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  • Articles  (81)
  • oxidation  (72)
  • Theoretical, Physical and Computational Chemistry
  • temperature
  • Springer  (79)
  • Wiley-Blackwell  (2)
  • American Meteorological Society
  • 1995-1999  (54)
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  • 1965-1969
  • 1955-1959
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  • 1987  (13)
  • Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics  (81)
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  • Articles  (81)
Publisher
  • Springer  (79)
  • Wiley-Blackwell  (2)
  • American Meteorological Society
Years
  • 1995-1999  (54)
  • 1990-1994  (14)
  • 1985-1989  (13)
  • 1965-1969
  • 1955-1959
Year
  • 1
    ISSN: 1572-8862
    Keywords: Palladium ; carbene ; oxidation ; phosphonate ; carboxylate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Thermolysis of tetranuclear palladium clusters Pd4(μ-Q)4 Pd4(μ-Q)4(μ-O2CR)4 (Q=CPh2 or CO;R=Me, CMe3, Ph, CH2Cl or CF3) has been found to involve innersphere oxidation of carbene or carbonyl ligands during which an oxygen atom transfer occurs from the carboxylate group to the carbene or carbonyl ligand. The thermolysis of the carbonyl clusters gives rise to the products of CO2 insertion into the C–H bond of benzene or toluene used as solvents forming benzoic acid from benzene and a mixture of phenylacetic and toluic acids from toluene. The reaction of [Pd(OAc)2(PPh3)]2 with HCO2H includes the transfer of an O atom from formate ligand to the P atom and cleavage of the P-Ph bond accompanied by transfer of the Ph group from PPh3 ligand to the palladium atom. The structure of the complex formed, [Pd(μ-O2PPh2)(C6H5)(PPh3)]2, has been resolved by X-ray analysis.
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  • 2
    ISSN: 1572-8765
    Keywords: carbonado ; diamond ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of carbonado type synthesized polycrystalline diamonds produced from graphite together with catalytic Ni-Mo alloy doped with TiB2 and BNcub was investigated. It was found that the addition of these boron compounds increases the oxidation resistance of the carbonado type synthesized polycrystalline diamonds. The oxidation mechanism acting on the carbonado type synthesized polycrystalline diamonds and the role of boron compounds in increasing the resistance to the oxygen reaction are discussed.
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  • 3
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    Archive of applied mechanics 68 (1998), S. 128-136 
    ISSN: 1432-0681
    Keywords: Key words frictional heating ; temperature ; contact pressure ; punch indentation ; thermoelasticity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Summary An axisymmetric contact problem with frictional heating is considered in which a parabolic annular punch is pressed into a plane surface and rotates about its axis of symmetry at constant speed. The problem is formulated in terms of one governing equation with unknown pressure. This equation is solved numerically. The change of the geometry of the contact region and pressure has been investigated.
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  • 4
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    Archive of applied mechanics 67 (1997), S. 331-338 
    ISSN: 1432-0681
    Keywords: Key words frictional heating ; wear ; contact pressure ; temperature ; brake system
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Summary A transient contact problem with frictional heating and wear for two nonuniform sliding half-spaces is considered. One of the two half-spaces is assumed to be slightly curved to give a Hertzian initial pressure distribution: the other is a rigid nonconductor. Under the assumption that the contact pressure distribution could be described by Hertz formulas during all the process of interaction, the problem is formulated in terms of one integral equation of Volterra type with unknown radius of contact area. A numerical solution of this equation is obtained using a piecewise-constant presentation of an unknown function. The influence of operating parameters on the contact temperature and the radius of the contact area is studied.
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  • 5
    ISSN: 1572-8986
    Keywords: RF SiCl4 discharge ; mass spectrometry ; kinetics ; decomposition ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract Time-resolved mass spectrometry was used for analysis of the plasma reactions in radio frequency (RF) SiCl 4 and SiCl 4 −O 2 discharges as functions of starting partial pressure and electrical power. Molecular concentrations of the reactants and products from SiCl 4 alone and with O 2 were obtained from the mass spectra and used for plotting the kinetic curves. The SiCl 4 and O 2 consumption rates were calculated from the kinetic curves and compared with results of theoretical simulation of the reaction. Direct electron impact decomposition was found to be the main pathway for pure SiCl 4 conversion. On the contrary, the consumption of SiCl 4 in the SiCl 4 +O 2 mixtures was largely chemical. The experimental macrokinetics are in agreement with a model in which oxidation is caused by the atomic oxygen.
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  • 6
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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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  • 7
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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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  • 8
    ISSN: 1573-4889
    Keywords: dilute alloys ; oxidation ; Wagner-Hauffe rule
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Concerning the parabolic oxidation of alloys with a low content of a different valence element, we show that the Wagner-Hauffe valence approach contains some inaccuracies. This paper is devoted to the growth of an oxide MO with metal excess or oxygen deficit. The analytical processing consists in solving the differential equation connecting the point defect flux to the oxygen pressure. This equation has been solved analytically in the case where the foreign-element concentration is very high compared to that of the point defects in the pure oxide. On this assumption with a lower-valence dopant, as long as the oxide conductivity remains essentially electronic, the oxidation is limited only by the transport of ionic defects across the scale under the electric-potential gradient. Moreover, an increase of the dopant concentration may lead to an oxide exhibiting partial ionic conductivity. Consequently, the parabolic constant variations as a function of the dopant concentration is not monotonic, contrary to results published before. With a higher-valence dopant, the conductivity always remains electronic, and this result agrees with predictions based on the Wagner Hauffe approach, though the demonstrations are fundamentally different.
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  • 9
    ISSN: 1573-4889
    Keywords: oxidation ; copper ; Li-doped copper ; Cr-doped copper ; short-circuiting ; Mott's parabola ; Wagner's parabola
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The influence of shorting circuitry attachment between metal-oxide and oxideoxygen interfaces on the oxidation kinetics of copper, lithium-doped copper (Li: 400 ppm), and chromium-doped copper (Cr: 12 ppm) have been studied in dry air $$(P_{O_2 } = 21.27kPa)$$ in the temperature range of 523–1073 K. Oxide film or scale growth under short-circuiting as well as under normal oxidation conditions conforms to the parabolic rate law. The oxidation kinetics under short-circuiting resulted in decreased rates for Cu and Li-doped Cu up to a temperature of 773 K, while Cr-doped Cu exhibited an enhancement in rate compared to its normal oxidation in the same temperature range. However, above 873 K, all three systems under shorting circuitry attachment exhibited enhanced rates compared to their normal oxidation rates in conformity to the existing theoretical model. Use of additional resistances in series in the outer short-circuit Pt path have clearly established that below 773 K Mott's fieldinduced migration plays the most important role, while at elevated temperatures Wagner's electrochemical potential-gradient factor acts as the main driving force in the scale-growth process. The results have been interpreted on the basis of average defect concentration, the electrochemical potential gradient, electrical field gradient, and transport coefficient in the Cu2O layer.
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  • 10
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    Oxidation of metals 46 (1996), S. 109-127 
    ISSN: 1573-4889
    Keywords: oxidation ; Ni3Al base alloy ; chromium ; cobalt ; titanium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation behavior of Ni3Al+2.90 wt.% Cr, Ni3Al+3.35 wt% Co, and Ni3Al+2.99 wt.% Ti alloys was studied in 1 atm of air at 1000, 1100, and 1200°C. Isothermal tests revealed parabolic kinetics for all three alloys at all temperatures. Cyclic oxidation for 28 two-hour cycles produced little spallation at 1000°C, but caused partial spallation at 1100°C. Especially, at 1200°C severe spallation in all three alloys was observed. Although additions of Cr, Co, or Ti to Ni3Al alloys slightly increased the isothermal-oxidation resistance, the additions tended to decrease the cyclic-oxidation resistance. The major difference in the oxidation of the three alloys compared with the oxidation of pure Ni3Al alloys was the existence of small α-Al2O3 particles in the middle of the α-Al2O3 scale and the formation of irregularly shaped Kirkendall voids at the alloy-scale interface.
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  • 11
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    Oxidation of metals 47 (1997), S. 381-410 
    ISSN: 1573-4889
    Keywords: Ni-Base superalloys ; Astroloy ; Waspaloy ; Udimet 720 ; oxidation ; chromia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Several commercially available Ni-base superalloys were exposed isothermally in air at temperatures between 750° and 1000°C and also under cyclic conditions at 1000°C. The kinetics of oxidation were determined and the scales were analyzed by electron microscopy and X-ray diffraction. Thin adherent chromia-rich scales formed on the alloys at 750°C after 1000 hr. Although Waspaloy showed the lowest weight gain in this test, it also showed the deepest internal corrosion due to oxidation of the grain-boundary carbides. At temperatures up to 1000°C the external scales were also chromia-rich but there was greater internal corrosion. Titanium in the alloys oxidized, diffusing through the chromia scale to form faceted rutile (TiO2) grains at the surface as well as forming TiO2 and TiN internally. The amount of rutile at the oxide surface increased with temperature and alloy Ti concentration. Alumina formed as discrete internal oxides below the chromia scale, although Astroloy when oxidized isothermally at 1000°C developed a semicontinuous internal layer of alumina due to its higher Al content. Under cyclic conditions Astroloy formed a thicker, less-protective scale of transition oxides probably due to its lower Cr content.
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  • 12
    ISSN: 1573-4889
    Keywords: oxidation ; Incoloy 909 ; superalloy ; scale ; high temperature ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of an Fe-38Ni-13Co-4.7Nb-1.5Ti-0.4Si superalloy (Incoloy 909 type alloy), was investigated at temperatures between 1000 K and 1400 K in Ar-(1, 10%)H20 atmosphere using metallographic, electron probe microanalysis, and X-ray diffraction techniques. The oxide scales consist of an external scale and an internal scale which has an intergranular scale (above 1200 K) and an intergranular scale. The oxide phases in each scale are identified asα-Fe2,O3 (below 1200 K) or FeO (above 1300 K) and CoO · Fe2O3 and FeO · Nb2O5, respectively. The morphologies, the oxide phases and the oxidation rates do not depend on the partial pressure of H2O in the range between one and ten percent in Ar gas. The rate constants for the intergranular-scale formation in this alloy are about one-tenth as large as those in Fe-36%Ni alloy reported previously. At all the temperatures the scales grow according to a parabolic rate law and the apparent activation energies for the processes are estimated.
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  • 13
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    Oxidation of metals 47 (1997), S. 445-464 
    ISSN: 1573-4889
    Keywords: oxidation ; Fe-Cr-Al alloy ; water vapor ; ESCA ; RHEED
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Fe-21.5 wt. %Cr-5.6 wt. %Al oxidation, at 1000°C, in dry or wet oxygen shows that steam has an influence on the oxide-scale growth mechanism. Steam modifies the kinetics of early-stage oxidation. In dry oxygen, an initial fast linear regime is observed during one hour. Under wet conditions, weight-gain curves follow the same parabolic regime over the entire oxidation test. The scale structure strongly depends on the presence of steam in the gaseous environment. With dry oxygen, the scale is composed mainly ofα-Al2O3 after the initial formation ofγ-Al2O3 identified by ESCA and RHEED. The kinetics transient stage corresponds to the necessary time for the internal part of the initialγ-Al2O3 scale to transform into a continuousα-Al2O3 diffusion barrier. Under wet oxygen conditions, transient oxides are identified as (Mg, Fe) (Cr, Al)2O4, MgAl2O4 (orthorhombic), Al2O3 (hexagonal), these oxides transform into MgAl2O4 (cubic), Cr3O4, Fe2O3,α-Al2O3, with time. When water vapor does not change drastically oxidation kinetics, the induced presence of iron and chromium in the oxide scale could be responsible for weakening the protectiveness of alumina scales.
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  • 14
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    Oxidation of metals 47 (1997), S. 507-524 
    ISSN: 1573-4889
    Keywords: alloys ; high temperature ; oxidation ; transient state
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The initial transient high-temperature oxidation stage for binary alloys forming the most-stable oxide has been examined by means of a numerical procedure based on the finite-difference method. At variance with previous models, the present treatment takes into account the effect of the rate of the reaction at the scale/gas interface over the corrosion kinetics. The calculations concerning the transient stage are developed either using the general parabolic rate law to represent the overall scaling kinetics or using the rate law of the reaction at the scale/gas interface as a boundary condition without imposing any particular rate law to the overall process. A correct analysis of the oxidation behavior of binary alloys during the transient stage must take into account the kinetics effect of the rate of the surface reaction. The concentration of the most-reactive element at the alloy/scale interface changes regularly with time, decreasing gradually from the initial bulk value to its final steady-state value. The present results are in good agreement with those obtained by means of an approximate analytical model developed previously.
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  • 15
    ISSN: 1573-4889
    Keywords: high temperatures ; oxidation ; transient state
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The transient state in the oxidation of solid solutions of a most-noble componentA in a most-reactive componentB (beta phase) for binaryA-B alloys presenting a limited reciprocal solubility of the two metals has been examined assuming that theirB content is sufficient for the exclusive growth of externalBO scales. Above a criticalB content of the alloy theBO scales may grow directly on the surface of the beta phase, while below this limit they can only form over a layer ofB-depleted solid solution ofB inA (alpha phase), which appears after a critical time. An approximate analytical expression for the profile of concentration ofB in the alloy has been adopted to calculate the flux ofB in the metal. Moreover, the effect of the reaction between the gas and the external oxide surface has been taken into account using a procedure developed by Wagner for the oxidation of pure metals. The corrosion kinetics as well as all the parameters involved, such as the concentration ofB at the alloy-scale interface, have been calculated as functions of the corrosion time. The results show that, as time proceeds, the instantaneous parabolic rate constant increases and the concentration ofB at the alloy-scale interface decreases, both tending gradually to their corresponding steady-state values. It is also predicted that if the rate of transformation of the beta phase in the alpha phase after the alloy reaches the composition of equilibrium at the interface with the oxide is lower than the corresponding rate of displacement of the alloy surface due to scale growth, the corrosion of beta phase alloys may eventually lead to the formation of two phase mixtures of alpha phase andBO which are expected to grow at much larger rates than in the presence of a uniform continuous alpha layer.
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  • 16
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    Oxidation of metals 48 (1997), S. 1-39 
    ISSN: 1573-4889
    Keywords: Ni-base ODS superalloys ; oxidation ; initial stages of oxidation ; alumina ; chromia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Mechanically-alloyed Ni-base ODS superalloys currently receive attention for application in future gas turbines because they exhibit outstanding mechanical properties at high temperatures. They also protect themselves against oxidation by forming chromia and/or alumina scales. However, little attention has been given so far to the initial stages of oxidation of Ni-base ODS superalloys, containing Cr as well as Al in considerable amounts. In the current work, oxidation at 1150°C was studied for different holding times up to 200 hr for the commercial materials MA6000 and PM3030 which contain. Al in increasing amounts. MA 754, a chromia former, was investigated as a reference. It was shown that for the potential alumina formers MA6000 and PM3030 the continuity and therefore protectiveness of the secondary Al2O3 at later stages is indeed determined by the initial stages of oxidation.
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  • 17
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    Oxidation of metals 48 (1997), S. 129-141 
    ISSN: 1573-4889
    Keywords: decarburization ; nickel ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A commercial-grade nickel containing small amounts of carbon, manganese, and silicon was exposed to air for periods up to 288 hr at 1050°C to study the effect of oxidation on the formation of oxides of these impurity elements. Exposure of nickel to air led to decarburization. The maximum amount of decarburization occurred during the initial period of air exposure and the loss in carbon was more in the metal with a smaller section size. Decarburization in the metal produced voids in the oxide scale due to the formation of CO2 gas. It has been shown further that CO and/or CO2 gas bubbles, which form in high purity nickel on grain boundaries during exposure to air at elevated temperatures, cannot exist in commercial-grade nickel where manganese is present as an impurity. Instead, oxides of manganese form in the grain boundaries as well as in the matrix. This is because manganese oxide is more stable than CO or CO2 gas.
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  • 18
    ISSN: 1573-4889
    Keywords: oxidation ; kinetics ; iron ; iron-nitride
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of α-Fe and ɛ-Fe2N1−z at 573 K and 673 K in O2 at 1 atm was investigated by thermogravimetrical analysis, X-ray diffraction, light-optical microscopy, scanning electron microscopy and electron probe X-ray microanalysis. Upon oxidation at 573 K and 673 K, on α-Fe initially α-Fe2O3 develops, whereas on ɛ-Fe2N1−z initially Fe3O4 develops. In an early stage of oxidation the oxidation rate of ɛ-Fe2N1−z appears to be much larger than of α-Fe. This can be attributed largely to an effective surface area available for oxygen uptake, which is much larger for ɛ-Fe2N1−z than for α-Fe due to the porous structure of ɛ-Fe2N1−z as prepared by gaseous nitriding of iron. The development of a magnetite layer in-between the hematite layer and the α-Fe substrate, at a later stage of oxidation, enhances layer-growth kinetics. After 100 min oxidation at 673 K the (parabolic) oxidation rates for α-Fe and ɛ-Fe2N1−z become about equal, indicating that on both substrates the oxide growth is controlled by the same rate limiting step which is attributed to short-circuit diffusion of iron cations. Oxidizing ɛ-Fe2N1−z increases the nitrogen concentration in the remaining ɛ-iron nitride, because the outward flux of iron cations, necessary for oxide growth, leads to an accumulation of nitrogen atoms left behind.
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  • 19
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    Oxidation of metals 48 (1997), S. 201-214 
    ISSN: 1573-4889
    Keywords: titanium-aluminum alloys ; niobium ; intermetallics ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In a recent study, CO2 has been reported to enhance the oxidation rate of binary titanium-aluminum alloys. The detrimental effect of CO2 was not, however, observed in a ternary alloy containing niobium. In this paper, possible explanations for these observations are examined. First, results from the literature regarding the effects of niobium in improving the resistance of titanium-aluminum alloys are briefly reviewed. Second, a thermodynamic analysis which offers a possible explanation for the beneficial effect of niobium in eliminating the CO2-enhanced oxidation of titanium-aluminum alloys is presented.
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  • 20
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    Oxidation of metals 48 (1997), S. 215-224 
    ISSN: 1573-4889
    Keywords: nanocrystallization ; oxidation ; mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Many mechanisms for the effect of reactive elements on the selective oxidation and scale adhesion of alloys have been proposed. However, nanocrystallization (or microcrystallization) has recently been found to have almost the same effect as that of reactive elements. This note reviews the effect of nanocrystallization on the selective oxidation and adhesion of Al2O3 scale with particular reference to the author's own results.
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  • 21
    ISSN: 1573-4889
    Keywords: oxidation ; titanium ; rutile ; scale ; high temperature ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation behavior of pure titanium has been investigated in the temperature range of 1000 K to 1300 K in CO2 or Ar-10%CO2. Optical microscopy, electron probe microanalyses, and X-ray measurements on the oxide scales formed during oxidation indicate that their structures are nearly independent of temperature and the corrosion atmosphere. The scales consisted of two layers, an external one and an internal one, having a rutile (TiO2) structure. The parabolic rate law was confirmed for growth of the external scale and the permeation depth of oxygen in titanium with apparent activation energies of 266 and 226 kJ/mol, respectively. The rate-determining diffusion species in the oxidation processes are discussed.
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  • 22
    ISSN: 1573-4889
    Keywords: zirconium ; X-ray diffraction ; oxidation ; phase analysis ; texture
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of zirconium at high temperature (T〉 400°C) leads to reaction products of two allotropic oxide (ZrO2 monoclinic and ZrO2 tetragonal). The distribution and proportion of these two phases were studied as a function of time and space by X-ray diffraction techniques. Quantitative analyses are possible after some corrections, and we demonstrate the presence of a phase gradient in the oxide scale. The interest of this nondestructive method is then discussed.
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  • 23
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    Oxidation of metals 48 (1997), S. 357-380 
    ISSN: 1573-4889
    Keywords: chromium ; copper ; binary alloys ; two-phase alloys ; oxidation ; high temperatures
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation in air of three two phase Cu-Cr alloys with nominal Cr contents of 25, 50, and 75 wt. % was studied at 700–900°C. The alloys corroded nearly parabolically, except at 900°C, when the corrosion rates decreased with time more rapidly than predicted by the parabolic rate law. The corrosion rate decreased for higher Cr contents in the alloy under constant temperature and generally increased with temperature for the same alloy composition. The scales were complex and consisted in most cases of an outermost copper oxide layer free from chromium and an inner layer composed of a matrix of copper oxide or of the double oxide Cu2Cr2O4, often containing particles of chromium metal surrounded by chromia and then by the double oxide. Metallic copper was also frequently mixed with chromia. Cr-rich regions tended to form continuous chromia layers at the base of the scale, especially at the highest temperature. No chromium depletion was observed in the alloy.
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  • 24
    ISSN: 1573-4889
    Keywords: iron ; oxidation ; CeO2 coating ; in situ ; growth stress ; residual stress ; texture ; X ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In situ XRD stress determinations have been performed during oxidation of pure iron (p(O2=2 × 10−3 Pa,T=800°C)). The compressive stress, initially present in the substrate due to surface preparation, is completely released at 400°C. Under the test conditions, the in situ compressive-stress level determined in the FeO scale during oxidation is not strongly dependent upon the presence of a ceria coating. On blank and coated specimens, the compressive stress varies from −400 ± 80 MPa to −150 ± 100 MPa during 30 hr oxidation. The decrease is quicker at the beginning of the test performed on blank specimens. Epitaxial relationships between the wüstite scale and iron (under low-pressure starting conditions) caused thein situ compressive stress in the oxide scale to be two times greater compared to the usual test conditions. This indicates that epitaxial relationships can be a source of stress in an oxide scale that ceria coatings may lower compressive stresses.
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    Oxidation of metals 48 (1997), S. 527-551 
    ISSN: 1573-4889
    Keywords: chloridation ; oxidation ; Fe-Cr alloys ; Ni-Cr alloys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The chloridation-oxidation behavior of Fe-Cr (0–25 wt. %Cr) and Ni-Cr (0–20 wt.%Cr) alloys was studied at 800°C in three different H2-HCl-H2O(ν) environments. In a low-HCI and low-H2O(ν) environment, where Cr2O3 is thermodynamically stable, the corrosion resistance of the Fe-Cr alloys increased with increasing Cr content in the alloys. In a high-HCl and high-H2O(ν) environment, where FeCr2O4 is stable and CrCl2 is metastable, the corrosion resistance of the Fe-Cr alloys depended similarly on the Cr content. Low-Cr-Fe-Cr alloys exhibited large weight losses, while Fe-Cr alloys with higher than 19 wt. %Cr showed good corrosion resistance. In an environment of high-HCl in the absence of H2O(ν), the evaporative corrosion rate was fast and limited by gas phase diffusion, and independent of the Cr content in the Fe-Cr alloys. Ni and Ni-Cr alloys generally showed good corrosion resistance in the environments of high H2O(ν) because of the low NiCl2 vapor pressure and formation of a protective Cr2O3 scale. However, in the environment of high HCl in the absence of H2O(ν), selective formation and evaporation of CrCl2 occur, which results in Cr depletion and networks of voids for even a high-Cr Ni-Cr alloy.
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  • 26
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    Oxidation of metals 48 (1997), S. 553-596 
    ISSN: 1573-4889
    Keywords: chloridation ; oxidation ; HCl ; high-temperature alloys ; high-temperature corrosion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Chloridation-oxidation studies of nine commercial high-temperature alloys were carried out at 800°C in three different H2-HCl-H2O(ν) environments: (A) both low HCl and H2O(ν) partial pressures, where either Cr2O3 or FeCr2O4 is stable, (B) both high HCl and H2O(ν) partial pressures, where FeCrO4 is stable and CrCl2 is metastable, and (C) high HCl partial pressure in the absence of H2O(ν), where either CrCl2 or Cr2O3 is stable. Although alloy 600 has the lowest Cr content of these nine alloys, it showed excellent corrosion resistance in all three environments because of its high Ni content. Alloy 304, with the lowest Ni content of the nine alloys, exhibited poor corrosion resistance in the environment C, fair resistance in the environment B and good resistance in the environment A. Alloy 800 showed very good resistance in Environment A, and fair corrosion resistance in Environment B; however, it suffered linear weight-loss kinetics when exposed to Environment C The alloys 617, 214, HR-160, X, 230 and 86 have good corrosion resistance in Environments A and B because of their relatively high contents of oxide-scale-forming elements Cr and/or Al. In Environment C, chlorine dramatically decreased the adhesion of the scale on the surface, and aluminum in alloys 617 and 214 hardly showed its usual beneficial effect in combating corrosion, nor does silicon in alloy HR-160. Different corrosion mechanisms are proposed for the alloys in the different environments.
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  • 27
    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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  • 28
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    Oxidation of metals 27 (1987), S. 83-93 
    ISSN: 1573-4889
    Keywords: silicon carbide ; oxidation ; constructional ceramics
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    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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  • 29
    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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  • 30
    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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  • 31
    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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  • 32
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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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  • 33
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    Oxidation of metals 37 (1992), S. 167-187 
    ISSN: 1573-4889
    Keywords: H2-H2S-H2O ; sulfidation ; NbO2 ; oxidation ; CoNb3S6
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The corrosion of Co-Nb alloys containing up to 30 wt.% Nb in H2-H2S-H2O gas mixtures was studied over the temperature range of 600–800°C. The gas composition falls in the stability region of cobalt sulfide and Nb2O5 in the phase diagrams of the Co-O-S and Nb-O-S systems at all temperatures studied. Duplex scales, consisting of an outer layer of cobalt sulfide and a complex, heterophasic inner layer, were formed at all temperatures studied. In addition to cobalt sulfide and CoNb3S6, a small amount of NbO2 was found in the inner layer. The reason for the formation of NbO2 over that of Nb2O5 in the scale is that the outer sulfide scale lowers the oxygen activity within the scale into the NbO2-stability region. Two-stage kinetics were observed for all alloys, including an initial irregular stage usually followed by a steady-state parabolic stage. The steady-state parabolic rate constants decreased with increasing amounts of Nb, except for Co-20Nb corroded at 700°C. Nearly identical kinetics were observed for Co-20Nb corroded at 600°C and 700°C. The presence of NbO2 particles leads only to a limited decrease of the available cross-section area for the outward-diffusing metal ions. The activation energies for all alloys are similar and are in agreement with those obtained in a study of the sulfidation of the same alloys. The primary corrosion mechanism involves an outward Co transport.
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  • 34
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    Oxidation of metals 37 (1992), S. 217-252 
    ISSN: 1573-4889
    Keywords: mixed gas ; Nb2O5 ; NiNb3S6 ; NiNb2S4 ; multi-layered scales ; oxidation ; sulfidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The corrosion behavior of Ni-Nb alloys containing up to 40 wt.% Nb was studied over the temperature range of 550–800°C in a mixed H2/H2O/H2S gas. The scales formed on all alloys were multilayered. The outer scale was single-phase Ni3S2, while the structure and constitution of the inner scale depended on alloy composition and reaction conditions. Internal oxidation has been found in Ni-20Nb and Ni-30Nb, external oxidation has been observed on Ni-34Nb. Platinum markers were located at the interface between the outer scale and inner scale. The decrease in corrosion rate with increasing Nb content may be attributed to the presence of increasing amounts of Ni-Nb double sulfides as well as to the presence of Nb2O5 in the inner region of the scale.
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  • 35
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    Oxidation of metals 38 (1992), S. 45-72 
    ISSN: 1573-4889
    Keywords: intermetallic-matrix composites ; oxidation ; NiAl ; fiber/matrix interfaces
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The 1200°C and 1300°C isothermal and cyclic oxidation behavior of Al2O3 continuous fiber (Saphikon™)-reinforced/ NiAl composites were studied. Oxidation resulted in formation of Al2O3 external scales in a similar manner as scales formed on monolithic NiAl. The isothermal oxidation of an Al2O3/NiAl composite resulted in oxidation of the matrix along the fiber/matrix interface near the fiber ends. This oxide acted as a wedge between the fiber and matrix, and, under cyclic oxidation conditions, led to further oxidation along the fiber lengths and eventual cracking of the composite. The oxidation behavior of composites in which the Al2O3 fibers were sputter coated with nickel prior to processing was much more severe. This was attributed to open channels around the fibers which formed during processing most likely as a result of the diffusion of the nickel coating into the matrix.
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  • 36
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    Oxidation of metals 38 (1992), S. 89-98 
    ISSN: 1573-4889
    Keywords: kinetics ; oxidation ; zirconium hydride
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation kinetics of zirconium-hydride powders were studied in the temperature range of 298–1378 in air at atmospheric pressure. TG, DTA, DSC, x-ray analysis, and scanning electron microscopy were used. The results obtained are in accordance with the proposed pseudo-parabolic model of zirconium-hydride oxidation. This model includes the initial linear mode of oxide growth with oxygen diffusion through a non-solid film of ZrO2 of variable depth and a stationary diffusion process followed by oxide sintering. It has been established that the activation energy of the limiting stage of oxidation (238.3 kJ/mol) coincides with the activation energy of oxygen self-diffusion in monocline ZrO2.
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  • 37
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    Oxidation of metals 38 (1992), S. 267-287 
    ISSN: 1573-4889
    Keywords: oxidation ; electrons ; electrolyte ; ionic conduction ; electric field
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The imposition of a dc voltage across an oxide-ion-conducting solid electrolyte, upon which a gradient in the chemical potential of neutral oxygen (O, O2) is maintained, causes coupled gradients in the electrochemical potentials of oxygen ions and electrons. The concept of balancing these gradients to provide oxidation protection at high temperatures is discussed. Experimental results show a significant reduction in the oxidation of a zircaloy substrate under an applied electric field near the open-circuit potential. The current densities required are small enough to allow the use of electrically-conducting-ceramic electrodes.
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  • 38
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    Oxidation of metals 38 (1992), S. 299-307 
    ISSN: 1573-4889
    Keywords: microcrystal ; sputtering ; oxidation ; superalloy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of sputtered and cast superalloy K38G specimens was studied. The sputtered alloy was microcrystalline, with an average grain size 〈0.1 μm. The mass gains of the sputtered alloy were much less than those of the cast alloy at 800, 900, and 1000°C up to 500 hr, and were even less than those of pack aluminide on the cast alloy. K38G is a chromia-forming cast nickel-base superalloy, so the oxide scale formed on it is composed of Cr2O3, TiO2, Al2O3, and a spinel. The oxide scale formed on the sputtered alloy was Al2O3. This scale is thin, compact, and adherent. This result implied that micro crystallization reduced the critical aluminum content necessary to form alumina on the surface of this superalloy. No oxide spoliation, as typically observed for cast of aluminized alloys, occurred on the sputtered superalloy. The reduction of the critical aluminum content for the formation of alumina and the improvement of the spoliation resistance may be attributed to the microcrystalline structure formed during sputtering. The numerous grain boundaries favor outward aluminum grain-boundary diffusion, provide increased nucleation sites, and reduced stresses in the oxide scales.
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  • 39
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    Oxidation of metals 45 (1996), S. 153-181 
    ISSN: 1573-4889
    Keywords: oxidation ; 18O diffusion ; nickel ; stress effects on diffusion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract This study deals with the influence of various mechanical loadings (fatigue, creep, creep-fatigue) on oxygen diffusion in a particular system, oxidizing nickel. A distinction between the behavior of the oxide layer and underlying nickel was noted during the first step of oxidation at 550°C, in PO 2=1 atm. Mechanical loading causes a decrease of the oxygen mobility through the oxide scale (factor of 103). The oxide thicknesses on nickel undergoing mechanical loadings are different than for an unloaded sample, due to distinct contributions of the oxygen and nickel fluxes in the growing oxide. In the substrate, the ingress of oxygen becomes easier with a constant tensile load (creep). The intergranular-oxygen diffusion coefficient, Di, is increased by a factor of 102 with respect to other samples. In creep, oxygen diffusion takes place along grain boundaries of a structure with smaller grains than in unstrained Ni. A short fatigue period during creep-fatigue decreases the sensitivity of nickel to intergranular-oxygen diffusion.
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  • 40
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    Applied composite materials 5 (1998), S. 69-94 
    ISSN: 1573-4897
    Keywords: modelling ; notch strength ; damage ; fatigue ; environment ; temperature ; prediction ; design
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A predictive design methodology based on modelling the fracture stress (notched tensile strength) and post-fatigue residual strength of laminated fiber composites is presented. The approach is based explicitly on the development of models of the physical processes by which damage accumulates at a notch-tip and the application of these models to cross-ply laminates for a variety of material systems, including thermosetting and thermoplastic matrices containing carbon, glass and Kevlar fiber reinforcements. The effects of temperature and humidity on composite fracture can also be examined in the context of this modelling strategy. A pre-requisite of the model is that it has to be calibrated for each material system by performing tensile tests on notched and unnotched cross-ply laminate. From this initial calibration, which takes relatively little time, it is possible to apply the model to a prediction of the dependence of fracture stress on notch size; to an understanding of the effects of laminate stacking sequence (within the same cross-ply family) on fracture stress; and to provide insight into the effects of thermal or load cycling history on fatigue damage-growth and residual or fatigue strength. The advantages and deficiencies of this modelling strategy are assessed, as well as the applicability of such a physical modelling approach to the predictive design and failure of composite materials in general.
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  • 41
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    Journal of materials synthesis and processing 6 (1998), S. 191-195 
    ISSN: 1573-4870
    Keywords: Transmission electron microscopy observation ; interfacial microstructure ; oxidation ; ZrC ; cubic ZrO2 ; amorphous carbon film
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Microstructure at the interface of ZrC and ZrO2 formed by oxidation of a single crystal of ZrC with 100 faces at 600°C at an oxygen pressure of 2 kPa was observed by high-resolution transmission electron microscopy and scanning electron microscopy. The ZrO2 scale was shown to consist of two subscales, zones 1 and 2. The interfacial area in zone 1 was composed of regular lattice fringes corresponding to the 111, 200, and 220 lattices of cubic ZrO2 (c-ZrO2) crystallites 2 to 10 nm in size and an amorphous phase. The growth of crystallites occurred in zone 2, which visualized the interface of zones 1 and 2. Black thin films reminiscent of zone 1 were successfully separated, which were composed of amorphous carbon in which c-ZrO2 particles 2 to 20 nm in size were included.
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  • 42
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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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  • 43
    ISSN: 1573-4889
    Keywords: non-isothermal ; oxidation ; Al2O3+Cr2O3 coatings ; Fe, Fe-Cr alloys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The non-isothermal oxidation behavior of electrolytic-grade iron and Fe-Cr alloys in dry air has been studied using linear heating rates of 6 K/min, 10 K/ min, and 15 K/min up to a final temperature of 1273–1473 K. Some of the iron and iron-chromium alloy samples were given a surface treatment by dipping them in an aqueous solution containing both Cr and Al ions before their oxidation studies. This pretreatment has resulted in improved oxidation resistance and scale adherence as depicted by no scale rupture even after a second thermal cycle. Mass changes were recorded gravimetrically, and scales have been characterized by SEM, EPMA, and x-ray diffraction analyses.
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  • 44
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    Oxidation of metals 37 (1992), S. 111-124 
    ISSN: 1573-4889
    Keywords: oxidation ; titanium aluminide ; oxidation kinetics ; oxidation products
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Static oxidation kinetics of Ti-25Al-10Nb-3V-1Mo (atomic percent) were investigated in air over the temperature range of 650–1000°C using thermogravimetric analysis. The oxidation kinetics were complex at all exposure temperatures and displayed up to two distinct stages of parabolic oxidation. Breakaway oxidation occurred after long exposure times at high temperatures. Oxidation products were determined using x-ray diffraction techniques, electron microprobe analysis, and energy dispersive x-ray analysis. Oxide scale morphology was examined using scanning electron microscopy of the surfaces and cross-sections of oxidation specimens. The oxides during the parabolic stages were compact and multilayered, consisting primarily of TiO2 doped with Nb, a top layer of Al2O3 and a thin bottom layer of TiN. The transition between the first and second parabolic stage is linked to the formation of a TiAl layer at the oxide-metal interface. Porosity also formed in the TiO2 layer during the second stage, causing degradation of the oxide and breakaway oxidation.
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  • 45
    ISSN: 1573-4889
    Keywords: molybdenum ; molybdenum trioxide ; oxidation ; oriented growth ; growth mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of polycrystalline Mo plates and of Mo(100), Mo(110), and Mo(111) single-crystal plates in pure oxygen at 8 × 104 and 2.7 × 103 Pa, at 743–1023 K leads to the growth of orthorhombic MoO3 only, as shown by X-ray diffraction and SEM observations. The stable oxides MoO2 and Mo4O11 were not identified. At each side of the molybdenum plate, the oxide scale is a stacking of MoO3 crystals with their [100] axes oriented normal to the surface of the initial Mo plate. The MoO3 crystals are very thick in the [010] direction, compared with the well-known shape of the MoO3 crystals grown from the vapor phase. Two main factors determine the oriented growth of MoO3 crystals from Mo oxidation. A growth mechanism involving a structural rearrangement of the Mo atoms at the reactional interface and oxygen diffusion through the oxide is proposed.
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  • 46
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    Oxidation of metals 37 (1992), S. 23-37 
    ISSN: 1573-4889
    Keywords: aluminum-lithium alloys ; oxidation ; second-phase particles ; secondary ion mass spectrometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Oxidation behavior of Al-Li alloys, containing a high volume fraction of Ferich second-phase particles, was studied at 530°C and 200°C. Morphological studies showed enhanced growth of Li-rich oxides in the vicinity of the insoluble second-phase particles. Microanalytical depth profiling of the oxide layer with a high resolution scanning ion microprobe indicated rapid diffusion and subsequent oxidation of Li at the free surface. Examination of the alloy surface after removal of the oxide layer suggested that the initial oxide growth occurred in the lateral direction. Secondary ion image depth profiling of the alloy surface after oxide removal revealed Li segregation to the alloy/second-phase interface, supplying Li for accelerated oxidation. A microstructural model of the oxidation process in this case is presented.
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  • 47
    ISSN: 1573-4889
    Keywords: binary alloys ; oxidation ; transient state ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The initial transient stage in the oxidation of binary alloys forming scales exclusively composed of the most stable oxide is examined by means of a simplified approach which avoids the numerical integration of the diffusion equation for the transport of the metal components in the alloy. At variance with previous solutions to this problem obtained by means of numerical methods, this treatment takes into account also the effect of the gas-scale reaction at the outer surface of the oxide. The concentration of the most-reactive component at the alloy surface changes gradually with time from the initial bulk value towards the corresponding steady-state value without involving any minimum, while the overall rate of the reaction presents a gradual transition from an initial nearly linear towards final parabolic behavior.
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  • 48
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    Oxidation of metals 47 (1997), S. 247-258 
    ISSN: 1573-4889
    Keywords: Ni3Al-base alloy ; sputtering ; nanocrystalline coating ; oxidation ; 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 Isothermal and cyclic oxidation resistance at 1000°C in air were investigated for a cast Cr-containing Ni3Al-base alloy and its sputtered nanocrystalline coating. The results indicated that both the cast Ni3Al alloy and its sputtered coating exhibit excellent isothermal oxidation resistance as a result of the formation of Al2O3 scales. However, the cast alloy possesses very poor cyclic oxidation resistance because of the spallation of the initially formed Al2O3 scale during cooling and subsequent formation of NiO. On the contrary, the sputtered Ni3(AlCr) nanocrystalline coating exhibits very good cyclic oxidation resistance due to the significant improvement of the adhesion of Al2O3.
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    Journal of materials synthesis and processing 6 (1998), S. 335-338 
    ISSN: 1573-4870
    Keywords: PbZrO3 ; oxidation ; nonstoichiometry
    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 the results of work function (WF) changes of undoped PbZrO3 during subsequent isothermal oxidation and reduction experiments at 500°C in the p(O2) range between 10 and 2.1 × 104 Pa. The results, obtained during three consecutive runs, indicate that heating at 500°C leads to continuous changes of surface properties resulting in a complex WF vs. time characteristic. The WF changes during the first oxidation are determined by a p(O2)-induced structural transition. The second oxidation results in two competitive processes, such as rapid increase of oxygen non-stoichiometry followed by a structural transition. Finally, the third oxidation is determined by changes of oxygen nonstoichiometry.
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    Journal of materials synthesis and processing 6 (1998), S. 373-377 
    ISSN: 1573-4870
    Keywords: Zirconia ; oxidation ; preparation
    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 surface electrical properties of zirconia studied using work function measurements in the temperature range 297–1173 K during oxidation. It was found that surface preparation procedures, such as grinding and polishing, result in a change of its reactivity with oxygen. The effects produced by the preparation can be removed during thermal treatment at 1473 K.
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  • 51
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    Journal of materials synthesis and processing 6 (1998), S. 407-410 
    ISSN: 1573-4870
    Keywords: CaB6 ; oxidation ; weight gain ; calcium borate ; 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 of CaB6 powders at high temperatures was investigated. The sample oxidized at 873 to 973 K for 25 hours exhibited weight gain with increasing oxidation temperature; the oxidation proceeded in accordance with the parabolic law during the initial oxidation stage. On the other hand, the weight gain of the sample oxidized at and above 1073 K for 4 h was approximately 80%; however even if the oxidation time was prolonged, an additional weight change did not occur. Based on the results of the X-ray diffraction analysis, calcium borate (CaB4O7) was present on the surface of the sample oxidized at 1073 K. The sample showed a good oxidation resistance at 1273 to 1373 K, because the surface film of calcium borate (CaB2O4) formed by oxidation acted as an oxidation resistant layer.
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  • 52
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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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  • 53
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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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  • 54
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    Oxidation of metals 27 (1987), S. 315-332 
    ISSN: 1573-4889
    Keywords: chromium ; NaCl ; oxidation ; hot corrosion ; mechanism
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    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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  • 55
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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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  • 56
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    Oxidation of metals 38 (1992), S. 73-87 
    ISSN: 1573-4889
    Keywords: Fe-Al alloys ; oxidation ; scale morphology ; ternary additions
    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 briefly summarizes studies related to the oxidation of Fe-Al alloys. Emphasis is placed on oxide phase composition, morphology, and the development of protective α-Al2O3 scales on oxidation-resistant Fe-Al alloys both with and without ternary additions.
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  • 57
    ISSN: 1573-4889
    Keywords: oxidation ; ion implantation ; yttrium ; amorphous
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Yttrium ions were implanted into an alloy of nickel containing 20 wt.% chromium. The oxidation weight gains of the implanted alloy, as well as unimplanted Ni-20Cr, were measured in 1 atm. of oxygen at temperatures between 815°C and 1100°C. Though a yttrium fluence of 2×1015 ions/cm2 increased the weight gained at a given time for the implanted alloy compared to the unimplanted alloy, a fluence of 7.5×1016 ions/cm2 considerably retarded the oxidation process. This retardation was caused both by a reduction in the duration of transient oxidation and by a reduction in the rate of parabolic oxidation that follows the transient stage. Examination of oxidized specimens revealed that the higher fluence yttrium implantation caused an earlier formation of Cr2O3, thus shortening the time during which NiO forms and contributing to the reduced time and weight gain during transient oxidation. This accelerated formation of Cr2O3 is explained by reference to the yttrium-implantation-induced amorphous phase present on the alloys, the formation of small grains of nickel-chromium solid solution within this amorphous phase, and the presence of NiCr2O4 at the oxide/gas interface. Potential causes of the reduced rates of parabolic oxidation are also discussed.
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    Oxidation of metals 45 (1996), S. 109-131 
    ISSN: 1573-4889
    Keywords: Fe−Al−C ; Fe−Al−Si−C ; inoculation ; scale ; characterization ; oxidation ; high temperature
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Isothermal-oxidation characteristics of cast irons containing aluminum (5–15% Al) from 700 to 1000°C in air have been studied. In addition to massgain measurements, the morphology and composition of the oxide scales have been examined by SEM-EDX system and XRD analysis. A normal Fe−5Al−C alloy does not develop protective, adherent scales. Even the addition of misch metal and calcium silicide to such an alloy does not improve its oxidation resistance. But aluminum cast iron develops considerable oxidation resistance only when a sufficient quantity of silicon is also present in the alloy. Treatment of the alloy with misch, metal and calcium silicide together assists in protective scale formation. Among the alloys investigated Fe−15Al−Si−C treated with misch metal and calcium silicide shows minimum oxidation at 1000°C.
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  • 59
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    Oxidation of metals 45 (1996), S. 469-486 
    ISSN: 1573-4889
    Keywords: iron ; sulfur dioxide ; oxidation ; tracer
    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 iron with sulfur dioxide at 0.1 MPa and 1073 K was studied. The composition and morphology of the scales, transport phenomena occurring in the growing scales, and kinetics of the process were investigated. Scanning electron microscopy and various techniques of X-ray analysis were used. The transport phenomena were studied by marker and by radiotracer techniques. The scales were composed of sulfide and oxides and grew by the outward diffusion of metal. It was concluded that the process initially took place through the reaction of iron with sulfur dioxide molecules. During the next stage of the process the reaction with sulfur dioxide molecules as well as with oxygen molecules is possible.
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    Oxidation of metals 45 (1996), S. 507-527 
    ISSN: 1573-4889
    Keywords: oxidation ; sulfidation ; oxides ; sulfides ; Ti ; Ti-6Al-4V alloy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Pure titanium and Ti-6Al-4V were exposed at 750°C in an H2/H2O/H2S PO 2≈10−18 Pa and PS 2≈10−1 Pa), H2/H2O (PO 2≈10−18 Pa) and air environments for up to 240 hr. The corrosion kinetics, obtained by the discontinuous gravimetric method, showed that the sulfidation/oxidation kinetics were linear for Ti and linear-parabolic for Ti-6Al-4V in the H2/H2O/H2S environment. Both materials obeyed parabolic rate laws in the H2/H2O atmosphere after a transient period, and linear-parabolic rate laws in air. After exposure to the H2/H2O/H2S atmosphere, the titanium specimen displayed a double scale of TiO2 with an intervening TiS2 film between the double-layered scale of TiO2 and the substrate. Ti-6Al-4V also contained a double layer of TiO2 together with a stratum consisting of Al2S3, TiS2 and vanadium sulfide at the junction of the inner TiO2 layer and substrate. Some Al2O3 precipitated in the external portion of the outer TiO2 layer. Following oxidation in the low-PO 2 atmosphere a double-layered oxide of TiO2 scale formed on both Ti and Ti-6Al-4V. The scale on Ti-6Al-4V also contained an α-Al2O3 film situated between the outer and inner (TiO2) layers. For both materials, multilayered-scale formation characterized air oxidation. In detail a multilayered oxide scale of TiO2 formed on the air-oxidized Ti, while a multilayered oxide scale with alternating layers of Al2O3/TiO2 developed on Ti-6Al-4V oxidized in air.
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    Oxidation of metals 45 (1996), S. 487-505 
    ISSN: 1573-4889
    Keywords: sulfidation ; oxidation ; gasification ; austenitic steel 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 major use of high-temperature steel alloys in gasifiers is in heat exchangers for cooling hot syngas, consisting mainly of CO and H2 with lesser amounts of H2O and CO2 and minor quantities of H2S and HCl. Metal temperatures range from 250 to 600°C, gas temperatures from 250 to 1200°C. Because of rapid cooling the composition of the gas does not change with temperature. Therefore the gas is not in equilibrium at the metal surface. Calculations show that such gases have lower oxygen and sulfur pressures than equilibrated gases at the same temperature. This makes the results of previous laboratory studies less appropriate for predicting mixed oxidant corrosion in gasifiers. For this reason the present study was carried out using nonequilibrium gas mixtures, similar to gases, produced in entrained-slagging gasifiers. Most corrosion experiments were carried out at 540°C, as this is a common temperature for superheaters and hot-gas cleanup systems. Iron-base model alloys containing 35% Ni, 20% Cr, and various minor alloying additions were studied. Three corrosion regimes were identified over the range of conditions studied, depending on the sulfur-to-oxygen pressure ratio of the gas and the alloy composition. At high PS 2/PO 2 ratios a somewhat protective FeCr2S4 scale formed on all alloys. Below this layer internal oxidation and sulfidation occurred at a slow rate. At lower PS 2/PO 2 ratios nonprotective Fe(Ni, Cr)S external scales formed. These allow rapid internal oxidation of the chromium in the alloy, resulting in high corrosion rates. Under the same conditions very low corrosion rates are obtained when silicon is added to the alloy, because the presence of SiO2 precipitates makes the internal-oxidation layer protective. Thus, the same corrosion model is operative in all three corrosion regimes: external sulfidation of iron and nickel, together with internal oxidation of chromium and other strong-oxide formers.
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    Oxidation of metals 46 (1996), S. 255-285 
    ISSN: 1573-4889
    Keywords: electron diffraction ; intermetallic ; oxidation ; TEM ; titanium aluminide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The early stages of TiAl oxidation at 900°C and 1000°C in air have been investigated by transmission electron microscopy (TEM). The investigations revealed that at the beginning of oxidation, i.e., after 4 min, TiO2 and Al2O3 grow in a preferential orientation on the γ-TiAl substrate. After 4 h of oxidation an oxide scale structure can already be found similar to that known from long-term oxidation. In addition, besides α-Al2O3, the formation of a second aluminum oxide phase and of titanium nitrides is observed. The processes at the metal-oxide interface of oxidation in the early stages, consisting of a repeated cycle of Al2O3 formation, Al2O3 dissolution, outward migration of Al through the scale, and reprecipitation of Al2O3 in the outer scale, are described by a model. The four stages observed in the kinetics of TiAl oxidation are explained on the basis of the results obtained and the structure of the oxide scale.
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    Oxidation of metals 46 (1996), S. 287-297 
    ISSN: 1573-4889
    Keywords: pure niobium ; oxidation ; sulfidation ; oxidation-sulfidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The corrosion of pure niobium has been studied at 600–800°C in various environments as part of a study of the corrosion resistance of its alloys with iron, cobalt, and nickel to atmospheres of low-oxygen and/or high-sulfur activities. The results have shown that not only the sulfidation but also the corrosion in mixed atmospheres and particularly the oxidation under low oxygen pressures of pure niobium are quite slow, with kinetics rather similar in the three types of gas mixtures used. The good corrosion resistance of niobium to attack by oxygen under low pressures is quite interesting because this element is corroded very rapidly by oxygen under high oxygen pressures, due to the formation of the nonprotective highest oxide Nb2O5 as a main corrosion product.
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  • 64
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    Oxidation of metals 46 (1996), S. 335-364 
    ISSN: 1573-4889
    Keywords: Fe−Cr ; oxidation ; exhaust gas ; oxide adherence ; titanium ; rare earths
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Oxidation tests of rare-earth-modified and Ti-modified Fe−20Cr alloy foils, which are under consideration for catalytic converter supports, were performed in a synthetic exhaust-gas atmosphere (N2+H2O+CO2) between 900°C and 650°C. Between 900°C and 750°C, the rare earths had no effect on oxide growth rates while Ti increased growth rates. Oxide growth rates for the rareearth alloys at 800°C and 750°C are much lower than those found in the literature for oxidation of Fe−Cr alloys or pure Cr in O2-rich atmospheres. The slow growth rates for the rare-earth alloys agree with literature data for oxidation of stainless steels containing 〉20% Cr in wet atmospheres and are caused by growth of an oxide scale only one grain thick. At temperatures ≤700°C, Fe−20Cr alloys grow massive Fe oxides; however, this can be suppressed by adding rare earths or Ti. To ensure good oxide adherence, free sulfur must be eliminated in the alloy by tying it up with a reactive-element addition. Both Ti and the rare earths can be used to tie up S, but the rare earths are more effective. For converter applications, the optimum alloy composition may contain rare earths for good oxide adherence and a small amount of Ti to suppress growth of Fe-rich oxides.
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  • 65
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    Oxidation of metals 46 (1996), S. 365-381 
    ISSN: 1573-4889
    Keywords: oxidation ; steel ; Raman ; scale ; transient oxides
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Using Raman scattering we have investigated the oxidation, in air, of the Fe-Cr-Ni stainless steels Fe-25Cr-20Ni, Fe-25Cr-20Ni-3Zr, and Fe-24Cr-3Zr (wt.%) as a function of temperature in the range 300 to 1000°C. The Raman technique is very sensitive to, and provides a clear identification of, the oxides Fe2O3 and Cr2O3. However, the technique is insensitive to NiO, FeO, and does not give a clear identification of spinels. The Fe−Cr−Ni alloys form chromia scales at temperatures greater than ∼800°C. At lower oxidation temperatures, transient phases are observed. With a 1-h heat treatment at 300°C, we observe the formation of an unidentified scale; we speculate that it is either amorphous or consists of disordered spinel(s). Near 400°C we begin to observe hematite (Fe2O3). The intensity of the Fe2O3 signal increases with temperature to ∼600°C and then decreases, being largely replaced by the signal from Cr2O3. The thickness of the Cr2O3 scale increases with temperature up to ∼1000°C above which spallation becomes apparent. Spinel phases also apparently persist in the scale to 1000°C.
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    Oxidation of metals 46 (1996), S. 383-398 
    ISSN: 1573-4889
    Keywords: high temperatures ; binary alloys ; two-phase 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 The steady-state kinetics in the high-temperature oxidation of binary A-B alloys containing a mixture of the conjugated solid solutions of B in A (alpha phase) and A in B (beta phase) with exclusive formation of the most-stable oxide BOv have been examined, assuming that the external scale grows on top of a subsurface layer of alpha phase. The results obtained are compared with the corresponding behavior of alloys which are single phase in the whole range of composition. Under identical values of all the parameters involved the concentration of B at the alloy-scale interface is smaller for two-phase than for single-phase alloys under the same concentration of B in the alloy as a result of the restricted flux of B through the alpha-phase layer. As a consequence of this, the two-phase alloys corrode more slowly than single-phase alloys and this difference increases as the solubility of B in the alpha phase decreases. Finally, the simultaneous formation of BOv both externally and as internal oxide is more likely for two-phase than for single-phase materials.
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  • 67
    ISSN: 1573-4889
    Keywords: niobium alloys ; oxidation ; high temperatures
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The corrosion of M−Nb alloys based on iron, cobalt, and nickel and containing 15 and 30 wt% Nb has been studied at 600–800°C under low oxygen pressures (10−24 atm at 600°C and 10−20 atm at 700–800°C). Except for the Co−Nb and Ni−Nb alloys corroded at 800°C, which formed external scales of niobium oxides, corrosion under low O2 pressures produced an internal oxidation of niobium. This attack was much faster than expected on the basis of the classical theory. Furthermore, the distribution of the internal oxide in the alloys containing two metal phases was very close to that of the Nb-rich phase in the original alloys. These kinetic, microstructural, and thermodynamic aspects are examined by taking into account the effects of the limited solubility of niobium in the various base metals and of the two-phase nature of the alloys.
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  • 68
    ISSN: 1573-4889
    Keywords: oxidation ; scaling ; surface temperature ; heat of reaction
    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 the oxidation behavior of low-carbon steel samples in binary gas mixtures of oxygen and nitrogen, at oxygen concentrations ranging between 1% and 15% and temperatures ranging between 1000 and 1250°C. Sample weight gains versus time were analyzed, along with measurements and calculations of sample heating rates due to exothermic heat of reaction at the sample surface. It was found that initial rates of oxidation depended on oxygen content in the gasmixture and that these reaction rates were linear up to oxide thicknesses of 0.4 to 0.5 mm. Calculations of linear oxidation rate constants based on equations for mass transport of oxygen in the gas mixture to the sample surface showed good agreement with those measured experimentally, indicating that the initial period of oxidation is controlled by the mass transport of oxygen to the reaction interface. The linear rate constants showed little dependency on temperature, an activation energy of approximately 17kJ/mole being obtained. Measurements of sample surface temperatures have shown that within this linear-oxidation regime, interfacial temperatures of the samples increase with increasing oxygen contents in the gas mixture, owing to exothermic heats of oxidation. Subsequent oxidation kinetics were found to be parabolic. Measured parabolic rates constants were in good agreement with previous investigations, with activation energy values of approximately 127kJ/mole.
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  • 69
    ISSN: 1573-4889
    Keywords: ODS Alloy ; oxidation ; SIMS ; microstructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Alumina-forming ODS superalloys are excellent oxidation-resistant materials. Their resistance relies upon the establishment of a stable, slow-growing, and adherent α-alumina. In the present investigation, these alloys exhibited unstable and relatively less adherent θ-alumina phase, which increased the oxidation rate in the transient stage and converted into α-alumina in the later part of the exposure. The oxide-growth process was found to depend upon various parameters such as temperature, time, and presence of an active elecment in the superalloy. Characterization carried out by XRD, SEM/EDAX, and AES on oxidized ODS and non-ODS alloys demonstrated a significant influence of the active element, Y, on the transformation of θ- to α-alumina. SIMS analysis of two-stage oxidation at 900°C for two different durations evidently showed that the change in the transport process is due to θ-to-α-alumina transformation. On the basis of these results, a new and consistent mechanism is proposed to explain the influence of θ-alumina and its transformation on growth kinetics and the effect of yttrium on the transformation leading to good scale adherence and oxidation resistance.
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    Oxidation of metals 47 (1997), S. 21-52 
    ISSN: 1573-4889
    Keywords: copper ; silver ; high temperature ; oxidation ; two-phase 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 corrosion of three two phase Cu-Ag alloys containing 25, 50, and 75 wt% Ag has been studied at 650 and 750°C. In all cases the alloys formed external scales of copper oxides. At the same time, an internal precipitation of Cu2O within a silver matrix was also produced, with an oxide volume fraction larger for the alloys richer in Cu. Beneath this mixed layer a region of single-phase solid solution of Cu in silver formed for Cu-50Ag and especially for Cu-75Ag. Silver metal remained in the metal-consumption zone, acting essentially as an inert marker, except for a few particles with were incorporated into the growing scales. Both pure Cu and the alloys corroded parabolically, but the rate constants for the alloys decreased with increased Ag content under constant temperature. The various aspects of the corrosion of these alloys are examined by taking into account the possible effects associated with the presence of two metal phases.
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    Oxidation of metals 47 (1997), S. 69-89 
    ISSN: 1573-4889
    Keywords: duplex-layer formation ; dynamic oxygen-diffusion path ; Ni-Cr alloy ; 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 results of an investigation of oxidation of a Ni-1 at.% Cr alloy are presented. Photolithographic marker experiments revealed that the markers were found to reside at the interface between a predominantly columnar outer NiO layer and a very fine grain inner layer of NiO, indicating that substantial oxygen ingress had occurred through the columnar scale. New oxide growth at the metal-oxide interface requires the oxidant to be transported across the oxide layer. Since the measured diffusion rate of oxygen ions along grain boundaries and through the lattice is much too slow to account for the observed microstructural growth (∼1: 1 ratio of inner and outer layers), it is necessary to postulate that the oxidant traverses the scale along some type of short-circuit path other than grain boundaries. Extensive formation of elongated pores and pipelike channels was observed along columnar oxide grain boundaries. Thus, it appears that the transport of oxygen occurs via voids (pores) formed by vacancy coalescence at the columnar grain boundaries. These pores appear to open and close continuously. Formation of new fine-grained oxide in these pores was observed to have sometimes completely resealed the void, suggesting a dynamic nature of the voids.
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    Oxidation of metals 47 (1997), S. 139-203 
    ISSN: 1573-4889
    Keywords: oxidation ; MoSi2 ; TiSi2 ; air ; oxygen ; O and Si transport in SiO2
    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 two MoSi2 variants, one Mo-rich and one Si-rich, and TiSi2 was investigated between 1000 and 1400°C in air, oxygen and an 80/20-Ar/O2 mixture. A protective SiO2 scale develops on MoSi2 in all atmospheres in the temperature range investigated. The SiO2 modification changes around 1300°C from tridymite to cristobalite. This change in SiO2 modification seems to cause an enhanced formation of SiO2 and evaporation of MoO3. The SiO2 grows at the MoSi2-scale interface. In air a two-layer scale grows on TiSi2 between about 1000 and 1200°C with an inner inwards growing fine-grain mixture of SiO2 + TiO2 and an outer outward-growing TiO2 partial layer. TiN formation in the transient oxidation is responsible for the formation of the inner mixed partial layer because in N -free atmospheres a scale of a SiO2 matrix with some Ti oxide precipitates inside is formed. A one-layer scale structure similar as that in N-free atmosphere is found on TiSi2 in air at T 〉 1200°C. In oxygen the TiO2 precipitates grow as needles mostly oriented perpendicular to the surface. Due to the faster oxygen transport in TiO2 compared with SiO2, these TiO2 needles act as “oxygen pipes,” causing an enhanced oxidation of TiSi2 in front of these needles. The SiO2 scale dissolves about 1–2% TiO2. This doping causes a mixed oxygenand Si transport with the consequence that the SiO2 scale on TiSi2 grows partly by oxygen transport inwards and Si transport outwards. The SiO2 modification is cristobalite over the entire temperature range investigated.
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  • 73
    ISSN: 1573-4889
    Keywords: high temperature ; oxidation ; binary alloys ; steady-state
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The steady-state, high-temperature oxidation kinetics of single phase alloys rich in a most-reactive componentB in binaryA-B systems presenting a limited solubility of the two components (beta phase alloys) have been examined assuming the exclusive formation of the most-stable oxideBO v. Alloys sufficiently rich inB can form externalBO v scales directly in contact with the beta phase, while below a criticalB content the growth ofBO v involves also the appearance of an intermediate layer ofB-depleted solid solution ofB inA (alpha phase). The parabolic rate constants for the oxidation of single-phase beta alloys are lower than those of alloys of identicalB content which are single-phase over the whole range of composition (solid-solution alloys) but higher than for two-phase alpha + beta alloys under the same values of all the relevant parameters. Moreover, the tendency of single-phase beta alloys to form the most-stable oxide simultaneously as an external scale and internally to the alloy is greater than for solid-solution alloys but smaller than for two-phase alloys.
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  • 74
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    Oxidation of metals 47 (1997), S. 259-275 
    ISSN: 1573-4889
    Keywords: laser surface alloying ; aluminum ; superalloys ; oxidation ; microstructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The high-temperature oxidation resistance of laser-surface-alloyed Incoloy 800H with Al has been investigated. Several samples have been exposed to 1000°C in air and subsequently analyzed by optical microscopy, SEM, and electron microprobe X-ray fluorescence spectroscopy in order to determine their microstructure and composition. The results show that the laser-treated materials have a considerably higher oxidation resistance than the nontreated materials due to the formation of an Al-rich layer close to the surface, which acts as a barrier against oxygen diffusion into the bulk.
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  • 75
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    Colloid & polymer science 275 (1997), S. 467-473 
    ISSN: 1435-1536
    Keywords: Key words Block copolymers ; micelle ; temperature
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract  The association behaviour of triblock copoly(ethylene oxide/tetrahydrofuran/ethylene oxide), in particular E100T27E100, in aqueous solutions has been investigated by means of static and dynamic light scattering, nuclear magnetic reso-nance (NMR) and surface tension techniques. On raising the polymer concentration at room temperature, the copolymer aggregates to form micelles with an aggregation number of about 105 (R G, mic≈15 nm and R H, mic≈13 nm, as revealed by light scattering and FT-PGSE NMR measurements, respectively). The micelles are kinetically quite stable, the micellar lifetime is shown to be more than 1 h. The residence time of a single unimer in a micelle is more than 140 ms. The apparent radius of gyration R G, mic is fairly independent of concentration, but large effects are observed on varying the temperature. Raising the temperature initially results in an increase of the apparent micellar size, followed by a maximum at an intermediate temperature (≈45 °C). At higher temperatures a contraction of the micelles is observed. The shape of the micelles also appear to vary in this temperature interval. The interactions responsible for these phenomena are discussed in terms of, e.g., the temperature-dependent solubility of the alkylene oxide segments in water and polydispersity effects.
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  • 76
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    Colloid & polymer science 270 (1992), S. 1035-1041 
    ISSN: 1435-1536
    Keywords: Elongated micelles ; cetyltrimethylammonium bromide (CTAB) ; non-Newtonianviscosity ; shearrate ; concentration ; temperature
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract We report in this work new results of the study on the non-Newtonian viscosity of aqueous micellar solutions of cetyltrimethylammonium bromide (CTAB) in the presence of potassium bromide (KBr), in the concentration range where the elongated micelles overlap. The experiments have been performed as a function of the surfactant concentration, temperature and shear rate by use of a Couette-viscosimeter. In the non-Newtonian range, at relatively low surfactant concentration (≲0.25 M/l), our results show that the flow curves obtained at different temperatures converge to a single liner curve with a characteristic slope varying with the surfactant concentration. These same data can be superposed on a master curve when appropriate reduced variables are used. The shape of the flow curves obtained at different temperatures for a sufficiently high surfactant concentration is similar to that obtained for monodisperse polymer solutions at different molecular weights. The slope obtained of about −1 is also predicted by Graessley's model in the theory of microviscoelasticity based on the concept of entanglement for polymer solutions. However, at surfactant concentration higher than 0.25 M/l our results show an unusual behavior. Above some critical shear rate it is possible to obtain an increase of the apparent viscosity with temperature. One possible explanation of this effect can be found in the increase of the entanglement with concentration coupled with the temperature and direct now effects on scission and recombination rate of the micelles.
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  • 77
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    Colloid & polymer science 105 (1997), S. 322-325 
    ISSN: 1435-1536
    Keywords: Rheology ; surfactant solutions ; micelles ; phase transition ; temperature
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Aqueous solutions of cationic surfactant with binding counterions exhibit a transition under shear. In this paper the steady shear properties of semidilute aqueous micellar solutions (cetylpyridinium chloride and sodium salicylate in brine) are presented as a function of concentration and temperature. The shear thinning behavior of this system could be described by the Carreau model at low shear rate and by a power law at higher shear rate. The temperature dependence of the zero shear viscosity follows an Arrhenius relationship. The critical shear rate at which the viscosity departs from its zero shear value is found to increase with temperature indicating the influence of this parameter on transition.
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  • 78
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    Journal of elasticity 44 (1996), S. 229-254 
    ISSN: 1573-2681
    Keywords: thermoelasticity ; surface ; nearly-planar ; dynamic ; temperature
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract The effects of non-planarity on the dynamic surface temperature changes induced for plane-strain and 3D problems on the nearly-planar surfaces of, respectively, coupled thermoelastic half-planes and half-spaces by surface heat fluxes are treated. The nearly-planar nature of the surfaces allows the problem solutions to be written, following a standard perturbation scheme, as series expansions in a dimensionless surface contour amplitude parameter. The first, or zero-order, terms represent the ideal (planar) surface solutions, while the second, or first-order, terms represent corrections for non-planarity. Because the characteristic thermoelastic time is of O(10−7)μs, large-time asymptotic forms of the exact integral transform solutions can be used. These can be inverted exactly and used in Green's function operations to yield analytic, or integrals of analytic, expressions. Two types of thermal loading for the half-plane and yet a third type of thermal loading for the half-space are considered. Comparison of the zero- and first-order surface temperature changes for each case indicate that non-planarity gives rise for large times to changes in surface regions beyond those predicted by an ideal surface analysis. Moreover, the magnitudes of these changes can be more significant than the ideal surface results.
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  • 79
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    Tribology letters 2 (1996), S. 263-272 
    ISSN: 1573-2711
    Keywords: wear ; temperature ; coatings ; Ni-P coatings ; lubrication
    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 temperature on the wear of as-deposited electroless Ni-P coating under lubricated reciprocating sliding conditions has been investigated using the ball-on-block test method. It was shown that the temperature increase from 25 to 100°C reduces the lubricated wear of EN coatings, especially at high loads. The wear mechanism has also changed as the temperature rises from 25 to 100°C. X-ray mapping and EDS analyses have shown that there are more sulfur and phosphorus on the wear track at high temperature which may be responsible for reduced friction and the wear of the coating.
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  • 80
    ISSN: 1042-7147
    Keywords: particle size ; temperature ; PCS ; polyacrylate core-shell emulsion ; polystyrene suspension ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: The dependence of the particle size of a polyacrylate core-shell emulsion on temperature has been investigated in the temperature range of 10-55°C by photon correlation spectroscopy. To compare, the dependence of the particle size of an aqueous suspension of a polystyrene standard on temperature has been also investigated under the same conditions. This showed that as the temperature increases, the particle size of both samples decreases, but the rate of size decrease of the polystyrene standard is larger than that of the polyacrylate core-shell emulsion. By linear regression analysis, two regression equations of both samples have been set up. Furthermore, the apparent moving activation energy has been worked out from the size-temperature data.
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    New York, NY : Wiley-Blackwell
    Polymers for Advanced Technologies 7 (1996), S. 73-75 
    ISSN: 1042-7147
    Keywords: oxidation ; methanol ; polymer-copper complex ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Silica-supported polystannazane-copper complex has been prepared and used as a catalyst for the oxidation of methanol. The results showed that the catalyst could catalyze the oxidation of methanol to formaldehyde at a high yield and selectivity at 30°C and under 1 atm mild conditions. The N/Cu mole ratio in the complex, temperature and the amount of NaOH additive had much influence on the catalytic activity. The complex was stable during the reaction and could be used repeatedly.
    Additional Material: 4 Ill.
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