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  • 1
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Journal of Chromatography A 623 (1992), S. 123-127 
    ISSN: 0021-9673
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. ; Stafa-Zurich, Switzerland
    Materials science forum Vol. 251-254 (Oct. 1997), p. 73-80 
    ISSN: 1662-9752
    Source: Scientific.Net: Materials Science & Technology / Trans Tech Publications Archiv 1984-2008
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1573-4803
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A kinetic and fluodynamic description of processes that may take place near the liquid-vapour interface in the presence of an inert carrier flow containing definite oxygen amounts is presented, in relation to surface tension measurements. The evaluation of the Thiele modulus, φ, and of the parameter ε0 (which compares the magnitude of the fluxes of interest to and from the surface), allows definition of the regimes in which fast or slow reactions in the gas phase surrounding a drop of liquid metal are possible in the presence of variable oxygen concentrations. The kinetic features of the process are described in terms of these different reaction regimes, and on the basis of the thermodynamic stability of the possible oxidation products. Diagrams on a plane log φ2/log ε0 are drawn, immediately allowing one to know the range of $$P_{O_2 }^0 $$ and T in which the reaction considered is thermodynamically possible, and to foresee the evolution in this field from a kinetic point of view, as a function of $$P_{O_2 }^0 $$ and T. Therefore, the treatment presented here (and applied to selected cases of technological interest) allows a “stability field” for a chosen oxide on the log φ2/log ε0 plane to be defined, and the behaviour of the system from a kinetic-fluodynamic point of view to be predicted when the flow parameters and the geometry of the experimental set-up are known. In particular, the reactive gas fluxes at the liquid-vapour interface can be evaluated as a function of the different experimental conditions. Kinetic-fluodynamic diagrams for liquid metal-oxygen systems containing Pb, Sn, Zn, Cu and Al are presented, as well as an application of the model to surface tension measurements on liquid tin, which gives semi-quantitative confirmation of the theory developed here.
    Type of Medium: Electronic Resource
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  • 4
    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.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 49 (1998), S. 71-89 
    ISSN: 1573-4889
    Keywords: COBALT ; CERIUM ; 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 sulfidation behavior of a Co-Ce alloycontaining approximately 15 wt.% Ce has been studied at600-800°C in H2-H2S mixturesproviding a sulfur pressure of 10-8 atm, butalso of 10-7 atm at 800°C. At 600 and 700°C the alloy corrodes moreslowly than pure cobalt, but more rapidly than purecerium. At 800°C under 10-8 atmS2, which is below the stability of thecobalt sulfides, the alloy corrodes quite slowly, but under 10-7 atmS2 it corrodes very rapidly and practicallyat the same rate as pure cobalt. The sulfidationkinetics are generally irregular, except for a few casesof nearly parabolic behavior. The sulfidation of the alloy produces duplexscales, containing an outermost layer of practicallypure cobalt sulfide and an inner complex layer where thetwo components are simultaneously present. Cerium is not able to diffuse out of thealloy-consumption region, where it forms a ceriumsulfide mixed with cobalt sulfide and an innermostregion where cerium sulfide is mixed with cobalt metal.The cobalt sulfide forms a continuous network which allowsthe growth of the external CoSy layer, eventhough at rates reduced with respect to pure cobalt.Thus, a cerium content of 15 wt.% is not sufficient toprevent the sulfidation of the base metal. Theseresults as well as the details of the microstructure ofthe scales grown on the alloy are interpreted by takinginto account the limited solubility of cerium in the base metal and the presence in the alloy ofan intermetallic compound rich in cerium.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 49 (1998), S. 237-260 
    ISSN: 1573-4889
    Keywords: BINARY ALLOYS ; INTERNAL OXIDATION ; SUPERSATURATION
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract According to the theory of Bohm and Kahlweit ofthe internal oxidation of binary A-B alloys, theparabolic rate constant for the formation of reasonablystable internal BOν oxides as well as theconcentrations of O and B at the oxidation front arecontrolled only by the degree of supersaturationnecessary for the nucleation of new oxide particles. Theeffects of this factor on the previous parameters arecalculated for various values of the solubility product ofthe oxide and of the diffusion coefficients of O and B.Moreover, an alternative procedure for the calculationof the critical degree of supersaturation behind the precipitation front required for oxideprecipitation, which is a function of the concentrationof the reactants at the internal oxidation front, isproposed. A simple modification of Wagner's theory of internal oxidation is also presented, andits results are compared with those of the treatment byBohm and Kahlweit. Finally, the limitations of the twomethods are examined.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 49 (1998), S. 583-610 
    ISSN: 1573-4889
    Keywords: OXIDATION ; DIRECTIONALLY SOLIDIFIED ALLOYS ; MULTIPHASE ALLOYS ; THIRD-ELEMENT EFFECT
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation behavior of a directionallysolidified Ni-Al-Cr3C2 alloy ofover all composition Ni-12.3Cr-6.9Al-1.8C (wt.%) hasbeen investigated at 1100 and 1200°C under 1 atmoxygen. Experiments have also been carried out on specimens having the samecomposition but with a nonaligned structure. At1100°C, in both cases and unlike conventionalnickel-base superalloys with the same chromium andaluminum contents, aluminium was found to oxidize internallybeneath an external Cr2O3 scale.Although the volume fraction of the internalprecipitates was significant, they showed no tendency tocoalesce into a compact subsurface layer, but formed randomly distributed clustersin the alloy matrix. The kinetics of oxidation andmorphologies of the oxide scales were not substantiallyaffected either by thermal cycling or by the alloy microstructure. At the higher temperature,continuous Al2O3 scales formedbeneath thick layers of transient nickel andnickel-chromium-rich oxides; no internal precipitationof aluminum-rich oxides was observed. However, internal degradation of thedirectionally solidified specimens at 1200°C wasquite significant, due to in situ oxidation of primarycarbides. The multilayered scales formed at 1200°C spalled extensively on cooling as a consequenceof loss of contact, starting preferentially at theintersections of the Cr2C3 fiberswith the alloy-scale interface. The observed behaviorcan be attributed to a reduction in the availability of chromiumbecause of the multiphase structure of the alloy; this,in turn, resulted in an increase in the flux of oxygeninward, leading to internal oxidation of aluminum at 1100°C. The almost exclusive externaloxidation of aluminum becomes possible at 1200°C,probably because of an increase in the diffusivity ofaluminum in the alloy matrix.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 52 (1999), S. 403-426 
    ISSN: 1573-4889
    Keywords: SULFIDATION ; IRON-COPPER ; 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 sulfidation behavior of three two-phaseFe-Cu alloys containing 25, 50, and 75 wt.% copper hasbeen investigated in H2-H2Smixtures at 500-700°C under gas-phase sulfur pressures, which is significantly abovethose for the dissociation of both FeS andCu2S. In all cases, the three alloyssulfidized more slowly than both pure metals under thesame conditions. At all temperatures, Fe-25Cu showed the slowestgrowth rates, whereas Fe-50Cu sulfidized more rapidlythan the other two alloys. However, the kinetics curvesfor the three alloys tended to overlap, particularly at the higher temperatures. The scales werecomplex and contained an outer layer composed of amixture of two different Cu-Fe double sulfides,Cu5FeS4 and CuFeS2,plus an inner zone containing a mixture of metalliciron with the double sulfideCu5FeS4formed by completesulfidation of the copper-rich phase and partialsulfidation of the iron-rich phase. This region also contained large voids,possibly because of outward diffusion of metal cations,whereas the iron-rich islands were mainly unattacked.The depth of internal attack increased with increasing temperature and/or iron content. Finally,particles of almost pure copper metal, probably formedduring cooling from the reaction temperature, werepresent at the scale-subscale interface, as inclusions in the scale and as whiskers protruding out ofthe external scale surface.
    Type of Medium: Electronic Resource
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  • 9
    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.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    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.
    Type of Medium: Electronic Resource
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