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  • Artikel  (115)
  • kinetics  (115)
  • Nitrogen fixation
  • Springer  (115)
  • Maschinenbau  (115)
  • 1
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 261 (1983), S. 188-189 
    ISSN: 1435-1536
    Schlagwort(e): Polymerization ; kinetics ; redox polymerization ; acrylamide
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 266 (1988), S. 958-964 
    ISSN: 1435-1536
    Schlagwort(e): a-Se colloids ; photoadsorption ; kinetics ; activation energy ; compensation effect
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract In this study, a model is developed to explain in microscopic terms the results obtained from thermally activated photoadsorption experiments in a-Se colloids. The observed compensation effect can be described for two different cases. At low efficiency adsorption, the process is controlled by the potential at the boundary layer. In the high efficiency adsorption case, the process is controlled by diffusion transport.
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  • 3
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 262 (1984), S. 366-373 
    ISSN: 1435-1536
    Schlagwort(e): kinetics ; isothermal crystallization ; polymer ; spherulite ; differential scanning calorimetry
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract In the DSC technique, isothermal crystallization experiments are usually performed on thin flat specimens, but their interpretation generally uses theories developed for an unbounded volume. In this paper, isothermal crystallization of spherical entities in the volume limited by two parallel infinite planes is considered. Our model, derived from Avrami's theory, gives an analytical expression for the transformed volume fraction as a function of time. It is shown that the influence of thickness becomes important when thickness becomes of the order of or smaller than the average spherulite radius. The main effects of a decreasing thickness are a slower crystallization kinetics and a decrease in the Avrami exponent. These results can be used to interpret experimental data obtained in isothermal polymer crystallization.
    Materialart: Digitale Medien
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  • 4
    ISSN: 1435-1536
    Schlagwort(e): Phospholipid bilayer ; kinetics ; laser temperature jump ; phase transition
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract The iodine-laser temperature-jump technique has been used to investigate the main phase transition in single shell vesicles of dimyristoylphosphatidylcholine. The probe molecules DPH and TMA-DPH were incorporated into the lipid bilayer and laserT-jump experiments with turbidity and flourescence polarization detection were performed. We found three well separated relaxation processes between 5 μs and 10 ms. The relaxation signals showed strong cooperativity in the relaxation times as well as in their corresponding amplituedes. We attributed the relaxation to the formation and dissolution of clusters of different order inside the bilayer.
    Materialart: Digitale Medien
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  • 5
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 265 (1987), S. 58-64 
    ISSN: 1435-1536
    Schlagwort(e): Polymerisation ; emulsion ; styrene ; methylmethacrylate ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract The dependence of emulsion polymerisation rates on a number of important parameters is considered. Attention is paid to the use of seeded emulsion systems for the evaluation of radical desorption coefficients (k o). Experimental conditions are shown to be important. When the average number of radicals per particle is low, large changes in the rate coefficient for chain termination do not have a large effect on the kinetics. With styrene and methylmethacrylate, radical re-absorption by the polymer particles is shown to be important and radical capture efficiences can be high. Consistency is established between the results of a number of workers and values fork o are shown to be lower than those calculated from chain transfer rates.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 261 (1983), S. 621-625 
    ISSN: 1435-1536
    Schlagwort(e): Polyamide 6 ; crystallisation ; kinetics ; titania
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract The kinetics of isothermal and nonisothermal crystallization of polyamide-6 (PA6) containing titania was studied by means of DSC. It was found thatTiO 2 causes an acceleration in the crystallization of polyamide-6 and lowers the value of the Avrami exponent,n. The presence of TiO2 does not affect equilibrium melting pointT m 0 , glass temperatureT g, or surface free energiesσ e andσ of the basal and lateral surfaces.
    Materialart: Digitale Medien
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  • 7
    ISSN: 1572-8900
    Schlagwort(e): Cellulose ; alkaline degradation ; peeling off ; degree of polymerization ; kinetics ; (gluco)isosaccharinic acid
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Energietechnik , Maschinenbau
    Notizen: Abstract The degradation of cellulosic materials, differing mainly in the degree of polymerization and the number of reducing end groups, was studied under the alkaline conditions similar to those existing in a cementitious repository for low- and intermediate-level radioactive waste (pH 13.3, T = 25°C). The kinetics of alkaline degradation (peeling-off reaction) were studied and the data analyzed by the model of Haas et al. [13]. The observed kinetic parameters for the propagation reaction and overall stopping reaction were compared with literature data. Although measured under different experimental conditions, literature data and data from this study show a consistent picture. Differences in the extent of degradation observed for the different cellulosic materials could be satisfactorily explained by differences in reducing end group content and, consequently, by differences in the degrees of polymerization. Besides the number of reducing end groups, the degree of amorphousness also plays an important role. The main degradation products formed under the experimental conditions used are α- and β-(gluco)isosaccharinic acid. This is in agreement with many other studies on alkaline degradation of cellulose. The two isomers are formed in roughly equal amounts.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    Springer
    Plasma chemistry and plasma processing 1 (1981), S. 19-35 
    ISSN: 1572-8986
    Schlagwort(e): Decomposition of NH3 ; kinetics ; optical spectroscopy ; gas chromatography
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Technik allgemein
    Notizen: Abstract The plasma decomposition of NH3 has been studied as a function of the residence time, power input, and pressure. The process follows apparently zero-order kinetics, which can be interpreted on the basis of a kinetic mechanism involving as initial step the rupture of an N-H bond from vibro-rotationally excited modecules. Simultaneous spectroscopic observations of the emission light due to electronically excited NH2, NH, H, and N2 have been used to confirm the suggested mechanism and to show that NH2 and NH are successive intermediate species and that the final step of the decomposition process is the bimolecular recombination NH+NH→N2+H2.
    Materialart: Digitale Medien
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  • 9
    Digitale Medien
    Digitale Medien
    Springer
    Plasma chemistry and plasma processing 1 (1981), S. 233-245 
    ISSN: 1572-8986
    Schlagwort(e): Plasma ; kinetics ; polymerization ; propylene
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Technik allgemein
    Notizen: Abstract Flowing microwave plasma of propylene and propylene with argon was studied by mass spectrometry. Plasma composition was investigated as a function of external parameters such as pressure, argon/propylene ratio, and microwave-induced power. It was found that the propylene broke down to C2H2 and CH4, or reacted further with propylene. Two main products, leading to the determination of three main chain reactions for the polymerization of propylene by ion-molecule interactions, were observed, namely, C2H2 and CH4. These were the propylene, acetylene, and ethylene chain reactions. It was also found that the propylene disappeared in a pseudo-first-order reaction. Consequently an overall rate constant for the polymerization was determined (50 sec−1 at 1 torr pressure for propylene plasma). This constant is found to be linearly dependent upon the propylene percent concentration, and nonlinearly dependent upon plasma pressure.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    Springer
    Plasma chemistry and plasma processing 5 (1985), S. 293-316 
    ISSN: 1572-8986
    Schlagwort(e): Plasma chemistry ; halocarbon decomposition ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Technik allgemein
    Notizen: Abstract For the case of weak feed gas decomposition, where the concentration of CCl4 exceeds those of decomposition and built-up products, the emission of CCl* is shown to originate from dissociative excitation of CCl4. With electron concentration measured independently, the kinetics of CCl4 decomposition has been extracted from the time dependence of the CCl* intensity. Supported by EPR determinations of radical concentrations in rapidly flowing CCl4 and CCl4/O2 afterglows, the primary decomposition reaction is shown to be the electron impact dissociation into CCl3 and Cl. Its rate constant (k 1=4×10−8 cm3s−1) indicates strongly that dissociative electron attachment is the main reaction channel at least at r.f. power densities just above the threshold of a self-maintaining discharge. At extremely low mean electron energies the emission of a continuum is observed, which is tentatively ascribed to the radiative CCl3-Cl recombination.
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  • 11
    Digitale Medien
    Digitale Medien
    Springer
    Plasma chemistry and plasma processing 6 (1986), S. 429-436 
    ISSN: 1572-8986
    Schlagwort(e): Plasma ; laser ; diagnostics ; free radicals ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Technik allgemein
    Notizen: Abstract The plasma of a pulse discharge (0.05 J/cm3) in methane at low pressure (200 Pa) is studied. The dynamics of formation and decay of C2(a3IIu, v″=0) is monitored using a stroboscopic laser absorption method. It was found that substantial amounts of C2, 1015 cm−3, arise with a 1-µs delay after the current pulse.
    Materialart: Digitale Medien
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  • 12
    Digitale Medien
    Digitale Medien
    Springer
    Plasma chemistry and plasma processing 8 (1988), S. 101-110 
    ISSN: 1572-8986
    Schlagwort(e): Plasma ; laser ; diagnostics ; hydrocarbons ; free radicals ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Technik allgemein
    Notizen: Abstract The dynamics of the formation and decay of excited hydrogen during a pulse discharge in methane at a pressure of 200 Pa and energy density of 0.05 J/cm3 has been studied. The population of hydrogen in the n=2 state was monitored by the laser absorption method. The time constant of the decay of the excited hydrogen was measured to be 95±15 ns. The concentration of free electrons reached a maximum value of 7×1014 cm−3, and the time constant of their recombination was 220±50 ns. The formation of appreciable amounts of atomic hydrogen in the ground state during the discharge, H(n=1)〉1016 cm−3, was estimated on the basis of a kinetic model.
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  • 13
    ISSN: 1572-8986
    Schlagwort(e): RF SiCl4 discharge ; mass spectrometry ; kinetics ; decomposition ; oxidation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Technik allgemein
    Notizen: Abstract Time-resolved mass spectrometry was used for analysis of the plasma reactions in radio frequency (RF) SiCl 4 and SiCl 4 −O 2 discharges as functions of starting partial pressure and electrical power. Molecular concentrations of the reactants and products from SiCl 4 alone and with O 2 were obtained from the mass spectra and used for plotting the kinetic curves. The SiCl 4 and O 2 consumption rates were calculated from the kinetic curves and compared with results of theoretical simulation of the reaction. Direct electron impact decomposition was found to be the main pathway for pure SiCl 4 conversion. On the contrary, the consumption of SiCl 4 in the SiCl 4 +O 2 mixtures was largely chemical. The experimental macrokinetics are in agreement with a model in which oxidation is caused by the atomic oxygen.
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  • 14
    ISSN: 1572-8986
    Schlagwort(e): Arc ; gliding arc ; gas temperature ; electron temperature ; ion composition ; ion bombardment ; liquid electrode ; dye oxidation ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Technik allgemein
    Notizen: Abstract The plasma–solution interaction processes for gliding and “point” arcs between the aqueous solution surface and the metal electrode in the gas phase are studied. The plasma, liquid, and surface zones are taken into consideration. The electric field strength is measured, and the gas and electron temperatures and ion composition are estimated for the plasma zone. The cathode fall, water vaporization rate, and active species current yield due to the radiation chemistry mechanism are determined for the surface zone. The efficiency of oxidation of iodine ions and organic dyes by different types of discharge in the liquid zone are investigated. The difference in action of the various discharge types may be connected with various influences of the plasma and surface zone on the oxidation processes.
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  • 15
    Digitale Medien
    Digitale Medien
    Springer
    Plasma chemistry and plasma processing 5 (1985), S. 283-291 
    ISSN: 1572-8986
    Schlagwort(e): Methane ; acetylene ; kinetics ; modeling
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Technik allgemein
    Notizen: Abstract It is shown that it is basically possible to model plasma-chemical methane conversion using a kinetic concept regardless of the kind of plasma, i.e., the kind of activation. While the temporal plasma-chemical decomposition of methane is controlled by a first-order rate equation, the temporal product formation can be described by a set of first-order consecutive reactions. Prolonged portions of constant product concentrations in the temporal product formation curves were explained by the assumption of an equilibrium between forward and reverse reactions. The modeling revealed the special role of the re-formation of dissociated molecules.
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  • 16
    Digitale Medien
    Digitale Medien
    Springer
    Journal of materials synthesis and processing 6 (1998), S. 305-309 
    ISSN: 1573-4870
    Schlagwort(e): Fractals ; solid state reaction ; kinetics ; nucleation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract In the present research we theoretically studied the kinetics of nucleation-limited solid state reactions as influenced by the fractal properties of solid reagent. We consider the model of equal-sized primary particles assembled in fractal cluster. The geometry of such an object is assumed to be described solely by its fractal dimension D and by upper (R max) and lower (R min) cutoffs of fractality further identified with the overall size of the object and the size of the primary particle correspondingly. Depending on the ratio between R max, R min and the radius of the critical nucleus R nucl the following cases are considered: (1) R max ∼ R nucl. In this case the reaction kinetics is described by the equation: α = 1 − B{ln(k′ τ + 1)}D/(D−3), where B, k′ are constants. Numerical solution of this equation gives rise to n-order reaction kinetics with n & 1. (2) R min ≪ R nucl ≪ R max. In this case under certain conditions there can exist non-trivial critical density ρcrit ≠ 0, 1 that favors the formation of the critical nuclei of the new phase. The asymptotic kinetic equation for large times corresponds to n-order reaction with n = (D + 3)/(D + 1). (3) R min ≪ R nucl ∼ R max′. In this case the reaction follows the first-order kinetics with D-dependent rate constant.
    Materialart: Digitale Medien
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  • 17
    Digitale Medien
    Digitale Medien
    Springer
    Journal of materials synthesis and processing 8 (2000), S. 139-144 
    ISSN: 1573-4870
    Schlagwort(e): TiO2 ; phase transformations ; mechanical alloying ; kinetics ; modeling
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract A high-pressure and high-temperature phase of TiO2 : TiO2 II is formed transiently during room-temperature high-energy ball milling of anatase TiO2 : TiO2 anatase → TiO2 II → TiO2 rutile. Rutile is the only phase present after prolonged ball milling. The present paper focuses on the influences of physical and chemical processing conditions on the transformation kinetics. The effects of two milling parameters on the kinetics of phase transformation of anatase TiO2 were investigated: the nature of milling tools and the powder-to-ball weight ratio R. Granulometric characterizations and TEM observations have demonstrated that the transformation of TiO2 anatase into TiO2 II occurs without fracturing of particles and that TiO2 II nanograins form at the surface of anatase particles. The parameter R affects only the transformation rate. For a given R, the transformation rate is the largest with alumina grinding tools, intermediate with zirconia tools, and the smallest with steel tools. The parameters involved in current models of the mechanical alloying process do not suffice to explain the differences in transformation rates observed here. A parameter, which takes into account the influence of the mechanical properties of grinding materials, is considered.
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  • 18
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 10 (1976), S. 291-309 
    ISSN: 1573-4889
    Schlagwort(e): tantalum alloy ; oxygen ; dissolution ; kinetics ; oxides
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Oxygen was added to T-111 (Ta-8W-2Hf, wt.%) at 820 and 990°C at an oxygen pressure of about 3×10−4 Torr (4×10−2N/m2). The technique employed permitted predetermined and reproducible doping of T-111 up to 3.0 at% oxygen. Based on the temperature dependence of the doping reaction, it is concluded that the initial rates of oxygen pickup are probably controlled by solution of oxygen into the T-111 lattice. Although hafnium oxides are more stable than those of tantalum or tungsten, analyses of extracted residues indicate that the latter oxides predominate in the as-doped specimens, presumably because of the higher concentrations of tantalum and tungsten in the alloy. However, high-temperature annealing promotes gettering of dissolved oxygen and of other oxides to form hafnium oxides. Small amounts of tantalum and tungsten oxides were still present after high-temperature annealing. Tungsten oxide (WO3) volatilizes slightly from the surface of T-111 at 990°C. The vaporization of WO3 has no apparent affect on the doping reaction.
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  • 19
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 11 (1977), S. 127-132 
    ISSN: 1573-4889
    Schlagwort(e): Duplex oxides ; copper oxidation ; kinetics ; oxygen partitioning
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The theory for the growth of a double oxide layer proposed by Yurek, Hirth, and Rapp, has been applied to copper using experimental rate-constant data obtained by Valensi. Calculated thicknesses of the layers agree very well with experimentally measured values.
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  • 20
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; Incoloy 909 ; superalloy ; scale ; high temperature ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation of an Fe-38Ni-13Co-4.7Nb-1.5Ti-0.4Si superalloy (Incoloy 909 type alloy), was investigated at temperatures between 1000 K and 1400 K in Ar-(1, 10%)H20 atmosphere using metallographic, electron probe microanalysis, and X-ray diffraction techniques. The oxide scales consist of an external scale and an internal scale which has an intergranular scale (above 1200 K) and an intergranular scale. The oxide phases in each scale are identified asα-Fe2,O3 (below 1200 K) or FeO (above 1300 K) and CoO · Fe2O3 and FeO · Nb2O5, respectively. The morphologies, the oxide phases and the oxidation rates do not depend on the partial pressure of H2O in the range between one and ten percent in Ar gas. The rate constants for the intergranular-scale formation in this alloy are about one-tenth as large as those in Fe-36%Ni alloy reported previously. At all the temperatures the scales grow according to a parabolic rate law and the apparent activation energies for the processes are estimated.
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  • 21
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; kinetics ; iron ; iron-nitride
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation of α-Fe and ɛ-Fe2N1−z at 573 K and 673 K in O2 at 1 atm was investigated by thermogravimetrical analysis, X-ray diffraction, light-optical microscopy, scanning electron microscopy and electron probe X-ray microanalysis. Upon oxidation at 573 K and 673 K, on α-Fe initially α-Fe2O3 develops, whereas on ɛ-Fe2N1−z initially Fe3O4 develops. In an early stage of oxidation the oxidation rate of ɛ-Fe2N1−z appears to be much larger than of α-Fe. This can be attributed largely to an effective surface area available for oxygen uptake, which is much larger for ɛ-Fe2N1−z than for α-Fe due to the porous structure of ɛ-Fe2N1−z as prepared by gaseous nitriding of iron. The development of a magnetite layer in-between the hematite layer and the α-Fe substrate, at a later stage of oxidation, enhances layer-growth kinetics. After 100 min oxidation at 673 K the (parabolic) oxidation rates for α-Fe and ɛ-Fe2N1−z become about equal, indicating that on both substrates the oxide growth is controlled by the same rate limiting step which is attributed to short-circuit diffusion of iron cations. Oxidizing ɛ-Fe2N1−z increases the nitrogen concentration in the remaining ɛ-iron nitride, because the outward flux of iron cations, necessary for oxide growth, leads to an accumulation of nitrogen atoms left behind.
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  • 22
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 48 (1997), S. 171-184 
    ISSN: 1573-4889
    Schlagwort(e): TiAl, corrosion ; high-temperature ; kinetics ; nitrogen dependence
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxide scale formation on γ-TiAl at 800 and 900°C was studied using high temperature X-ray diffraction as anin situ-method. The experiments were performed in air and in He with 20 vol.% O2. The formation of alumina in the form of α-Al2O3 and of TiO2 in the form of rutile was observed in both atmospheres and the formation of TiN was detected in air. Depending on the atmosphere the diffraction peaks of two different additional phases were detected, which do not exist in any data base nor in the Ti-Al-O phase diagram. One of them, the Z-phase, appears in He with 20 vol.% O2 and the other, the X-phase, in air. The Zphase was also found at room temperature after oxidation at 900°C in air. The growth of both phases, X and Z, starts immediately with the oxidation process and follows the parabolic rate law.
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  • 23
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 48 (1997), S. 289-302 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; titanium ; rutile ; scale ; high temperature ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation behavior of pure titanium has been investigated in the temperature range of 1000 K to 1300 K in CO2 or Ar-10%CO2. Optical microscopy, electron probe microanalyses, and X-ray measurements on the oxide scales formed during oxidation indicate that their structures are nearly independent of temperature and the corrosion atmosphere. The scales consisted of two layers, an external one and an internal one, having a rutile (TiO2) structure. The parabolic rate law was confirmed for growth of the external scale and the permeation depth of oxygen in titanium with apparent activation energies of 266 and 226 kJ/mol, respectively. The rate-determining diffusion species in the oxidation processes are discussed.
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  • 24
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 9 (1975), S. 459-472 
    ISSN: 1573-4889
    Schlagwort(e): Cr ; oxidation ; kinetics ; Cr2O3 grain size ; short-circuit diffusion ; surface ; preparation ; Fe-Cr
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Cr was oxidized in 1 aim O2 at 980, 1090, and 1200°C. ElectropolishedCr and some orientations of etched Cr oxidize rapidly and develop compressive stress in the growing Cr2O3; other orientations oxidize slowly, apparently free of stress. SEM examination of fracture sections shows that the thick oxide is polycrystalline whereas the thin oxide on etched Cr is monocrystalline. It is deduced that the monocrystalline oxide grows by lattice diffusion of cations outward, and the polycrystalline layer by the two-way transport of cation diffusion outward and anion diffusion inward along oxide grain boundaries. The consequent formation of oxide within the body of the polycrystalline layer generates compressive stress and leads to wrinkling by plastic deformation. The activation energy for oxidation of Cr by cation lattice transport is 58 kcal/mole. Polycrystalline Cr2O3 forms on Fe-26Cr alloy, whether electropolished or etched; oxidation is accordingly rapid and accompanied by compressive stress.
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  • 25
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 10 (1976), S. 85-95 
    ISSN: 1573-4889
    Schlagwort(e): boron carbide ; oxidation ; kinetics ; chromatography method
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Thermogravimetry and gas-adsorption chromatography were used to study the kinetics of formation of solid and gaseous products during the hightemperature oxidation of compact boron carbide in oxygen at 740 Torr. Oxidation resistance was observed at temperatures up to 1200°C. The main oxidation products were B2O3 and CO2. Oxidation was paralinear; the carbon consumption exceeded the consumption of boron as compared to the ratio of these elements in the compound B4C. This difference resulted in carbon depletion of the carbide layer in the substrate near the scale〉.
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  • 26
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 10 (1976), S. 361-376 
    ISSN: 1573-4889
    Schlagwort(e): metals ; scale structure ; epitaxy ; kinetics ; diffusion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract An explanation of the deviation from the parabolic law is the treatment which considers both shortcircuit and lattice diffusion in the oxide scale. In this study we examine how the oxidation kinetics are influenced by changing the structure of the scale of copper oxide in order to confirm the role of short-circuit diffusion in determining the oxidation rate. In addition we explain the oxidation kinetics of copper and nickel by using a model of the scale structure which includes recrystallization and grain growth. Results are as follows: (1) The nucleation and growth behavior of oxide have a direct effect on the structure and in turn the oxidation kinetics due to short-circuit diffusion. (2) A modified treatment is valid in the region where volume diffusion and short-circuit diffusion play an important role in which it is necessary to consider the scale structure such as the grain size distribution and the boundary width. (3) When recrystallization takes place it is necessary to consider the model of a two-layered scale structure which is different in properties and morphology. (4) In this region the rate curves are S-shaped when oxide recrystallization takes place and exhibit a transition from a parabolic to an nth-power relationship (n〉2) when grain growth takes place.
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  • 27
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 11 (1977), S. 225-239 
    ISSN: 1573-4889
    Schlagwort(e): tantalum ; oxidation ; high temperature ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation of tantalum in oxygen-nitrogen and oxygen-inert gas mixtures at925°C has been studied. The oxygen pressure was close to 0.5 atm in all experiments, and partial pressures of the second component of from 0 to 180 Torr were employed. Spherical specimens were used to provide quantitatively significant kinetic data. A model has been proposed which suggests that the oxygen pressure at the reaction interface close to the metal surface is lower than the external pressure because of the finite permeability of the porous outer oxide layer, and that the inert gas effectively reduces the permeability. The model gives good quantitative agreement with the experimental results.
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  • 28
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 11 (1977), S. 365-381 
    ISSN: 1573-4889
    Schlagwort(e): cobalt oxidation ; kinetics ; parabolic rate constant
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Precise values of parabolic rate constants of cobalt oxidation have been determined over a wide range of temperature (950–1300°C) and oxygen pressure (6.58× 10−4−0.658 atm). The dependence of the calculated values of parabolic rate constants k″p on oxygen pressure and temperature can be described by the following empirical equation: $$k''_p = const. \cdot {\text{p}}_{O_2 }^{{\text{1/n}}} \cdot exp ( - {\text{E}}_{\text{k}} /RT)$$ The exponent 1/n decreases with an increase in temperature from 1/3.40 at 950°C to 1/3.96 at 1300°C, whereas the activation energy Ek decreases with an increase in the oxygen pressure from 41.7 to 38.1 kcal/mole.
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  • 29
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 13 (1979), S. 77-88 
    ISSN: 1573-4889
    Schlagwort(e): BaTiO3 ; kinetics ; solid state
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The solid-state reaction between barium carbonate and rutile powders to form barium metatitanate BaTiO3 was studied by thermogravimetric analysis, X rays, and microscopy. Phase-stability domains were drawn in a temperature— $${\text{p}}_{CO_2 } $$ , diagram. The dependence of the reaction kinetics on $${\text{p}}_{CO_2 } $$ , $${\text{p}}_{O_2 } $$ or $${\text{p}}_{N_2 } $$ is discussed. In particular, the rate continuously decreases when $${\text{p}}_{CO_2 } $$ , or $${\text{p}}_{N_2 } $$ increases, but it reaches a maximum as a function of $${\text{p}}_{O_2 } $$ .
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  • 30
    ISSN: 1573-4889
    Schlagwort(e): Cu-Si alloys ; oxidation ; kinetics ; silica
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation of Cu-Si alloys (containing up to 4.75 wt. % Si) in $${\text{p}}_{O_2 } $$ =0.01 atm from 800 to 1000°C has been investigated using thermogravimetry and other techniques. A 0.04% Si alloy followed a parabolic oxidation law with a rate similar to that of pure Cu. As the Si concentration increased the rate decreased and became irregular owing to SiO2 particles or flakes at the alloy-scale interface. It is considered that sintering of SiO2 particles and rupture of the sinter because of contraction during sintering are responsible for the irregular kinetics. A SiO2 layer forms directly on the 4.75% Si alloy which oxidizes uniformly. The SiO2 was always amorphous. In pure CO2 a similar pattern of amorphous SiO2 particles, flakes, and layers occurs.
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  • 31
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 13 (1979), S. 283-298 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; surface alloys ; Fe-Cr alloys ; iron ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation behavior of several surface and bulk Fe-Cr alloys and iron at 300°C and 4×10−6 Torr oxygen was studied. The surface alloys were fabricated by implantation of 25 keV Cr ions into the outermost 300Å of polycrystalline iron samples. The oxide thickness as a function of oxygen exposure was obtained using proton-excited X-ray analysis, and composition profiles of oxide films were obtained using Auger electron spectroscopy and ion sputtering. The addition of Cr to Fe by surface and bulk alloying caused the oxidation rate to decrease and changed the oxidation kinetics from parabolic (for Fe) to logarithmic (for Cr concentrations ≥4.7at.%). Interpretation of the data in terms of simple oxidation theories indicates that the Cr additions may reduce the oxidation rate by altering the electronic properties of the metal-oxide interface.
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  • 32
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 13 (1979), S. 255-272 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; Fe-C ; graphite deposition ; nonadherent oxide ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation of Fe-C alloys containing 0.5 and 1.0% C was studied in 1 atm O2 at 700° C. The oxidation rate is considerably slower than for pure Fe. The oxide scale formed is detached, multilayered, and overoxidized, containing little or no FeO. A thin film of graphite was identified at the metal-oxide interface by electron diffraction. It is proposed that the slow oxidation and abnormal scale are caused by a residue of graphite left at the metal surface from the oxidation of Fe3C. This inhibition of the oxidation of Fe by carbon at 700°C is in contrast to the stimulation observed at 500°C.
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  • 33
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 13 (1979), S. 301-309 
    ISSN: 1573-4889
    Schlagwort(e): NiO ; Electrical conductivity ; gas-solid equilibria ; kinetics ; equivalent circuit
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract In a previous work it has been stated that the NiO electrical conductivity changes connected to the oxygen pressure changes may be considered as a transitory phenomenon. A mixed kinetics case controlled by the formation of surface cation vacancies and their diffusion in the bulk is proposed to explain the reaction process. By means of an equivalent electrical circuit in good agreement with the kinetics model it was possible to reproduce the experimental phenomenon.
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  • 34
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 13 (1979), S. 481-504 
    ISSN: 1573-4889
    Schlagwort(e): kinetics ; sulfidation ; Fe-Cr-Al alloys
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The influence of aluminium on the kinetics and mechanism of high-temperature sulfidation of Fe-Cr alloys containing 20 at.% chromium has been investigated. It has been found that the addition of aluminum greatly improves the scaling resistance of Fe-Cr alloys against attack by sulfur vapors at high temperatures.
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  • 35
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 17 (1982), S. 359-369 
    ISSN: 1573-4889
    Schlagwort(e): Oxidation ; microhardness ; oxide thickness ; kinetics ; oxygen partition
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Oxidation kinetics of Ti-1 wt. % Si and Ti-5 wt. % Si alloys in either pure oxygen or air under a pressure of 0.93 bar and in the temperature range of 1171–1473 K are reported. For the exposure period investigated (up to 12 h) both alloys oxidized slower than pure Ti. The amount of oxygen dissolved in the Ti-1 wt. % Si alloy has been calculated. X-ray diffraction analyses indicate that the oxide scale is mainly TiO 2 ,except for the Ti-5 wt. % Si alloy oxidized at 1473 K where some evidence of SiO 2 was obtained. Hardness profiles were taken across the Ti-1 wt. % Si alloy matrix.
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  • 36
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 20 (1983), S. 37-65 
    ISSN: 1573-4889
    Schlagwort(e): Alloy oxidation ; cobalt-chromium-tungsten ; scale formation ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Oxidation rates in air at 1000–1250°C are reported for a series of Co-Cr-W alloys with 34–40 wt. % Cr and up to 10 wt. % W. Alloys with larger W contents exhibited slower oxidation rates and their parabolic rate constants agreed well with those for binary and ternary, Cr2O3 protected, Ni-base and Co-base alloys in the Co-Cr and Ni-Cr-W systems. The resulting scales were characterized by optical and scanning electron metallography, and electron microprobe analysis. The favorable effect of W additions to a Cr2O3-forming Co-Cr base alloy was the opposite of that reported for Ni-Cr-W alloys. The resupply of Cr to a Cr-depleted matrix beneath a protective CrO3 scale is achieved by the dissolution (denuding) of Cr-rich second phases in the Co-Cr-W alloys. Thus, the internal oxidation of Cr beneath the Cr2O3 scale is avoided for high W alloys. No catastrophic failure by liquid phase formation was observed for high-W alloys oxidized 20 hr at 1250°C.
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  • 37
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 26 (1986), S. 139-155 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; Co-Cr-Ti alloys ; kinetics ; scale morphology
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Cobalt-based alloys containing 3,5,10,15, and 20% Cr with 1 and 3% Ti were oxidized at 1000°C in slowly flowing oxygen gas. In general, titanium additions decreased the oxidation rate with the most pronounced effect being observed at the 10% Cr level. Titanium accelerated the formation of Cr2O3 layers at the metal-oxide interface. Faceted CrxTiyOz spinel particles were found at the metal-oxide interface which varied in composition according to microprobe results. There was no evidence of spalling on the Co-Cr-Ti alloys studied in contrast to the severe spalling normally encountered in Ni-Cr-Ti alloys. Distinct morphological differences existed on the outer CoO layer of the 1% Ti alloys in comparison to the O and 3% Ti alloys.
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  • 38
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 26 (1986), S. 417-430 
    ISSN: 1573-4889
    Schlagwort(e): cyclic carburization-oxidation ; carbides ; austenite ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Several austenitic heat-resistant steels were exposed to alternating periods of carburization at 1273 K [a c= 1,po2〈10−28 atm] and oxidation at 973°K [a c≈ O,po2 = 0.2 atm]. In all cases the depth of internal carbide precipitation increased with cumulative carburization time. It was found that the carburization rates of high nickel content alloys were unaffected by intermittent oxidation cycles, whereas the low nickel, high iron content alloys experienced a reduction in carburization rate subsequent to oxidation treatment. The latter group of alloys formed external scales of chromium-rich M7C3 which were shown by sulfur tracing experiments to be gas permeable. It was concluded, therefore, that oxidation of these materials led to blockage of cracks and holes in the scales, thereby decreasing the surface carbon activity and hence the carburization rate. High nickel, low iron alloys formed external scales of chromium-rich M7C3 covered by Cr3C2. These scales were shown to have very low gas permeabilities. It was concluded that the carbon activity at the surface of these alloys was controlled by scale-alloy equilibration, and was therefore not affected by brief periods of oxidation. The pattern of carbide scale formation is qualitatively consistent with the thermodynamics of the Fe-Cr-C system.
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  • 39
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 37 (1992), S. 65-80 
    ISSN: 1573-4889
    Schlagwort(e): internal oxidation ; kinetics ; alloys ; silver ; oxide particles ; coalescence
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Gravimetric measurements at low temperatures (〈600°C) and for dilute Ag-Mg alloys have given further information about the mechanism of oxide formation. This investigation shows that the fixation rate of oxygen is very high, which assumes the existence of species in an oxidized form, including one or two magnesium atoms called “elementary species” and denoted as MgO* and Mg2O*. When there are no free magnesium atoms, there is a coalescence process with the fixation of oxygen atoms or MgO* and Mg2O*: this process leads to the formation of the first “clusters” including an oxygen excess. At low temperatures, the thermal fluctuations do not permit significant changes. There is no significant increase in cluster size, but a rearrangement of these clusters toward a compact structure with the release of excess oxygen. Their size is less than 1 nm.
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  • 40
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 38 (1992), S. 89-98 
    ISSN: 1573-4889
    Schlagwort(e): kinetics ; oxidation ; zirconium hydride
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: 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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  • 41
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 8 (1974), S. 379-391 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; sulfidation ; kinetics ; parabolic rate law
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The conditions necessary to determine the oxidation kinetics of metals and alloys are discussed quantitatively, and a new method of calculating the rational rate constants was suggested. It was shown that the size and the shape of a metal sample has an effect on the kinetics of oxidation. Further, it was established that the values of the parabolic rate constants of corrosion, calculated from the empirical Pilling and Bedworth equation, contain a serious systematic error, if changes in the metallic core surface area during the oxidation process are neglected.
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  • 42
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 9 (1975), S. 357-365 
    ISSN: 1573-4889
    Schlagwort(e): kinetics ; zirconia ; defect structure ; ionic conductivity ; yttria dopant
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract A Zr-0.5 Y alloy was found to oxidize about 6 times faster than pure zirconium over the temperature range of 400 to 565°C. The activation energies were nearly identical (∼32 kcal/mole). The activation energies correspond to grain boundary diffusion of oxygen through the scale. The higher oxidation rate of the alloy was attributed to a higher anion vacancy concentration and the assumption that diffusion sites in the lattice and boundaries were in local equilibrium. Measurements on yttria-doped zirconia showed that ionic conductivity was increased markedly by yttrium and extended over a wide range of oxygen pressure. The defect structure of the doped oxide was changed to one of oxygen vacancies, even at the high end of the oxygen pressure range, 10−8 to 0.2 atm, over which pure ziconia contains oxygen interstitials. The doped oxide was found to be extrinsic over the entire range of oxygen pressure and, although ionic conductivity predominated, electronic conductivity was still appreciable. The electronic conductivity, however, was still sufficiently high so that electron transport was not rate-controlling in the predominantly ionic-conducting scale.
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  • 43
    Digitale Medien
    Digitale Medien
    Springer
    Journal of materials synthesis and processing 6 (1998), S. 161-167 
    ISSN: 1573-4870
    Schlagwort(e): Alumina ; surface ; kinetics ; diffusion ; SALK
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The kinetics of shape evolution of a completely faceted crystal/internal void by surface diffusion was modeled. Arrays of micron-sized cavities were generated in sapphire substrates with known surface orientations using microlithography and ion beam etching and converted to internal intragranular pores of nonequilibrium shape by diffusion bonding of the etched substrate to an identical-orientation unetched sapphire substrate. Pore shape evolution rates during high-temperature anneals were monitored and found to be highly sensitive to the orientation of the substrate surface. The observed evolution rates were compared with the predictions of the kinetic model using diffusivity values for alumina that span the range from the highest to the lowest diffusion constants reported in the literature. The comparison suggests that surface-attachment-limited kinetics (SALK) play a major role in surface mass transport on stable low-index planes of alumina.
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  • 44
    Digitale Medien
    Digitale Medien
    Springer
    Journal of materials synthesis and processing 8 (2000), S. 271-277 
    ISSN: 1573-4870
    Schlagwort(e): Comminution ; kinetics ; mechanical alloying ; phase transformation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract It has been shown that structural evolution occurring in powder mixtures subjected to mechanical treatment by milling follow well-defined conversion trends as a function of milling time. Sigmoidal curves were observed in the case of the mechanical alloying of transition metal mixtures, whereas a simpler kinetic course with a progressively decreasing transformation rate was found to characterize the disordering process of intermetallic equilibrium compounds by mechanical milling. Under the stipulation that collisions are the dominant energy transfer events, a kinetic model is developed to relate the observed macrokinetic features to the discrete powder fractions, which transform at each impact. Because of its intrinsic qualities, the milling process was regarded as discrete processing. A statistical approach was followed to work out a set of differential equations, solutions of which provide a sound description of the transformation kinetics in terms of conventional rate expressions. The model allows one to reproduce the different kinetic behaviors by means of a single, unifying mathematical formalism. Furthermore, quantifying the structural evolution rate by suitable kinetic constants permits the exploration of the reactive behavior of a system treated under different milling regimes or to compare, on an absolute basis, different systems processed under similar conditions.
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  • 45
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 10 (1976), S. 97-103 
    ISSN: 1573-4889
    Schlagwort(e): silicon carbide ; oxidation ; molecular oxygen ; glow-discharge oxygen plasma ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation kinetics and structure of the oxide scales formed on high-density SiC were studied in molecular oxygen at 740 Torr and in a glow-discharge oxygen plasma at 0.1 Torr at temperatures of 1000, 1100, and 1200°C. The monatomic oxygen formed by the glow discharge markedly increased the reaction rate and the vaporization of some of the oxidation products. The marked differences in kinetics suggest that the rate-controlling step during oxidation in molecular oxygen is the dissociation of adsorbed diatomic oxygen to the monatomic species. Films formed in molecular oxygen were mostly amorphous SiO2 with small inclusions of SiC and graphite, whereas films formed in dissociated oxygen were primarily amorphous SiO2 containing SiO, S2O3, and the coesite form of SiO2.
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  • 46
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 12 (1978), S. 215-225 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; Fe-Ni alloys ; kinetics ; scale morphology ; EPMA
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation of an Fe—19.34 wt. % Ni alloy in dry CO2 has been studied at 700—1000°C using thermogravimetry, metallography, and EPMA. Weight gains for oxygen consumption followed a linear-parabolic-linear sequence at all temperatures. During the initial linear stage the scale consisted mainly of magnetite and the activation energy of 133±25 kJ · mole−1 is considered to be due to dissociation of CO2 into CO and adsorbed oxygen on the outer magnetite surface. During the parabolic oxidation stage a continuous Ni-rich layer containing ∼ 70% Ni forms a barrier to the diffusion which has an activation energy of 192±79 kJ · mole−1. The breakdown of the barrier layer causes a return to linear kinetics with an activation energy of 138±42 kJ · mole−1 for dissociation of CO2 on the outer surface. During the final linear stage there is pronounced general and intergranular subscale formation. Detailed information is presented of the Ni redistribution and concentrations during oxidation and its correlation with the kinetics and morphology.
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  • 47
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 14 (1980), S. 85-108 
    ISSN: 1573-4889
    Schlagwort(e): alloy oxidation ; nickel-chromium-tungsten ; scale formation ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation behavior in air at 1000–1250°C of four Ni-Cr-W alloys containing sufficient chromium content (∼22 at. % Cr) for protective Cr2O3 formation in a binary Ni-Cr alloy is reported. Generally for alloys high in W (10 and 16 at.% W), the rejection of tungsten into the alloy beneath the scale introduced a steep Cr concentration gradient and slower Cr diffusion such that continuous precipitation of Cr2O3 internal oxides prevented the formation of a Cr2O3 protective scale. The alloy most dilute in W (1.6 at. % W) formed a protective scale at short times with little outer NiO scale, but scale fractures led to internal oxidation and rapid nonprotective kinetics. After an initially rapid oxidation increment to form NiO, the 3 at.% Walloy formed a protective Cr2O3 scale with about the same steady-state parabolic kinetics as a binary Ni-30Cr alloy. The effect of ternary Wadditions on the development of Cr2O3 scales on Ni-Cr-W alloys is considered as a ternary analog to Wagner's description of the oxidation of Cu-Pt or Cu-Pd alloys.
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  • 48
    ISSN: 1573-4889
    Schlagwort(e): titanium ; oxidation ; oxide scale ; solid state diffusion ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation behavior of titanium was studied over the temperature range of 600 to 800°C in a pure oxygen atmosphere. A parabolic kinetics period is made up of a succession of short parts whose weight gain is nearly constant and whose beginning is characterized by an alteration of the oxidation rate. The kinetics curve is closely correlated with the morphology of the oxide scale which contains several layers separated by short cracks. These cracks decrease the diffusional flows of oxygen and titanium and alter the oxidation rate. A parabolic-linear kinetics transition is attributed to the formation of a continuous crack between the oxide scale and the matrix. The oxide scale then forms a porous barrier of constant thickness which induces a linear rate law due to the steady-state oxygen diffusion. Titanium cannot diffuse across the continuous crack. During the linear kinetics period several layers of constant thickness, separated by a continuous crack, spread out.
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  • 49
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 15 (1981), S. 437-445 
    ISSN: 1573-4889
    Schlagwort(e): chromium nitriding ; kinetics ; parabolic rate constant ; diffusivity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Parabolic rate constants of the reaction of chromium with nitrogen gas under oxygen-free conditions have been determined over a range of temperature (1000–1250°C) and nitrogen pressure (0.265–101.33 kPa). The growth rate of the subnitride was measured by a thermogravimetric technique using a single specimen. Wagner's oxidation theory is used to calculate the self-diffusivity and intrinsic diffusivity of nitrogen in the subnitride from a theoretical analysis of the parabolic rate constant. The calculated diffusivities varied with the composition of the subnitride, having minimum values at intermediate compositions of the nonstoichiometric chromium nitride “Cr2N.”
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  • 50
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 16 (1981), S. 175-191 
    ISSN: 1573-4889
    Schlagwort(e): Sulfidation ; Fe-Cr alloy ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The scaling of an Fe-20Cr alloy has been studied in H2-H2O-H2S mixtures between 973 and 1223 K. According to a simplified phase diagram, Cr2O3 and FeS should be the thermodynamically stable compounds in the gas mixtures chosen. The reaction followed a mixed rate law between linear and parabolic, indicating that the reaction rate at the scale-gas interface was comparable with the diffusion rate in the scale. At a constant H2/H2S ratio the scaling rate initially decreased slightly with increasing water-vapor pressure. A further increase of the water-vapor pressure resulted in localized sulfide formation, while the other parts of the surface were covered with a Cr2O3 film. Only Cr2O3 formed above a critical water-vapor content. Three zones could be distinguished when a sulfide scale is formed. The outer zone consisted of practically pure FeS; the intermediate zone was a solid solution of (Fe,Cr)S, partially decomposed to FeCr2S4 and metal during cooling; and the inner zone contained small Cr2O3 inclusions in an (Fe,Cr)S matrix.
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  • 51
    Digitale Medien
    Digitale Medien
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    Oxidation of metals 21 (1984), S. 21-37 
    ISSN: 1573-4889
    Schlagwort(e): internal oxidation ; kinetics ; alloy ; silver ; precipitation ; coalescence ; ageing
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The internal oxidation mechanism in silver alloys was studied by residual resistivity, gravimetric, and calorimetric measurements, and by transmission electron microscopy. If the flux, of oxygen atoms is very large with respect to the oxide formation, the mechanism of internal oxidation includes two stages. The first one is the fixation of oxygen in the form of oxidized elementary species, including only one solute atom. These species are stable and keep a certain mobility. The second one is the coalescence process of these elementary species with the formation of the first clusters. When the flux of oxygen atoms is slowed down, the oxide formation mechanisms are more complicated. The initially formed species can include more than one solute atom because of their diffusion. The two stages are not separate.
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  • 52
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 21 (1984), S. 103-118 
    ISSN: 1573-4889
    Schlagwort(e): duplex steels ; sulfidation ; kinetics ; transport processes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Two austeno-ferritic stainless steels were sulfidized at temperatures of 783, 873, and 963 K under sulfur pressures in the range 4×10−12 to 3×10−5 atm. In all cases a triplex scale developed, consisting of an outermost layer of (Fe, Cr)1−xS, an intermediate layer of FeCr2S4, and an innermost layer of porous (Cr, Fe)1−xS containing particles of Mo2S3. Parabolic kinetics were observed except at the lowest temperature where one of the steels reacted according to irregular kinetics. The Mo2S3 particles in the innermost layer acted as inert markers, imaging the former positions of the steels' ferrite phase in which Mo is enriched. The lamellar microstructure of the steel was thus reproduced in the innermost sulfide layer. The positions of the Mo2S3 particles together with the porosity of the inner layer are taken to imply inward sulfur transport through this layer and outward metal transport through all three layers.
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  • 53
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 25 (1986), S. 1-28 
    ISSN: 1573-4889
    Schlagwort(e): sulfidation ; yttrium ; duplex-sulfide scales ; lamellar sulfides ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The sulfidation of Ni-10Cr-5Al, Ni-20Cr-5Al, and Ni-50Cr-5Al, and of the same alloys containing 1% Y, was studied in 0.1 atm sulfur vapor at 700°C. The sulfidation process followed linear kinetics for all the alloys except Ni-50Cr-5Al-1Y, and possibly Ni-50Cr-5Al, which followed the parabolic law. The reaction rates decreased with increasing chromium content in alloys without yttrium, and the addition of yttrium reduced the rates by at least a factor of two for the alloys containing 10 and 20% Cr and by an order of magnitude for Ni-50Cr-5Al. Alloys containing 10 and 20% Cr (with and without yttrium) formed duplex scales consisting of an outer layer of NiS1.03 and an inner lamellar layer of a very fine mixture of Cr2S3 and A12O3 in a matrix of NiS1.03. The two alloys containing 50% Cr formed only a compact layer of Cr2S3, which was brittle and spalled during cooling. The lamellae in the duplex scales were parallel to the specimen surface and bent around corners. The lamellae were thicker than those on Ni-Al binary alloys. The lamellae were also thicker in scales on the 20% Cr alloy than on the 10% Cr alloy. The presence of yttrium refined the lamellae and increased the lamellae density near the scale/metal interface in the 10% alloy, but in the 20% Cr alloy the lammellae were thicker and more closely spaced. Platinum markers were found in the inner portion of the exterior NiS1.03 layer close to the lamellar zone. A counter-current diffusion mechanism is proposed involving outward cation diffusion and inward sulfur diffusion, although diffusion was not rate controlling for alloys containing 10 and 20% Cr. Auger analysis of scales formed on Ni-50Cr-1Y showed an even distribution of yttrium throughout the layer of Cr2S3, suggesting that some yttrium dissolved in the sulfide. The reduced sulfidation rate of samples containing yttrium is explained by the possible dissolution of yttrium as a donor. The presence of Y4+ would then decrease the concentration of interstitial chromium ions in the N-type layer of Cr2S3, which would decrease the reaction rate.
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  • 54
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 23 (1985), S. 207-235 
    ISSN: 1573-4889
    Schlagwort(e): stainless steel ; duplex oxide ; kinetics ; growth rates
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The nature of the first-formed oxide on 20% Cr/25% Ni/Nb stabilized steel during exposure to CO2 at high and low temperatures has been determined by surface analytical techniques. These results together with a consideration of gas/solid interactions show that the oxide produced may be determined by kinetics or thermodynamic factors, and a diagram is presented to show that rhombohedral Cr2O3 or spinel may be the oxide first formed. Under most standard conditions, a mixed spinel oxide is formed initially, and the subsequent growth of a duplex oxide is analyzed in terms of a solid-state reaction in which the spinel oxide is reduced to Cr2O3 at the metal/oxide interface. Diffusion control of growth by either spinel or Cr2O3 is incorporated in new equations describing the kinetics of oxidation, and weight-gain predictions are tested against experimental observations.
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  • 55
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 32 (1989), S. 225-240 
    ISSN: 1573-4889
    Schlagwort(e): Hot corrosion ; nickel ; TGA ; kinetics ; mechanism
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The accelerated oxidation of pure nickel in the presence of a molten carbonate mixture has been studied in O2 and CO2-containing atmospheres. The oxidation rate of nickel with carbonate coatings was at least four orders of magnitude faster than that without salt coatings. The extent of oxidation, in terms of unit area weight gain, depended on both the amount of carbonate mixture coatings and the gas atmosphere. The unit area weight gain due to oxidation increased with increasing amounts of salt coatings up to a certain value. These observations suggest that the termination of nickel oxidation results from the exhaustion of either the salt coatings or metallic nickel. Porous and particulate oxide products were observed from scanning electron microscopic (SEM) examinations. The energy-dispersive analysis of x-rays (EDAX) shows that no salt remains on the specimen surface after the oxidation experiment.
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  • 56
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 33 (1990), S. 279-299 
    ISSN: 1573-4889
    Schlagwort(e): corrosion SO2 ; chromium ; manganese ; kinetics ; scale analysis ; phase diagram stability
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The corrosion of chromium and manganese by pure SO2 has been investigated in the temperature range 890–1350 K at SO2 pressure from 0.01–0.5 atm. Both metals oxidize according to a parabolic rate law, and the scales consist of an inner region containing a mixture of oxide and sulfide (Cr2O3+ CrS or MnO and MnS) and an outer region of oxide (Cr2O3 or MnO). These two metals have similar thermodynamic behavior, and the main mechanism of reaction is considered to be the direct reaction of the metal with SO2. The results also indicate that in the absence of trace amounts of oxygen, and at sufficiently low temperature (〈950 K), the formation of Mn3O4 does not occur only if a complete description of the atmosphere generated by a SO2-O2-S2 mixture was considered.
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  • 57
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 34 (1990), S. 101-121 
    ISSN: 1573-4889
    Schlagwort(e): nonisothermal oxidation ; kinetics ; iron ; iron-chromium alloys ; reactive-oxide coating
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The nonisothermal oxidation behavior of pure iron and a few iron-chromium alloys in dry air has been studied. The effects of a superficial coating of a reactive oxide, CeO2, on the oxidation behavior were studied. Linear heating rates of 3 K/min and 6 K/min were maintained up to a final temperature ranging from 1273–1473 K. Coatings were applied either from a slurry or an aqueous bath. The CeO2 coating has been found to be effective not only in decreasing the nonisothermal oxidation rate but also in improving the scale adherence. Moreover, the coated samples withstood a number of heating cycles without scale rupture. The mass gain of the samples as a function of temperature was recorded by means of a sensitive balance, and the scales have been characterized by SEM, EPMA, and x-ray diffraction analysis.
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  • 58
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 34 (1990), S. 473-496 
    ISSN: 1573-4889
    Schlagwort(e): Internal nitriding ; 310 stainless steel ; austenitic ; kinetics ; microhardness
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The internal-nitriding behavior in ammonia-hydrogen atmospheres of type-310 stainless steel and 310 to which either 2 wt.% Ti or 3 wt.% Al were added was studied over the range of 550–950°C. An Fe-24Cr binary alloy was included to assess the role of a BCC crystal structure vs the FCC crystal structure of 310 stainless steel. The BCC alloy exhibited the most rapid kinetics as expected. X-ray diffraction showed only the presence of CrN in all the alloys up to 735°C. At 850°C and above, both CrN and Cr2N were detected. The nonformation of TiN and AlN at lower temperatures is attributed to nucleation problems. Precipitates were extremely fine (unresolvable even at 20,000×) at 563°C and became much coarser with increasing temperature. The precipitate density, size, and shape varied across the internal-nitriding zone at the higher temperatures. External scaling was noted at 850°C and above, however, it was not a continuous film. The activation energy of internal nitriding from 563–735°C ranged from 3.8 kcal/mol for 310+2Ti to 18.2 kcal/mol for 310+3Al; from 850–950°C, the activation energy ranged from 44 (310+2Ti) to 56.6 kcal/mol (310+3Al). Microhardness profiles show that an intermediate zone exists between the nitride case and the base metal. The origin of this zone is discussed.
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  • 59
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 36 (1991), S. 439-464 
    ISSN: 1573-4889
    Schlagwort(e): V-A1 alloy ; Cr and Ti additions ; oxidation ; kinetics ; V2O5 ; Al2O3
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation behavior in air of pure vanadium, V-30Al, V-30Al-10Cr, and V-30Al-10Ti (weight percent) was investigated over the temperature range of 700–1000° C. The oxidation of pure vanadium was characterized by linear kinetics due to the formation of liquid V2O5 which dripped from the sample. The oxidation behavior of the alloys was characterized by linear and parabolic kinetics which combined to give an overall time dependence of 0.6–0.8. An empirical relationship of the form: ΔW/A=Bt + Ct1/2 + D was found to fit the data well, with the linear contribution suspected to be from V2O5 formation for V-30Al and V-30Al-10Cr, and a semi-liquid mixture of V2O5 and Al2O3 for V-30Al-10Ti. The parabolic term is presumed related to the formation of a solid mixture of V2O5 and Al2O3 for V-30Al and V-30Al-10Cr, and TiO2 for V-30Al-10Ti The addition of aluminum was found to reduce the oxidation rate of vanadium, but not to the extent predicted by the theory of competing oxide phases proposed by Wang, Gleeson, and Douglass. This was attributed to the formation of a liquid-oxide phase in the initial stages of exposure from which the alloys could not recover. Ternary additions of chromium and titanium were found to decrease the oxidation rate further, with chromium being the most effective. The oxide scales of the alloys were found to be highly porous at 900° C and 1000° C, due to the high vapor pressure of V2O5 above 800° C.
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  • 60
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 36 (1991), S. 143-156 
    ISSN: 1573-4889
    Schlagwort(e): plasma nitriding ; Fe-18Cr-9Ni ; CrN precipitates ; nitrogen diffusion ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract To clarify the mechanism of plasma nitriding, we examined the optical microstructure, the hardness, the precipitation, and the concentration of dissolved nitrogen in Fe-18Cr-9Ni nitrided using plasma in the range of 723–823 K. Compared with ammonia-gas nitriding, the features of plasma nitriding are the formation of small chromium-nitride precipitates (CrN), the absence of an externally nitrided layer, the high concentration of dissolved nitrogen, and the high hardness (HV=1200). The diffusion coefficient of nitrogen in the present alloy was determined using the growth rate of the internally nitrided layer, based on calculations used in internal oxidation. Plasma- and gas-nitriding were also compared with respect to the growth rate of the nitrided layer.
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  • 61
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 41 (1994), S. 235-250 
    ISSN: 1573-4889
    Schlagwort(e): niobium ; oxidation ; morphology ; kinetics ; stresses
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation of niobium at high temperature (900°C) leads to reaction products with “exotic” morphologies. Morphological and kinetics analysis have been undertaken with Nb platelets. A growth mechanism of the oxide at the edges of the platelet is proposed.
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  • 62
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 42 (1994), S. 223-237 
    ISSN: 1573-4889
    Schlagwort(e): kinetics ; scale ; oxidation ; zirconium ; purity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation kinetics of zirconium of different purities were studied over the temperature range of 600–1300°C (α- and β-phases). The structure of the oxidized specimens was examined. TGA, XRD, EPMA, SEM, metallographic analysis, and microhardness measurements were carried out. Impurity elements were found to increase the oxidation rate of technical zirconium. The mechanism of the effect of impurity elements on zirconium oxidation was shown to differ for the α- and β-phases. Activation energies were calculated for the parabolic and linear stages of oxidation.
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  • 63
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 42 (1994), S. 249-263 
    ISSN: 1573-4889
    Schlagwort(e): kinetics ; scale ; oxidation ; hafnium ; purity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation kinetics of hafnium of different purities were studied in the temperature range of 800–1200°C. This paper concerns the structure studies of the oxidized samples. TGA, XRD, SEM methods, and microhardness measurements were used. Hafnium oxidation follows the parabolic rate law, changing with time to the linear one. Oxidation-reaction products are HfO2(moncl) and α-solid solution of oxygen in hafnium. Anomalous oxidation behavior of hafnium having a high impurity content was found in the range 800–950°C. Activation energies for the parabolic and linear oxidation stages were calculated.
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  • 64
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 43 (1995), S. 509-526 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; kinetics ; tantalum ; oxide ; suboxide ; impurities ; diffusion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The kinetics, structural aspects, and phase morphologies were studied for tantalum oxidation in air from 600 to 1000°C for samples of different purity (99.15%, 99.76%, and 99.95% Ta). Regardless of purity, tantalum oxidation in the temperature range of 600–800°C as a rule is governed by a linear rate law. From 900 to 1000°C the initial-stage oxidation is governed by the parabolic rate law, which changes to the linear rate law with time. TGA, XRD, SEM, and AES methods were used. The, effect of purity on tantalum oxidation was shown to be determined by the mechanism of intermediate-oxide formation. They are TaO z (Ta2O) at 600–800°C and TaO at 900–1000°C. The final product of oxidation was β-Ta2O5.
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  • 65
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 43 (1995), S. 543-560 
    ISSN: 1573-4889
    Schlagwort(e): stainless steel ; sulfidation ; hydrogen sulfide ; sulfur vapor ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The sulfidizing behavior of Fe−22Cr−4Al−0.15Zr (wt.%) was studied in two atmospheres: S2 vapor over the range 4.4–25.4 Pa and H2−H2S mixtures corresponding to aP S 2 range 0.2–1.297 Pa in the temperature range 973–1373 K. It was found that the constitution of the gaseous phase is of great importance on the corrosion kinetics and the morphology of the corrosion products. Furthermore, a stratification phenomenon during scale growth was observed during the initial sulfidation stage in H2−H2S mixtures containing a sufficiently high H2S partial pressure. This behavior was not observed during tests in puresulfur vapor.
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  • 66
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 44 (1995), S. 63-79 
    ISSN: 1573-4889
    Schlagwort(e): scale growth ; oxidation mechanism ; kinetics ; scale adherence ; reactive element effect ; intertacial segregation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Recent studies of the structure and dynamics of solid-solid interfaces have provided some understanding about the role of the scale-metal interface in the growth of reaction product scales on pure metals. The action of interfacial defects (misfit dislocations, misorientation dislocations and disconnections) in the creation and annihilation of the point defects suporting the diffusional growth of scales is considered. Anion point defects (vacancies/interstitials) supporting scale growth by anion diffusion are annihilated/created by the climb of misorientation dislocations or disconnections in the scale at the interface. For scale growth by cation diffusion, cation point defects (vacancies/interstitials) can be annihilated/created by the climb of interfacial misfit or misorientation dislocations in the metal. Because of their necessarily high density, in most cases, the dominant climb of misfit dislocations would be favored. The blocking of interfacial reaction steps can be a means to retard the scaling kinetics and to alter the fundamental scaling mode. For instance, the interfacial segregation of large reactive element ions can pin the interface dislocations, an action which poisons the usual interfacial reaction step. Such considerations are consistent with the well-known phenomena ascribed to the reactive element effect (REE).
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  • 67
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 53 (2000), S. 351-360 
    ISSN: 1573-4889
    Schlagwort(e): Co-base superalloy ; high-temperature oxidation ; kinetics ; structure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation behavior of the Co-base superalloy DZ40M was studied in air at900–1100°C for times of up to 2000 hr. The results indicated thatthis alloy can grow a protective oxide scale at 900 and 1000°C duringisothermal oxidation, but not at 1100°C because of serious cracking andspalling of the oxide scales. Moreover, an internal-precipitate zone formedin the subsurface region of the alloy at all temperatures and times. Theprecipitates were rich in Cr in the vicinity of the alloy–scaleinterface and rich in Al deep in the alloy. The internal-precipitatemorphology changed from a granular to needlelike shape with increasingoxidation temperature.
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  • 68
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 9 (1975), S. 99-116 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; kinetics ; ilmenite ; rutile ; pseudobrookite
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation of ilmenite (FeTiO3) in air and dry oxygen was investigated over the temperature interval 600 to 970°C. Dense platelets of ilmenite crystals as well as powder samples of ilmenite were oxidized. The weight data were recorded employing a thermobalance. The oxidation kinetics of ilmenite platelets were parabolic except for the initial stages during which logarithmic kinetics were observed. For powder samples the logarithmic rate law was followed primarily. The logarithmic rate law was attributed to free penetration of oxygen through cracks and short-circuit paths. The activation energies associated with the logarithmic rate law were nearly one-half of those obtained from parabolic oxidation. The growth morphology of the products of oxidation of ilmenite was observed with a scanning electron microscope. The effect of growth morphology on the kinetics is discussed, and a probable reaction mechanism is suggested for the oxidation of ilmenite.
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  • 69
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 9 (1975), S. 441-450 
    ISSN: 1573-4889
    Schlagwort(e): kinetics ; cobalt and nickel oxidation ; parabolic rate constant
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract A new fast method is proposed for the determination of parabolic rate constants of metal oxidation as a function of pressure and temperature. The method consists of determining rate constants by oxidation of a single metal sample in a continuous manner, periodically changing the oxidant pressure or temperature. This method eliminates a number of errors inherent in the classical method which involves the use of a new metal specimen in each experiment and it further shortens the time of evaluating the functions k p '' = f (p, T). The method is particularly suitable for the determination of rate constants of slow processes. To verify the proposed method measurements of the kinetics of oxidation of cobalt and nickel at different oxygen pressures over the temperature range 1000–1300° C were carried out.
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  • 70
    ISSN: 1573-4889
    Schlagwort(e): binary alloys ; oxidation ; transient state ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The initial transient stage in the oxidation of binary alloys forming scales exclusively composed of the most stable oxide is examined by means of a simplified approach which avoids the numerical integration of the diffusion equation for the transport of the metal components in the alloy. At variance with previous solutions to this problem obtained by means of numerical methods, this treatment takes into account also the effect of the gas-scale reaction at the outer surface of the oxide. The concentration of the most-reactive component at the alloy surface changes gradually with time from the initial bulk value towards the corresponding steady-state value without involving any minimum, while the overall rate of the reaction presents a gradual transition from an initial nearly linear towards final parabolic behavior.
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  • 71
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    Digitale Medien
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    Oxidation of metals 28 (1987), S. 237-258 
    ISSN: 1573-4889
    Schlagwort(e): Steel oxidation ; duplex scale ; steam ; activation energy ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The kinetics of the oxidation of ferrous alloys in steam (10–60 kPa) at 450–550°C have been studied by measuring both the rate of hydrogen emission and the amount of metal oxidized. Excellent agreement has been found between the amount of metal oxidized calculated from both the total mass of hydrogen produced in the reaction and the thickness of the oxide layer formed; rate constants calculated from the rate of hydrogen emission, the mass of hydrogen produced as the reaction proceeds, and the oxide formed agree within experimental error. The rate of oxidation of a 9%Cr-1%Mo alloy at 501°C was found to be independent of the partial pressure of the steam. For this alloy, the activation energy agreed with literature values obtained at higher temperatures and pressures. The effect of the chromium and silicon content on the oxidation rates is compared. The rate constants are compared with theoretical calculations, assuming that the rate is determined by diffusion of iron in the magnetite lattice. For the 9%Cr-1%Mo alloy, the parabolic rate constant and activation energy are in excellent agreement with values calculated using Wagner's theory. The experimental rate constants are greater for the alloys containing smaller amounts of chromium; diffusion of iron along magnetite grain boundaries may be the dominant mechanism.
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  • 72
    ISSN: 1573-4889
    Schlagwort(e): kinetics ; oxidation ; microcalorimetry ; thermogravimetry
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract In the kinetic theories of Bodenstein or Semenov the expression for the rate of a chemical reaction with several elementary stages can be expressed by different physical parameters. If two experimental methods are used, one method of necessity being microcalorimetry to measure the thermal flux produced by the reaction, it is possible to distinguish a pure kinetics case from a mixed one. The two-method technique has been verified by a study of the oxidation of niobium.
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  • 73
    ISSN: 1573-4889
    Schlagwort(e): titanium ; nitridation ; kinetics ; diffusion ; scaling
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The nitridation behavior of titanium has been examined in an atmosphere of nitrogen over the temperature range 900–1000° C. In addition to determining the reaction kinetics, microhardness and metallographic studies have been carried out on the nitrided substrates and nitride scales. Overall parabolic kinetics were exhibited, while a linear scaling reaction (associated principally with Ti2N formation) was observed. Extensive dissolution of nitrogen in the substrate was evident from the microhardness studies, and at 950 and 1000° C the growth of the nitrogen-stabilized αTi phase layer followed a parabolic law. Consideration of all the observed processes and derived data suggested that diffusion of nitrogen in the metal substrate was probably the rate-controlling mechanism.
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  • 74
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    Digitale Medien
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    Oxidation of metals 11 (1977), S. 263-276 
    ISSN: 1573-4889
    Schlagwort(e): nickel ; sulfidation ; kinetics ; mechanism
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The reaction between pure nickel and H2S-H2 mixtures containing 1–65% H2S has been studied over the temperature range 450–600°C. The sulfidation of nickel in the temperature range 560–600°C has been found to follow a linear rate law at low concentrations of H2S and a parabolic rate law at higher concentrations (10% and 65% H2S); X-ray examination of the scale formed on the metal showed it to be almost entirely β-Ni3S2. On the basis of the kinetics and marker studies it can be concluded that the sulfide scale on nickel is formed by the outward transport of the metal and the inward transport of sulfur. In the temperature range 450–500°C the sulfidation of nickel follows a parabolic rate law. In mixtures containing 10% H2S the scale formed contains voids, the occurrence of which is connected with formation of Ni7S6. It has also been shown that the rate of transport through the Ni3S2 layer has an essential influence on the formation of a continuous layer of Ni7S6. Marker studies have shown that both nickel and sulfur appear to be mobile in β′-Ni3S2.
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  • 75
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    Digitale Medien
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    Oxidation of metals 12 (1978), S. 67-82 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; Fe-C ; kinetics ; oxide grain size ; grain-boundary diffusion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Fe-C alloys containing 0.1, 0.5, and 1.0% C were oxidized in 1 atm O2 at 500°C. Two specimen preparations were used: annealed followed by slow cooling to form coarse pearlite plus proeutectoid ferrite or cementite; and cold-worked by abrading after annealing. The cold-worked alloys oxidize more rapidly. Annealed pearlite oxidizes faster than annealed ferrite. The differences in oxidation rate are caused by differences in the Fe3O4 grain size, that is, by the number of oxide grain boundaries available to act as easy diffusion paths for the outward diffusion of Fe through the Fe3O4. The oxidation rate constant is 10 times larger for fine-grained poly crystalline oxide than for oxide in which the Fe3O4 is monocrystalline.
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  • 76
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    Digitale Medien
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    Oxidation of metals 13 (1979), S. 437-456 
    ISSN: 1573-4889
    Schlagwort(e): Fe-Cr ; oxidation ; kinetics ; oxide morphology
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Ferritic polycrystalline Fe-24 wt.% Cr was oxidized in pure oxygen at 190 ≤ T≤490° C and pressures in the range 5.3×10−2–13.3 Pa for periods of up to 5 hr. The reaction proceeded in three stages. An initial period of accelerating rate was accompanied by oxide island nucleation and growth. Following island coalescence the rate was approximately logarithmic at low temperatures and somewhat slower than parabolic at high temperatures. Rate control during this period was thought to be due to mass transport through the oxide grain boundaries left by the island impingement process. During these first two stages the oxide formed was γ-M2O3 with possibly some spinel. The final stage of reaction involved the appearance of α-M2O3 on the outer oxide surface and a substantial slowing of the oxidation rate due to the low diffusivity in this phase.
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  • 77
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    Oxidation of metals 13 (1979), S. 89-104 
    ISSN: 1573-4889
    Schlagwort(e): BaTiO3 ; kinetics ; solid state ; mechanisms
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The authors propose a mechanism for the solid-solid reaction BaCO3+ TiO2→BaTiO3+CO2. This mechanism is based on the real structure of the present semiconductors. The reactions at different interfaces and the diffusing species are identified. The reaction rates are calculated and the dependence of the reaction rate upon O2, N2, and CO2 gas pressure is interpreted and discussed.
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  • 78
    Digitale Medien
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    Oxidation of metals 13 (1979), S. 119-158 
    ISSN: 1573-4889
    Schlagwort(e): nickel-chromium alloys ; oxidation ; high temperature ; kinetics ; mechanisms
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation of binary Ni-Cr alloys containing 44 and 50 wt. % Cr has been studied over a range of oxygen partial pressures at temperatures between 800 and 1100°C. The effects of cold work, surface preparation, and distribution of the Cr-rich second phase have been studied. The oxidation behavior is complex and cannot be described by a single model. The oxide grows by short-circuit diffusion as well as bulk transport through Cr 2 O 3 scales. The scale-growth mechanism includes extensive metal-oxide separation requiring Cr vapor transport to the scale, compressive stresses within the oxide which result in scale bulging and cracking, and the formation of a second oxide layer which results in voids being incorporated into the scale. Any factor which reduces the oxide grain size, such as cold work, finer distribution of the Cr-rich α phase or reduced oxygen pressure, results in an increased oxidation rate of binary alloys because of an increased number of grain-boundary short-circuit diffusion paths.
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  • 79
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    Oxidation of metals 14 (1980), S. 147-165 
    ISSN: 1573-4889
    Schlagwort(e): oxidation in air or oxygen ; kinetics ; oxide identification ; oxygen diffusion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation kinetics of Ti-4.32 wt.% Nb (2.27 at.%) alloy in either air or oxygen under 1 bar pressure have been investigated in the temperature range of 1255–1471 K. For oxidation in oxygen the kinetics follow consecutively decreasing parabolic rate laws. The kinetics become nonparabolic after prolonged oxidation in air. X-ray data reveal the presence of TiO2 (rutile) as the main oxide. The presence of Ti2O, δ-TiN, and ɛ-TiN is found on the metal surface after oxidation in air. Microhardness and electron microprobe measurements are used to determine Ti, Nb, O, and N profiles across the oxidized alloy. The oxygen diffusion coefficient in the alloy can be expressed byD=65.6 exp(−234.3/RT) with the activation energy in kilojoules per mole. The oxidation behavior of the alloy is explained.
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  • 80
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; titanium ; Ti-Ni alloy ; Ti-Cu alloy ; kinetics ; oxide scale ; solid-state diffusion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The kinetics and morphologic oxidation properties of titanium, Ti-1.5Ni and Ti-2.5Cu were compared. Titanium and Ti-1.5Ni have a similar behavior, concerning the kinetics and the oxide micro structure. Copper additions decrease the oxidation rate of titanium. The oxide scales formed on Ti-Cu are thinner and less cracked than those obtained on Ti or Ti-1.5Ni. Copper is found in the oxide scale of Ti-Cu, whereas nickel is not found in the oxide scale of Ti-Ni. The oxidation of titanium and its alloys is controlled chiefly by diffusional phenomena in the oxide scale. Thus the alterations of the oxide scale structure and the slower oxidation rate of Ti-2.5Cu can be attributed to the copper which diffuses towards the gas-oxide interface.
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  • 81
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    Oxidation of metals 16 (1981), S. 107-131 
    ISSN: 1573-4889
    Schlagwort(e): Oxidation ; iron ; kinetics ; sulfur ; surface analysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The growth of thin (0–200 Å) oxide films on iron at 200 and 300 °C has been studied as a function of time and oxygen partial pressure using proton-induced X-ray emission (PIXE) and Auger electron spectroscopy (AES). Oxidation was found to be initially retarded by sulfur which had segregated onto the iron surfaces during preoxidation annealing, but only if the iron surface contained the maximum or near-maximum sulfur coverage (ca. one-half monolayer). During and immediately following the oxygen-sulfur interaction, oxide buildup appeared to be limited by a surface reaction (adsorption, ionization, or dissociation). For most of the oxidation period, pressure-dependent logarithmic oxide growth was observed at 200°C, and pressure-independent parabolic oxide growth at 300°C. Interpretation of the data indicated that oxide growth at 200°C may be limited by quantum mechanical tunneling of electronic species through the previously formed oxide film, and oxide growth at 300°C may be limited by ionic diffusion through the previously formed oxide film. Comparison of AES and PIXE data indicated that the oxide films formed at 200°C were uniform in thickness over the surface of the metal, whereas films formed at 300°C had relatively thin areas where sulfur had remained.
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  • 82
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    Oxidation of metals 17 (1982), S. 43-54 
    ISSN: 1573-4889
    Schlagwort(e): Coatings ; oxidation ; titanium silicide ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Coatings of Ti 5Si3 on titanium have been prepared by means of decomposition of silane SiH4 on heated titanium ribbons. Oxidation of the coated titanium specimens was much slower than that of the noncoated ones. Gravimetric and morphological experiments allowed to propose a mechanism describing the oxidation process.
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  • 83
    Digitale Medien
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    Oxidation of metals 22 (1984), S. 45-57 
    ISSN: 1573-4889
    Schlagwort(e): Ni-Cr-Mo alloys ; sulfidation ; scale structures ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The effect of molybdenum additions 5, 10, 15, and 20 wt. %, on the sulfidation behavior of Ni-20Cr, and the effect of chromium additions, 5, 10, 15, and 20 wt.%, on the sulfidation of Ni-20Mo were studied in pure sulfur vapor at 700°C. In general, the alloys followed a linear or near-linear rate law, the sulfidation rate of Ni-20Mo being slightly less than that of Ni-20Cr. The alloys having the lowest ternary addition, e.g., Ni-Cr-5Mo and Ni-20Mo-5Cr. exhibited the most rapid reaction rates. The highest alloying additions of 20 wt.% had no appreciable benefit on reaction rates. Scale structures were complex but generally consisted of several layers. The outer layer was always NiS1.03, although both binaries formed Ni3S2 within the NiS1.03. An inner layer of Cr3S4 existed in which there was considerable dissolved molybdenum. A thin, intermediate layer of Cr2S3 generally formed between the Cr3S4 and the outer nickel sulfide. An innermost layer of MoS2 formed on all alloys containing more than 10 wt. % Mo, and a second phase of Mo2S3 formed within the MoS2 on Ni-20Mo. Although the scales changed with alloy composition, no significant changes in reaction rate were observed. Notable differences in both scale structure and reaction kinetics between this study and previous studies were apparent. The differences and possible reaction mechanisms are discussed.
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  • 84
    ISSN: 1573-4889
    Schlagwort(e): Ni-base alloy IN 617 ; reactor helium ; oxidation ; carburization ; decarburization ; kinetics ; mechanisms
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Application of the technical nickel-base alloy IN 617 in the primary circuit of the high-temperature gas-cooled reactor is limited essentially by the chemical reactions with the impurities (CO, CO2, H2, CH4, H2O) in the helium coolant. The interactions of the alloy with the reactive impurities in different helium-base gases were investigated by thermogravimetry in a gas-tight microbalance and by simultaneous measurement of the changes in gas composition by a continuous sensitive mass spectrometric analysis. The results demonstrate that the set of six reaction equations deduced in part 1 can be applied to describe the corrosion of the alloy. The occurrence of the various reactions is determined essentially by temperature. For the case of a standardized helium gas (HHT-He), three temperature regions can be distinguished. Below a critical temperature (about 1105 K), the presence of CO can cause simultaneous oxidation and carburization. Above this temperature, this reaction does not reverse itself. Rather, oxidation by CO2 and H2O takes place that shows, after a transient period, the same kinetics observed in undiluted oxygen-containing gases. At temperatures above about 1205 K, decarburization of the alloy accompanied by the production of CO takes place, leading to severe destruction of the carbide microstructure and, therefore, limiting the applicability of the material.
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  • 85
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    Oxidation of metals 30 (1988), S. 185-200 
    ISSN: 1573-4889
    Schlagwort(e): austenitic steels ; oxidation resistance ; protective αA12O3 film ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The cyclical oxidation behavior of an austenitic stainless steel (24% Ni, 10% Cr, 5% Al, and balance Fe) has been evaluated in the temperature range 800–1300°C. The effects of trace elements such as S, Y, Zr, and Ti on the oxidation of the austenitic stainless steel have also been evaluated. The results indicate that Fe-Ni-Cr-Al stainless steels exhibit superior oxidation resistance up to 1300°C due to the formation of a very adherent and thin film of α-Al2O3.
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  • 86
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    Oxidation of metals 35 (1991), S. 107-137 
    ISSN: 1573-4889
    Schlagwort(e): iron ; oxidation in CO2+CO mixtures ; kinetics ; reaction mechanisms
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Oxidation of high purity iron in CO 2 and CO2 + COmixtures at different total pressures (0.1–1 atm.) has been studied at 1000–1200°C. While paper I of this study emphasized studies of the relation between scale morphology and reaction kinetics, this paper focuses on the reaction mechanism during the initial oxidation involving growth of wüstite films and scales. The reaction behavior is analyzed in terms of coupled kinetics comprising a surface reaction and diffusional transport through the scale. A classical model derived by C. Wagner, based on the assumption that the properties and defect concentrations in the scale surface are exactly the same as in bulk wüstite equilibrated in CO 2 +CO mixtures, does not provide a satisfactory description of the reaction kinetics and the gas-pressure dependence of the surface reaction. As an alternative model, it is suggested that the gasous molecules/species interacts with the surface to form surface complexes, and that surface complexes withCO2 serve as preferred reaction sites for the surface reaction.
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  • 87
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    Oxidation of metals 33 (1990), S. 177-189 
    ISSN: 1573-4889
    Schlagwort(e): kinetics ; oxidation ; titanium hydride ; rutile
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation kinetics of titanium-hydride powders were studied in the temperature range of 298–1378 K in air at atmospheric pressure. DTA, DSC, X-ray analysis, and scanning electron microscopy were used. Oxidation was found to take place by TiHxOy oxyhydride phases formation. The oxidation reaction rate at temperatures above 870 K was limited by diffusion of oxygen atoms through a rutile scale formed on the surface. The activation energy and preexponential values of the Arrhenius equation for different interaction stages as well as transformation enthalpies were calculated.
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  • 88
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    Oxidation of metals 35 (1991), S. 397-404 
    ISSN: 1573-4889
    Schlagwort(e): copper alloys ; nitridation ; kinetics ; scale structure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract One of the characteristic features of Mn-Cu binary alloys nitrided by gaseous nitrogen is that one of the two constitutive elements (Mn) can form nitrides, while the other one (Cu) does not give any stable compound with nitrogen. The only mixed manganese-copper nitride is the CuMn 3 N compound. The reaction kinetics with nitrogen are very slow and there is no internal nitriding. For alloys containing less than 20 at.% Mn, nitrogen reacts very little. The nitride scale formed on the alloys of greater Mn concentrations is a mixed nitride whose formula is Cu 1−x Mn 3+x N. The techniques of examination used are SEM, EMA, and GDS analysis.
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  • 89
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    Oxidation of metals 38 (1992), S. 1-32 
    ISSN: 1573-4889
    Schlagwort(e): sulfidation ; Fe-Cr-Al alloys ; kinetics ; structures ; sulfide compositions
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Sulfidation of an Fe-23.4Cr-18.6Al (at.%) alloy was investigated in H2S-H2 atmospheres, $$10^{ - 6} \leqslant {\text{P}}_{{\text{S}}_{\text{2}} } \leqslant 10^2 $$ Pa, at 973 K. It was found over this pressure range that sulfidation after an early transient period followed the parabolic rate law, being diffusion controlled. An investigation was carried out of the scales formed during early transient sulfidation over the sulfur pressure range $${\text{p}}_{{\text{S}}_{\text{2}} } = 10^{ - 6} - 10^{ - 2} $$ Pa. Fully developed scales were multilayered consisting of an inner compact layer of equiaxed grains, an intermediate layer of equiaxed and columnar grains exhibiting a small degree of porosity, and an outer porous layer of distinct plates and needles. The grains of the inner and intermediate layers contained quarternary sulfide phases. The following phases were identified: spinels (CrFe)Al2S4 and (FeAl)Cr2S4, hexagonal (FeCr)Al2S4, (CrAlFe)2S3, and (CrAlFe)5S6. The plates and needles were composed of hexagonal (FeCr)Al2S4 and (CrAlFe)2S3 at $${\text{p}}_{{\text{S}}_{\text{2}} } \geqslant 10^{ - 6} $$ and 10−5 Pa from which pyrrhotite, FeS, grew at $${\text{p}}_{{\text{S}}_{\text{2}} } \geqslant 10^{ - 4} $$ .
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  • 90
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    Acta mechanica Sinica 12 (1996), S. 144-157 
    ISSN: 1614-3116
    Schlagwort(e): microstructural evolution ; energetics ; kinetics ; dynamic system
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau , Physik
    Notizen: Abstract An evolving material structure is in a non-equilibrium state, with free energy expressed by the generalized coordinates. A global approach leads to robust computations for the generalized thermodynamic forces. Those forces drive various kinetic processes, causing dissipation at spots, along curves, surfaces and interfaces, and within volumetric regions. The actual evolution path, and therefore the final equilibrium state, is determined by the energetics and kinetics. A virtual work principle links the free energy landscape and the kinetic processes, and assigns a viscous environment to every point on the landscape. The approach leads to a dynamical system that governs the evolution of generalized coordinates. The microstructural evolution is globally characterized by a basin map in the coordinate space; and by a diversity map and a variety map in the parameter space. The control of basin boundaries raises the issue of energetic and kinetic bifurcations. The variation of basin boundaries under different sets of controlling parameters provides an analytical way to plot the diversity maps of structural evolution.
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  • 91
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    Powder metallurgy and metal ceramics 39 (2000), S. 540-544 
    ISSN: 1573-9066
    Schlagwort(e): compaction ; facing ; cumulative charge ; powder ; composite ; heterogeneous structure ; particle ; kinetics ; surface ; die ; model ; xeroradiogram
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract An experimental and numerical (finite element method) study is carried out for the effect of forming scheme on property distribution for cumulative charge facings made from composite heterogeneous powder material. An experimental procedure is developed for studying powder particle flow kinetics. It is shown that use of composite punches and partition of the moulded material into a number of sub-divisions with their successive compaction achieves a more uniform density distribution for an article. It is demonstrated how the direction of the force of friction on the die walls during compaction affects the compaction of articles with faces that are not perpendicular to the direction of the pressing. The results obtained make it possible to select the optimum compaction regime taking account of production features connected with powder material composition as well as service characteristics.
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  • 92
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    Colloid & polymer science 265 (1987), S. 193-205 
    ISSN: 1435-1536
    Schlagwort(e): Poly(TMPS) ; in situ ; SAXS ; crystallization ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract The isothermal crystallization kinetics of poly(TMPS) has been measured by ISSAXS and results obtained for a molecular weight fraction (21,000) below the critical entanglement molecular weight (25,000) and another one above it (371,000). The SAXS intensity vs. time curves suggest that a single transformation mechanism exists. The SAXS long period is independent of crystallization time for both poly(TMPS) fractions. However the interlamellar thickness contribution to the long period is dependent upon molecular weight and crystallization temperature, increasing with temperature and molecular weight. The crystallite contribution also increases over the range studied. Both fractions exhibit a significant, but reversible decrease in thickness on cooling the sample from the crystallization temperature to room temperature and recyling again. The change is more pronounced for 371,000 specimen in keeping with its lower crystallinity. The path dependence of lamellar dimensions has significant implications in the morphological characterization of polymers annealed or crystallized at one temperature and then measured at another one.
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  • 93
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    Colloid & polymer science 275 (1997), S. 303-306 
    ISSN: 1435-1536
    Schlagwort(e): Key words Vesicle ; self-assembly ; hydrotrope ; stopped-flow ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract  The kinetics of vesicle formation from a hydrotrope (sodium xylenesulfonate) solution of a surfactant (Laureth 4) is studied by the use of a stopped-flow apparatus combined with a dynamic light scattering device to determine vesicle size in the system. The hydrotrope system studied presents a system with a high surfactant solubilization combined with vesicle formation simply by dilution with water. The kinetic results show a single exponential decay time. The kinetic analysis indicates that the vesicles are formed from a molecular solution which resulted from the shear in the stopped-flow device and grow by monomeric association.
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  • 94
    ISSN: 1435-1536
    Schlagwort(e): Key words 3-aminopropyltriethoxy silane ; silica gel ; interaction ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract  Three silica gel sample systems, modified with 3-amino-propyltriethoxy silane (APTS), were prepared by sequentially sampling the reaction mixture at various time intervals. The concentrations of 3-aminopropylsilyl groups (APS) bound on the silica surface were determined by elemental analysis. For the same sample systems, 29Si NMR intensities of an (–O)4Si species belonging only to the silica gel particles and corrected by a cross-polarization correction factor were also measured. Both the APS-concentrations and the correc-ted 29Si NMR intensities depended upon reaction time, reflecting the rate of the APTS–silica gel reaction. Kinetic analysis of these data was made by use of the Gauss–Newton method, and the overall reaction was found to consist of three reaction processes (an initial fast reaction, a slower second reaction and a much slower third reaction). In particular, the conversion of (–O)3SiOH to (–O)4Si is predominant in the second reaction process and the pore size of a silica gel particle affects the reaction mechanism.
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  • 95
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    Colloid & polymer science 267 (1989), S. 179-183 
    ISSN: 1435-1536
    Schlagwort(e): Gel ; swelling ; kinetics ; diffusion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract Tanaka and Fillmore treated the swelling of a gel as a process where a crosslinked polymer network having been initially under uniform stress is expanded by osmotic pressure, sucking up the surrounding fluid medium. We point out that their physical reasoning is unnatural and leads to an unacceptable conclusion; we propose a more sound approach to the same problem. Our treatment assumes that the gel network is extended not by the osmotic pressure of the gel, but rather by the swelling pressure which is generated by the excess fluid penetrating in against the real nature of a polymer network that tends to shrink. The diffusion equation of the fluid, hence, plays a dominant role and gives the distribution of fluid concentration in contrast to Tanaka-Fillmore's scheme. The expression for the distribution of local strain in a spherical gel is deduced from the relation of mechanical balance between two forces, the one is due to the elasticity of the network and the other due to the gradient in the chemical potential of the fluid. The results obtained have forms analytically similar to Tanaka-Fillmore's, but are differ in the physical meanings.
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  • 96
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    Colloid & polymer science 267 (1989), S. 460-464 
    ISSN: 1435-1536
    Schlagwort(e): Diffusion ; silica gel ; kinetics ; surface area ; proton
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract The effect of preparation pH of silica hydrogel on the effective diffusion coefficient of protons in silica hydrogel (D e , m2/s), on surface area of silica gel (S, m2/s) and on particle size of silica gel (D p , mm) was studied. Silica hydrosols were obtained by adding water glass to sulfuric acid. The effective diffusion coefficient of proton in silica hydrogel was determined by the method of diffusion from silica hydrogel plane sheet to a stirred solution of a limited volume. A numerical solution was obtained for the diffusion equation using the Regula Falsi method. Regression analyses of experimental data were conducted. Diffusion of protons in silica hydrogel is a complicated process due to a decelerating effect of the porous structure of silica hydrogel and to the accelerating effects of slow ions such as Na+ and surface diffusion. The effective diffusion coefficient increased with surface area of silica gel, indicating the diffusion of protons on the surface of the silica particles.
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  • 97
    ISSN: 1435-1536
    Schlagwort(e): Polystyrene seed ; poly(butyl acrylate-methacrylic acid) shell ; particle mophology ; location of carboxylic groups ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract Polystyrene (PS) (1)/Poly(n-butyl acrylate (BA)-methacrylic acid (MAA)) (2) structured particle latexes were prepared by emulsion polymerization using monodisperse polystyrene latex seed (118 nm) and different BA/MAA ratios. Three main aspects have been investigated: i) the polymerization kinetics; ii) the particle morphology as a function of reaction time; iii) the distribution of MAA units between the water phase and the polymer particles. The amount of MAA in the shell copolymer was found to be the main factor controlling the particle shape and morphology. The shape of the structured particles was, generally, non-spherical, and the shape irregularities increased as a particles was, generally, non-spherical, and the shape irregularities increased as a function of reaction time. At the beginning of the second stage reaction, new small particles were observed, which coalesced onto the PS seed as the polymerization proceeded. The distribution of the MAA groups in the latex particles and the serum was analyzed by alkali/back-acid titration, using ionic exchanged latexes. No MAA groups were detected in the latex serum. Due to the lowTg of the BA-MAA copolymers, alkali conductimetric titrations accounted for all the MAA groups on and within the polymer particles. Therefore, for these systems, this method is not only limited to a thin surface layer, as it is often assumed.
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  • 98
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    Colloid & polymer science 272 (1994), S. 777-783 
    ISSN: 1435-1536
    Schlagwort(e): Mn(III)-poly(ethylene glycol) ; acrylonitrile ; block copolymerization ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract The kinetics and mechanism of thermal polymerization of acrylonitrile initiated by Mn(III) pyrophosphate — poly(ethylene glycol) (PEG, molecular weight 6000) redox system in aqueous sulfuric acid medium was studied in the temperature range 30–60°C. The overall rates of polymerization and the disappearance of Mn3+ were determined. The polymerization was initiated by the organic free radical produced from the Mn3+-PEG reaction and the termination was by the metal ions. The rate of polymerization of acrylonitrile was found to be directly proportional to the square of the monomer concentration and first power of PEG concentration, and inversely proportional to the concentration of Mn3+. The rate of manganic ion disappearance was found to be directly proportional to manganic ion concentration and PEG concentration, and independent of the monomer concentration. Based on these observations, a plausible reaction scheme was suggested and suitable kinetic expressions were evaluated.
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  • 99
    Digitale Medien
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    Colloid & polymer science 273 (1995), S. 524-532 
    ISSN: 1435-1536
    Schlagwort(e): Blends ; tetramethyl polycarbonate ; polystyrene ; LCST ; phase separation ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract A new method for the detection of phase separation and its kinetics through real-time measurements is presented using the dielectric technique. The kinetics of phase separation were determined for a blend of tetramethyl bisphenol-A polycarbonate TMPC and polystyrene PS at different temperatures. The temperature dependence of the rate constant of phase separation was determined. The activation energy of phase separation process is found to be equal to 46 kcal/mole. In addition, it was possible to determine the variation in the composition of the TMPC-rich phase with time. The results obtained were compared with the literature data and were found to be in good agreement.
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  • 100
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    Colloid & polymer science 74 (1987), S. 55-63 
    ISSN: 1435-1536
    Schlagwort(e): Triplet energy transfer ; micelle ; solubilization ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract Triplet energy transfer from 9-methylanthracene to azulene or guajazulene has been used to probe the migration of azulenes between micelles in aqueous solution. The migration of the hydrophobic solutes between small ionic and nonionic micelles had the temperature dependence expected for a process controlled by diffusion through the intermicellar solution, although the rate in some cases was substantially less than calculated from the Smoluchowski equation. Under conditions in which the micelles grow into large, probably rod-like structures, there are severe difficulties in separating the inter- and intramicellar deactivation processes. The intermicellar migration was enhanced under these conditions, in cetyltrimethylammonium surfactants on addition of chlorate ions, and in hexaethylene glycol dodecylether at temperatures approaching the cloud-point. The mechanism of this migration is discussed and compared with pertinent results from micelle relaxation kinetics and surfactant self-diffusion measurements.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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