On the Mechanism of Formation of Thin Oxide Layers on Nickel

Häuffe, Karl; Pethe, L. D.; Schmidt, Randall G.; Morrison, Steven

doi:10.1149/1.2411269

Cited by 34 publications

(8 citation statements)

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“…5 and 6). 1 As mentioned earlier various rate laws have been previously reported for nickel oxidation at 400~176 including parabolic (2), two stage logarithmic (3,4), and logarithmic followed by fourth power (5). We would consider that the variety of results arise from the development of structurally different oxides whose formation has been influenced by the nature of the starting surface.…”

Section: Initial Stage--evaporated Metal Films Have Beenmentioning

confidence: 92%

On the Mechanism of Low-Temperature Oxidation (23°–450°C) of Polycrystalline Nickel

Graham

Cohen

1972

J. Electrochem. Soc.

112

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The oxidation of "clean" nickel has been investigated from 24 ~ to 450~ at oxygen pressures of 5 X i0 -s to 6 X 10-* Tort. Ultra-high vacuum techniques made it possible to start oxidation on specimens free of oxide and surface impurities such as C, Si, and S. Oxygen uptake was measured manometrically with a capacitance gauge of submonolayer sensitivity. Initial rapid oxygen adsorption (and place exchange) on nickel was followed by slower oxidation obeying a logarithmic rate law over the thickness range 8-30A. Growth of thicker films was in accord with a parabolic rate law, transport through the oxide occurring predominantly via easy diffusion paths. The value of 41 kcal. mole -I calculated from an Arrhenius plot of the parabolic rate constants from 300 ~ to 450~ is an approximate measure of the activation energy for growth via leakage paths. A pt/6 dependence of the parabolic growth rate on oxygen pressure was found at 450~ Nickel oxidation is considered to be one of the simpler systems of study since only one oxide, NiO, is produced, and partly for this reason has been the subject of numerous investigations (1). NiO, a p-type semiconductor, grows by the outward movement of nickel cations and electrons via vacancies and holes. At high temperatures, say >1000~ parabolic growth is generally observed. However, at moderate temperatures (around 500~ a variety of experimental kinetics have been reported. These include parabolic (2), two stage logarithmic (3, 4), and logarithmic followed by quartic (5) rates of oxidation. It may be that differences in material purity, surface preparation, and pretreatrnent could account for the variation in experimental data, and the present work on we]lcharacterized surfaces was u n d e r t a k e n in an attempt to resolve some of the discrepancies and, if possible, to present a simplified model for the low-temperature oxidation of nickel.

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Section: Initial Stage--evaporated Metal Films Have Beenmentioning

confidence: 92%

On the Mechanism of Low-Temperature Oxidation (23°–450°C) of Polycrystalline Nickel

Graham

Cohen

1972

J. Electrochem. Soc.

112

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“…GaAs electrodes have been the subject of various electrochemical studies (1)(2)(3)(4). It has been shown that the basic anodic process in aqueous electrolytes is the anodic dissolution of the GaAs electrode (2) whereas the cathodic process is mainly due to hydrogen evolution (2,4). The first process occurs via the valence band, i.e., holes are consumed.…”

Section: Discussionmentioning

confidence: 99%

“…Applying the equilibrium condition ~ #idni = 0 to Eq. [4] it can be shown, after some algebra, that the oxygen partial pressure, pa, in the presence of a stress is related to the stress-lree value, Pdiss., by…”

Section: And Noting That [M]/[m] ~ = [Vo"]/[vo"] ~mentioning

confidence: 99%

“…Simple models for the protective oxidation of metals based on reaction control by the diffusion of species across the oxide layer predict parabolic kinetics, vim = kptl/, [1] where ~ is the oxide thickness, t is" elapsed time, and kp is the parabolic rate constant. However, there are many instances where reaction rates decline more rapidly than parabolic kinetics predict, e.g., on zirconium (1), Zircaloy-2 (1), nickel (2)(3)(4), titanium (5), tantalum (5), and copper (5). No entirely satisfactory explanation has been given of this behavior.…”

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confidence: 99%

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Perturbation of Parabolic Kinetics Resulting from the Accumulation of Stress in Protective Oxide Layers

Evans

Norfolk

Swan

1978

J. Electrochem. Soc.

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A frequent observation in metal oxidation is the development of subparabolic kinetics, variously described as cubic or quartic. Although a number of detailed mechanisms have been proposed to account for this effect, none seem generally applicable. This paper presents a model of the oxidation process which is divorced from such restrictions. It is argued that deviations from parabolic behavior occur as a result of the concurrent development of stresses within the oxide. It is shown that the presence of stress fields can influence significantly the rate of transport of vacancy defects within the oxide such that tensile stresses produce positive deviations and compressive stresses, negative deviations from parabolic behavior. The model is applied in detail to Zircaloy‐2 oxidation at 773°K. It is predicted that the kinetics should be insensitve to the oxygen potential of the environment and this has been confirmed by previous experimental work. In addition, the absolute value of the oxidation rate is closely predicted using measured values of diffusion coefficients and the observed gradual departure from parabolic kinetics with increasing oxide thickness is accounted for.

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“…More complex are the conditions for the formation of thin tarnish layers (d < 103 A) in the range of low and medium temperatures, because in the first stages of surface film growth the effects of surface and space charges as well as of nucleation and recrystallization processes must be considered (HAUFBE, SCHOTTKY; CABRERA, MOTT; EVANS). The kinetics of the tarnish oxidation has been studied by a number of authors a t several metals in a wide range of temperatures and pressures (EVANS; N w o~o , UHLIG; WEISSMANTEL 1962, HAUFFE 1968. Mainly following time laws for layer formation have been observed and interpreted, however, usually they only give an accurate description of the real behaviour within limited ranges of time and temperature.…”

Section: Introductionmentioning

confidence: 99%

Nucleation and crystal growth during sulphidation and oxidation of thin zinc and cadmium films

Weißmantel¹,

Hecht²,

Herberger³

et al. 1970

Cryst Res and Technol

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The kinetics of sulphidation and oxidation of evaporated zinc and cadmium films in pure sulphur vapour and oxygen has been investigated. I n the temperature range from 100 to 250 "C a rapid gas sorption occurs which may be described by logarithmic expressions such as a = const . log ( t -t o ) . Subsequently a slow reaction is observed the time laws of which can also be represented by logarithmic expressions or by a general power law of the type a = const. t l / f i .Electron-optical and X-ray studies taken a t various stages of the reaction reveal a substantial effect of nucleation and recrystallization processes on the kinetics of layer growth. I n detail the following phases of layer growth could be confirmed: 2. Growth of oriented sulphide or oxide nuclei with diameters of lo2-lo3 a. Coalescence of these nuclei and formation of a coherent layer (in the case ofCdS and CdO formation of medium-size oriented crystallites). Formation of whiskers a t slightly higher temperatures.The results show that nucleation and recrystallization processes strongly affect the kinetics of the formation of surface films on metals. Therefore it can be concluded that it is necessary considerably to modify the theoretical attempts for a quantitative description of layer growth which in most cases are based on a homogeneous layer structure.An aufgedampften Zink-und Cadmiumfilmen wurde die Kinetik der Sulfidierung und der Oxydation in reinem Schwefeldampf bzw. Sauerstoff untersucht. Im Temperaturbereich zwischen 100 "C und 250 "C erfolgt zuniichst eine rasche Gasaufnahme, die durch logarithmische Ausdriicke der Form a = const * log ( t -to) beschrieben werden kann. Daren anschlieaend wird eine langsame Reaktion beobachtet, deren Zeitgesetz sich gleichfalls durch logarithmische Ausdrucke bzw. durch ein allgemeines Potenzgeset,z der Form a = const I tlifi wiedergeben 1aBt.Elektronenoptische

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On the Mechanism of Formation of Thin Oxide Layers on Nickel

Cited by 34 publications

References 1 publication

On the Mechanism of Low-Temperature Oxidation (23°–450°C) of Polycrystalline Nickel

On the Mechanism of Low-Temperature Oxidation (23°–450°C) of Polycrystalline Nickel

Perturbation of Parabolic Kinetics Resulting from the Accumulation of Stress in Protective Oxide Layers

Nucleation and crystal growth during sulphidation and oxidation of thin zinc and cadmium films

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