Kinetics high-temperature alloys

Compared with ferritic carbon and low-alloy steels, relatively little information is available in the literature concerning stainless steels or nickel-base alloys. From the preceding section concerning low-alloy steels in high temperature aqueous environments, where environmental effects depend critically on water chemistry and dissolution and repassivation kinetics when protective oxide films are ruptured, it can be anticipated that this factor would be of even more importance for more highly alloyed corrosion-resistant materials. 

Lithium alloys have been used for a number of years in the high-temperature "thermal batteries" that are produced commercially for military purposes. These devices are designed to be stored for long periods at ambient temperatures before use, where their self-discharge kinetic be-... 

It was quite recently reported that La can be electrodeposited from chloroaluminate ionic liquids [25]. Whereas only AlLa alloys can be obtained from the pure Hquid, the addition of excess LiCl and small quantities of thionyl chloride (SOCI2) to a LaCl3-sat-urated melt allows the deposition of elemental La, but the electrodissolution seems to be somewhat kinetically hindered. This result could perhaps be interesting for coating purposes, as elemental La can normally only be deposited in high-temperature molten salts, which require much more dilEcult experimental or technical conditions. Furthermore, La and Ce electrodeposition would be important, as their oxides have interesting catalytic activity as, for instance, oxidation catalysts. A controlled deposition of thin metal layers followed by selective oxidation could perhaps produce cat-alytically active thin layers interesting for fuel cells or waste gas treatment... 

It is important to realize that corrosion rates may be controlled by any of several thermodynamic or kinetic properties of the alloy-scale-environment system and not just by surface or interface reactions. The three stages of high temperature oxidation of a metal, shown schematically in Fig. 1, serve as an example (7). The first or transient stage includes initial gas adsorption, two-dimensional oxide nucleation, initial three-dimensional oxide formation and finally, formation of the dominant oxide that will control the oxidation rate in Stage II. Various portions of Stage I have been widely studied using surface analytical techniques, but its duration can be very short and it is usually assumed (not always correctly) that Stage I has little impact on ultimate corrosion properties of the material. 

The heart of corrosion science has been identified as electrochemical science coupled with the thermodynamic and kinetic values. Other limbs are oxidation and high-temperature oxidation of metals, protective coatings, passivity, inhibitors, microbial-induced corrosion, corrosion fatigue, hydrogen embrittlement and corrosion-resistant alloys. Having identified the limbs of corrosion science, it is instructive to examine how the various aspects came into existence over a period of time. 

In another study [35], the electrochemical emission spectroscopy (electrochemical noise) was implemented at temperatures up to 390 °C. It is well known that the electrochemical systems demonstrate apparently random fluctuations in current and potential around their open-circuit values, and these current and potential noise signals contain valuable electrochemical kinetics information. The value of this technique lies in its simplicity and, therefore, it can be considered for high-temperature implementation. The approach requires no reference electrode but instead employs two identical electrodes of the metal or alloy under study. Also, in the same study electrochemical noise sensors have been shown in Ref. 35 to measure electrochemical kinetics and corrosion rates in subcritical and supercritical hydrothermal systems. Moreover, the instrument shown in Fig. 5 has been tested in flowing aqueous solutions at temperatures ranging from 150 to 390 °C and pressure of 25 M Pa. It turns out that the rate of the electrochemical reaction, in principle, can be estimated in hydrothermal systems by simultaneously measuring the coupled electrochemical noise potential and current. Although the electrochemical noise analysis has yet to be rendered quantitative, in the sense that a determination relationship between the experimentally measured noise and the rate of the electrochemical reaction has not been finally established, the results obtained thus far [35] demonstrate that this method is an effective tool for... 

If one wants to obtain a comprehensive understanding of the interaction between a metal (or metal alloy) and a hydrothermal solution, then electrochemical kinetics and/or corrosion studies must be carried out. In particular, an electrochemical system capable of reliably operating at temperatures above 300 °C should be developed. It is a matter of fact that there are almost no data on the exchange current densities and the anodic and cathodic transfer coefficients for even the most fundamental electrochemical reaction in high-temperature subcritical and supercritical aqueous systems. Even the primary HERs and OERs have been poorly studied at temperatures above 100 °C. Therefore, the creation of a well-established method for measuring electrochemical kinetics and corrosion processes over a wide range... 

MICROSTRUCTURAL EFFECTS AND KINETICS OF HIGH TEMPERATURE OXIDATION IN NB-SI BASE ALLOYS... 

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