
    Keywords: oxidation ; titanium ; silicon ; adherence ; titanium-silicon alloys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation behavior of 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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    Oxidation of metals 27 (1987), S. 315-332 
    ISSN: 1573-4889
    Keywords: chromium ; NaCl ; oxidation ; hot corrosion ; mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation 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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    Oxidation of metals 27 (1987), S. 301-314 
    ISSN: 1573-4889
    Keywords: diffusion mechanisms ; point defects ; oxidation ; NiO-V2O5
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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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    Oxidation of metals 29 (1988), S. 153-167 
    ISSN: 1573-4889
    Keywords: zirconium ; oxidation ; parabolic kinetics ; linear kinetics ; cubic kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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.
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    Oxidation of metals 29 (1988), S. 409-418 
    ISSN: 1573-4889
    Keywords: Microstructure ; oxidation ; chromium oxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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.
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  • 59
    ISSN: 1573-4889
    Keywords: Ni-base alloy IN 617 ; reactor helium ; oxidation ; carburization ; decarburization ; kinetics ; mechanisms
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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.
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  • 60
    ISSN: 1573-4889
    Keywords: constant-extension-rate tests ; Incoloy 800H ; sulfidation ; oxidation ; sol-gel method ; cerium ; ceramic coatings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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.
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    Oxidation of metals 31 (1989), S. 305-323 
    ISSN: 1573-4889
    Keywords: oxidation ; sulfidation ; Fe-Cr-Ni alloys ; Nb addition ; Zn addition ; breakaway corrosion ; mixed-gas atmospheres
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: 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.
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    The journal of membrane biology 101 (1988), S. 179-188 
    ISSN: 1432-1424
    Keywords: sheep red cells ; ouabain-resistant K fluxes ; sulfhydryl groups ; diamide ; glutathione ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Summary The sulfhydryl (SH) oxidant diamide activated in a concentration-dependent manner ouabain-resistant (OR), Cl-dependent K flux in both low potassium (LK) and high potassium (HK) sheep red cells as determined from the rate of zero-trans K efflux into media with Cl or Cl replaced by NO3 or methane sulfonate (CH3SO3). Diamide did not alter the OR Na efflux into choline Cl. The diamide effect on K efflux appeared after 80% of cellular glutathione (GSH) was oxidized to GSSG, its disulfide. The stimulation of K efflux was completely reversed during metabolic restitution of GSH, a process that depended on the length of exposure to and the concentration of diamide. The action of diamide on both the K∶Cl transporter and GSH was also fully reversed by the reducing agent dithiothreitol (DTT). Diamide apparently oxidized the same SH groups alkylated by N-ethylmaleimide (NEM) (Lauf, P.K. 1983.J. Membrane Biol..73:237–246). Like NEM, diamide activated K∶Cl transport several-fold more in LK cells than in HK cells, and the effect on LK cells was partially inhibited by anti-L1, the allo-antibody known to inhibit OR K fluxes.
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    Plant and soil 116 (1989), S. 69-76 
    ISSN: 1573-5036
    Keywords: oxidation ; soil ; sulphur ; temperature ; tetrathionate ; thiosulphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The rate of oxidation of micronized elemental sulphur in three soils was measured over a range of temperatures between 2 and 20°C. Temperature had a marked effect with a Q10 (temperature coefficient) between 1.9–3.1. The period for 50% oxidation varied between 6–10 days at 20°C to between 36–42 days at 2°C. All the oxidation curves showed an initial lag. At 20°C the oxidation rate was four times that of flowers of sulphur and was related to the smaller particle size. Additives (wetting and dispersing agents) in the commercial micronized sulphur preparation used (‘Thiovit’) were inhibitory at high concentrations but stimulatory at low concentrations. The significance to field conditions is discussed.
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  • 64
    ISSN: 1573-5168
    Keywords: testosterone ; estradiol-17β ; oxidation ; metabolism ; cytochrome oxidase ; α-GPDH ; SDH ; LDH ; MDH ; G-6-PDH ; Mg2+ ATPase ; catalase ; Anabas
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Testosterone (T) administration to maleAnabas testudineus significantly stimulated the activities of cytochrome oxidase, α-glycerophosphate dehydrogenase (α-GPDH) and Mg2+ adenosine triphosphatase (Mg2+ ATPase) and inhibited lactate dehydrogenase (LDH), cytosolic and mitochondrial malate dehydrogenases (MDH). The activities of succinate dehydrogenase (SDH), glucose-6-phosphate dehydrogenase (G-6-PDH) and catalase were unaffected by testosterone treatment. Administration of estradiol-17β (E2) in female fish, significantly stimulated cytochrome oxidase activity, inhibited Mg2+ ATPase, SDH, catalase and cytosolic and mitochondrial MDH activity, and was without effect on other enzymes studied. The simultaneous injections of actinomycin D or chloramphenicol and T or E2 prevented the hormonal influence on hepatic enzyme activities. The present study demonstrates that inA. testudineus sex steroids influence hepatic oxidative metabolism by a mechanism sensitive to the action of inhibitors of protein synthesis.
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  • 65
    ISSN: 1573-1111
    Keywords: Metalloenzymes ; catalysis ; oxidation ; nickel ; alkene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract New nickel catalysts have been developed for the oxidation of alkenes to epoxides, alcohols, aldehydes and ketones. Mechanistic studies indicate that the oxidation reactions are very sensitive to the nature of the catalyst; only certain ligands including salen and the macrocycles cyclam and dioxocyclam render Ni(II) effective as a catalyst. A Ni(III) or Ni(IV)-oxo species has been postulated as the catalytically active oxidant which leads to oxygen atom transfer to alkenes in a stepwise process. Both iodosylbenzene and hypochlorite have been used as terminal oxidants; both systems give high yields of epoxidation of alkenes and varying amounts of C=C bond cleavage products. In order to reach an ultimate goal of hydrocarbon oxidation within a molecular recognition system, new molecular receptors for organic substrates have been investigated. The receptors are constructed from two subunits of cholic acid and display amphophilic character — a hydrophobic exterior and a hydrophilic interior. Conformational properties in the presence of polar guests in CDCl3 are described.
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    International journal of thermophysics 9 (1988), S. 1121-1130 
    ISSN: 1572-9567
    Keywords: heat-resisting alloy ; high-speed spectroscopy ; oxidation ; radiation property ; transient behavior ; transition metal
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract A high-speed spectrophotometer system is developed to study radiation characteristics of materials. The system allows measurements of the spectra at wavelengths of 0.35–10μm repeatedly with a period of less than 1 s. It is applied to the study of transient behaviors in reflection characteristics of heat-resisting alloys and the constituent transition metals in air-oxidation processes at high temperatures. An interference phenomenon due to the multiple reflection at the upper and lower boundaries of the oxide film is observed in the diffuse reflection spectra of oxidizing rough-finished surfaces as well as in the specular reflection spectra of oxidizing specular-finished surfaces. The phenomenon is found to be fairly reproducible and consistent over all the materials investigated. It is attributed to the interference and diffraction of radiation at three-dimensional nonparallel film elements of the polycrystalline oxide grains. A possibility is suggested for the theoretical modeling of radiation characteristics of real surfaces in the actual environments of industry.
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 395-411 
    ISSN: 0029-5981
    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: The design and implementation of software for real-time spectral analysis on an IBM 1130 with 8k core is described. The procedures for estimation of coherence and cross-spectra are discussed in detail.
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 381-394 
    ISSN: 0029-5981
    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: The Fast Fourier Transform is employed as a method of Laplace transform inversion to solve problems in the civil engineering fields of visco-elasticity and hydrology. When these problems are accurately represented by a linear time-invariant model, it is shown that the Fast Fourier Transform inversion procedure is often more accurate than standard convolution and inversion techniques. The speed and accuracy of solution resulting from this application of the Fast Fourier Transform is illustrated by referring to case studies solved on an IBM 1130 computer, model 3D processor with 32K memory.
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 427-439 
    ISSN: 0029-5981
    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: Stress fields near crack tips in an elastic body can be specified by the stress intensity factors which are closely related to the stress singularities arising from the crack tips. These singularities, however, cannot be represented exactly by conventional finite element models. A new method for the analysis of stresses around cracks is proposed in this paper on the basis of the superposition of analytical and finite element solutions. This method is applied to several two-dimensional problems whose solutions are obtained analytically, and it is shown that their numerical results are in excellent agreement with analytical ones. Sufficiently accurate results can be obtained by the conventional finite element analysis with rather coarse mesh subdivision. Computational efforts are then considerably reduced compared with other methods.
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 447-447 
    ISSN: 0029-5981
    Keywords: Engineering ; Engineering General
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 454-456 
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    Keywords: Engineering ; Engineering General
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 456-456 
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    Keywords: Engineering ; Engineering General
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 467-473 
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    Keywords: Engineering ; Engineering General
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    Topics: Mathematics , Technology
    Notes: A generalized variational principle is presented, which leads to a modified finite element approach for three-dimensional field problems. Both, potential function and velocity field, are approximated by expansions which are continuous across the inter-element boundaries. The rapid convergence of this mixed model is shown by two examples.
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 497-509 
    ISSN: 0029-5981
    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: A computer program for the in-core solution of large, sparse, unsymmetric systems of linear equations is presented in this paper. The program employs elimination techniques for solution of systems of linear equations. A limited number of zeros is stored and trivial arithmetic is by-passed to preserve computer storage and to reduce the time required for solution. Several techniques for selecting the pivotal elements are discussed and their effect on accuracy and computational time are examined.
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 521-527 
    ISSN: 0029-5981
    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: Numerical methods are used to investigate the two-dimensional motion of a viscous incompressible fluid impulsively started past a flat plate of finite breadth at zero incidence to the uniform motion of the fluid at large distances from the plate. A step by step integration in time of Helmholtz's vorticity equation is used for Reynolds numbers 10-500.The magnetohydrodynamic case is also considered with the applied magnetic field at infinity parallel to the uniform stream and the non-conducting plate. Results for the Magnetic Reynolds number 50 and infinite, Viscous Reynolds number 50 and 0≤β≤2, where β is the ratio of the square of the Alfvén speed to the square of the main stream velocity, are presented.
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 608-608 
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    Keywords: Engineering ; Engineering General
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 43-55 
    ISSN: 0029-5981
    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: A new family of triangular finite elements is described, useful for solving the axisymmetric vector Helmholtz equation, and a variety of scalar Helmholtz equation problems which lead to generalized Bessel equations of some order m. This family is similar in principle to the scalar axisymmetric Helmholtz elements derived earlier, but requires both reformulation of its describing equations and corresponding new universal element matrices, for successful computational implementation. The necessary formulation is given in this paper. Matrix elements to the sixth-order inclusive have been calculated and extensively tested computationally.
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 57-67 
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    Keywords: Engineering ; Engineering General
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    Topics: Mathematics , Technology
    Notes: The criteria for stability of the explicit finite difference solution of the one-dimensional, transient, conduction heat transfer problem with both radiant and convection heat transfer at the boundaries are considered in this paper. These criteria are governed by an inequality set from a functional relationship between the newly calculated and the old temperature at each node.From the node with the most stringent criteria, it is shown that setting the coefficient of the old temperature equal to zero in the governing difference equation is not sufficient for a general criterion. On the other hand, setting the derivative of the new temperature with respect to the old temperature equal to zero in the governing difference equation presents a simple, straightforward technique for obtaining a sufficient condition for a stable system. It is further shown that the second law of thermodynamics, written in explicit finite difference form, does present a necessary criterion for stability. However, the second law, because it is in the form of an inequality, does not present as simple a criterion as the derivative method does.The specific problem studied is a finite thickness slab, initially at a uniform temperature, but instantaneously subjected to both radiation and convection on its two surfaces. Temperature profiles were calculated on a digital computer and are presented in dimensionless graphical form over a range of five dimensionless parameters. A plot that relates stability to the maximum time-step size for the entire range of practical conditions of radiation numbers is also presented.
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    International Journal for Numerical Methods in Engineering 7 (1973) 
    ISSN: 0029-5981
    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 117-124 
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    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: A theorem expressing geometric conditions necessary and sufficient for the stiff stability of a linear multistep method is obtained. A corollary to this theorem provides sufficient conditions for stiff stability, for the class of algorithms characterized by a single essential root. By applying the Schur-Cohn criterion and employing a computerized algebraic manipulation program, the result provides a first step towards an exhaustive search technique for determining a continuum of members of this class.
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 175-183 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: A method is described for the solution of large sets of sparse equations arising in structural analysis. This method, called partial elimination, combines the concepts of elimination and iteration in such a way that good convergence rates can be obtained using a computer storage space not much greater than that required for other iterative methods.
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 211-223 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: A survey of recent developments in sparse matrix technology is presented. Two fundamental areas are reviewed: 1.Sorting and reordering techniques by which the non-zero elements of a given sparse matrix can be rearranged to obtain a form which leads to more efficient computations.2.Direct methods for solving systems of linear equations and computing inverses.
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    International Journal for Numerical Methods in Engineering 3 (1971), S. 63-87 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: The finite element method is applied to the stability analysis of structural systems subject to non-conservative forces. The development of the method is general, but the specific application considered here is the stability of thin-walled members subject to follower forces. The method predicts the type of instability, whether it be buckling or flutter. Example problems, for which exact solutions are known, illustrate the accuracy and convergence characteristic of the finite element formulation.
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 240-240 
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    Keywords: Engineering ; Engineering General
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 155-173 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: The present investigation examines the multibar truss optimization problem in the context of a general class of unconstrained optimization procedures in conjunction with various types of penalty function transformations. Specifically, the problem is transformed into a series of unconstrained minimization problems using the penalty function techniques of Heaviside and SUMT. These are solved using the methods of Rosenbrock (orthogonal directions), Powell (conjugate directions) and Nelder-Mead (Simplex). This resulted in many cases in substantial improvements being recorded over previously reported data. The paper includes a comparative study of the synthesis based on these procedures.
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    International Journal for Numerical Methods in Engineering 3 (1971), S. 103-117 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: The application of the finite element rank force method for the dynamic analysis of redundant structures is presented. The applied loading consists of discrete and distributed loads. Both forced and free vibrations are considered, the latter yielding latent vectors corresponding to dynamic redundancies.It is shown that the dynamic properties of an element are given by a static flexibility matrix, an inverse mass matrix, a damping parameter and a displacement vector representing the effect of the applied distributed loading.
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    International Journal for Numerical Methods in Engineering 3 (1971), S. 119-129 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: A stiffness matrix for a finite element having the planform of an annular segment is derived using the displacement approach. Numerical problems involved in the derivation are discussed and rapid convergence to exact solutions is demonstrated on three sample problems. It is concluded that the new element will be of great value to engineers concerned with the analysis of slabs of bridge decks curved in plan.
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    International Journal for Numerical Methods in Engineering 3 (1971), S. 89-101 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The point matching numerical method and its generalization, the method of boundary point least squares, have been successfully applied to numerous boundary value and eigenvalue problems. The present paper demonstrates the application of these techniques to problems in the micromechanics of fibrous composite materials, i.e. determination of elastic moduli and stress concentrations for parallel-fibre materials which are loaded transversely with respect to the fibres. The solution technique utilizes exact solutions of the governing equations of plane elasticity for each component fibre and its surrounding matrix material in a typical repeating section of the composite material. The continuity conditions for stresses and displacements between fibre and matrix and the repeatability conditions at the boundary of the repeating section are satisfied approximately in a pointwise manner. Some special numerical techniques which were found to be particularly useful in applying the point matching method to these problems are delineated. The method is demonstrated for composite materials having circular, elliptical and square fibres in regular, staggered arrays. Numerical results are given which show the accuracy of the method as well as stress concentration and composite elastic moduli data.
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    International Journal for Numerical Methods in Engineering 3 (1971), S. 131-144 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: This paper discusses the mathematical foundations of a technique that has been used extensively in structural optimization.1-6 Two basic problems are considered. The first of these is the concave programming problem which consists of finding the global minimum of ‘piece-wise concave functions’ on ‘piece-wise concave sets’. Since any function can be approximated by a piece-wise concave function, this method could in principle be used to find the global minimum in non-convex optimization problems. The second one is the piece-wise linear programming problem in which the objective function is convex and piece-wise linear. The iterative method outlined for handling this problem is shown to be much more efficient than the standard simplex method of linear programming.
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    International Journal for Numerical Methods in Engineering 3 (1971), S. 149-149 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 461-477 
    ISSN: 0029-5981
    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: Computer-oriented mesh generators, which serve as pre-processors to finite element programs, have recently been developed by several investigators to alleviate the frustration and to reduce the amount of time involved in the tedious manual subdividing of a complex structure into finite elements. Our purpose here is to describe how the techniques of bivariate ‘blending-function’ interpolation, which were originally developed for, and applied to, geometric problems of computer-aided design and numerically controlled machining of free-form surfaces such as automobile exterior panels, can be adapted and applied to the problems of mesh generation for finite element analyses. We concentrate attention on the problem of curvilinearly co-ordinating simply connected planar domains R by constructing invertible maps of the unit square S ≡[0, 1] × [0, 1] onto R. Extensions of the methods described herein to shells in 3-space is straightforward and is illustrated by a practical example taken from the automobile industry. Analogous mesh generators for three-dimensional solids can be developed on the basis of the trivariate ‘blending-function’ formulae found at the end of the second section.
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    International Journal for Numerical Methods in Engineering 3 (1971), S. 154-154 
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    Keywords: Engineering ; Engineering General
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 309-323 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: Various solutions of laminated plates by the finite element method are analysed. An efficient solution of skew (or rectangular) laminated plates with small effect of σz and ∊z stress and strain components is developed. It can be used with an arbitrary number of layer elements (sub-elements) in different plate elements. Some remarks to the possible modification of solution are presented. Numerical examples with a short discussion and conclusions complete the paper.
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    Notes: The hybrid-element concept and the complex variable technique have been adopted for constructing a special super-element to be used jointly with conventional finite elements for the analysis of elastic stress intensity factors for plane cracks. The use of the complex variable technique permits the proper consideration of the stress intensity at the crack tip, and it also leads to very efficient programming. The use of such a super-element in the finite element solution has been shown to be highly accurate when only a very coarse element mesh is used near the crack.
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 345-355 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: Consider a solid heat conductor with a non-linear constitutive equation for the heat flux. If the material is anisotropic and inhomogeneous, the heat conduction equation to be satisfied by the temperature field θ(x, t) is, \documentclass{article}\pagestyle{empty}\begin{document}$$ \rho c\frac{{\partial \theta }}{{\partial t}} = {\rm div}({\rm L}(\theta,{\rm x})[{\rm grad}\theta]) + q $$\end{document} Here L(θ, x) [grad θ] is a vector-valued function of θ, x, grad θ which is linear in grad θ, In the present paper, the application of the finite element method to the solution of this class of problems is demonstrated. General discrete models are developed which enable approximate solutions to be obtained for arbitrary three-dimensional regions and the following boundary and initial conditions: (a) prescribed surface temperature, (b) prescribed heat flux at the surface and (c) linear heat transfer at the surface. Numerical examples involve a homogeneous solid with a dimensionless temperature-diffusivity curve of the form κ = κ0(l + σT). The resulting system of non-linear differential equations is integrated numerically.
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 405-408 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: Several formulas are presented for the numerical integration of a function over a triangular area. The formulas are of the Gaussian type and are fully symmetric with respect to the three vertices of the triangle.
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    International Journal for Numerical Methods in Engineering 8 (1974), S. 45-54 
    ISSN: 0029-5981
    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: This paper deals with a finite element formulation and solution of the boundary value problem of a concentrated force acting on a semi-infinite micropolar solid. A stiffness matrix is derived for a flat micropolar rectangular element in a plane state and use is made of this element to solve the case of the semi-infinite micropolar solid both in a state of plane stress and plane strain. An immediate application of the plane strain case is the important practical problem of a long line load acting on a soil mass which may be simulated as a micropolar body.
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    International Journal for Numerical Methods in Engineering 8 (1974), S. 111-117 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: This paper presents an extension to the Matrix Transfer Method which gives quadratic convergence to a natural frequency from within a range on either side.The method is described and illustrated by application to: 1A torsional vibration problem, and2A lumped mass beam vibration problem.
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    International Journal for Numerical Methods in Engineering 8 (1974), S. 139-165 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: A finite element formulation is presented for the equations governing the steady thermohydrodynamic behaviour of liquid lubricated bearings. This formulation permits application of the iterative solution scheme to bearings of arbitrary geometry.A generalized Reynolds equation resulting from the combination of the mass and momentum conservation equations is cast into variational form and used to derive general finite element equations. The method of weighted residuals with Galerkin's criterion is used to generate finite element matrix equations for the thermal energy equation. In addition to the finite element formulation, a discussion of appropriate finite difference techniques is also given for problems without complex geometry.As an example, the formulations are applied to obtain numerical solutions for a three-dimensional sector thrust bearing operating in the thermohydrodynamic regime. Pressure, velocity and temperature distributions are give, and the thermohydrodynamic solutions are compared with the results of classical isothermal theory.
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    International Journal for Numerical Methods in Engineering 8 (1974), S. 203-209 
    ISSN: 0029-5981
    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
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