Corrosion additivity principle

Andersen et al. predicted that similar results would be expected for the corrosion of other multivalent metals oxidizing via lower oxidation states. They also pointed out that their interpretation was consistent with the kinetics of the corrosion of copper in oxygenated HCl solutions. Here the final product is Cu and thus there is no vulnerable intermediate. In consequence, the rate of copper dissolution from either Nj-saturated or 02-saturated HCl solutions was the same at a given potential in conformity with the additivity principle. 

The underlying problem in testing the validity of the additivity principle in corrosion, mineral extraction, and electroless plating is that the electrode metal itself forms part of one of the half-reactions involved, e.g., zinc in equation (5) and copper in equations (8) and (12). A much better test system is provided by the interaction of two couples at an inert metal electrode that does not form a chemical part of either couple. A good example is the heterogeneous catalysis by platinum or a similar inert metal of the reaction... 

Additivity principles in behavior of redox couples and corrosion processes. 

The principle of electrochemical corrosion protection processes is illustrated in Figs. 2-2 and 2-5. The necessary requirement for the protection process is the existence of a potential range in which corrosion reactions either do not occur or occur only at negligibly low rates. Unfortunately, it cannot be assumed that such a range always exists in electrochemical corrosion, since potential ranges for different types of corrosion overlap and because in addition theoretical protection ranges cannot be attained due to simultaneous disrupting reactions. 

Aqueous environments will range from very thin condensed films of moisture to bulk solutions, and will include natural environments such as the atmosphere, natural waters, soils, body fluids, etc. as well as chemicals and food products. However, since environments are dealt with fully in Chapter 2, this discussion will be confined to simple chemical solutions, whose behaviour can be more readily interpreted in terms of fundamental physicochemical principles, and additional factors will have to be considered in interpreting the behaviour of metals in more complex environments. For example, iron will corrode rapidly in oxygenated water, but only very slowly when oxygen is absent however, in an anaerobic water containing sulphate-reducing bacteria, rapid corrosion occurs, and the mechanism of the process clearly involves the specific action of the bacteria see Section 2.6). 

The principles of bimetallic corrosion have, in addition, been used in an elegant fashion for the development of highly corrosion-resistant alloys. 

Radioactivation Techniques Neutron and thin layer (TLA) activation are non-intrusive techniques ofi ering the prospect of continuous, direct component monitoring, in addition to coupon or probe, monitoring. In principle, localised corrosion can be monitored using a double-layer technique. Process plant applications of the technique have been limited to date. ... 

Literature Recent additions to the literature on the principles and practice of inhibition include books concerned with the subject as a whole, and reports of conferences and papers, or reports concentrating on particular aspects of the subject. Books include the volume by the late Professor I. L. Rozenfel d and collected data in the form of references, patents etc. from various sources Conferences include the recent quinquennial events at the University of Ferrara S, each providing substantial contributions to all aspects of corrosion inhibition. The uses of molybdates as inhibitors have been reviewed by Vukasovich and Farr in a paper with 221 references and test methods for inhibitors in a report from the European Federation of Corrosion with 49 references . 

Electroless deposition as we know it today has had many applications, e.g., in corrosion prevention [5-8], and electronics [9]. Although it yields a limited number of metals and alloys compared to electrodeposition, materials with unique properties, such as Ni-P (corrosion resistance) and Co-P (magnetic properties), are readily obtained by electroless deposition. It is in principle easier to obtain coatings of uniform thickness and composition using the electroless process, since one does not have the current density uniformity problem of electrodeposition. However, as we shall see, the practitioner of electroless deposition needs to be aware of the actions of solution additives and dissolved O2 gas on deposition kinetics, which affect deposit thickness and composition uniformity. Nevertheless, electroless deposition is experiencing increased interest in microelectronics, in part due to the need to replace expensive vacuum metallization methods with less expensive and selective deposition methods. The need to find creative deposition methods in the emerging field of nanofabrication is generating much interest in electroless deposition, at the present time more so as a useful process however, than as a subject of serious research. 

In addition to the active design principles for reducing the risk of sulfide problems, a number of more passive principles exist. The following design considerations are especially relevant for the reduction of corrosion selection of corrosion-resistant materials and design of a well-ventilated sewer system. 

For special purposes, more complex equipment is occasionally used (not covered by 4665) which additionally attempts to simulate corrosive or polluted atmospheres. There is an ISO standard for plastics for a salt spray exposure test93 which could in principle be applied to rubber should such an exposure be needed. Cyclic exposure to corrosive atmosphere could be more representative of service94,95. One particular circumstance is exposure to a marine environment and there is an ISO standard covering this for plastics96. 

Electrochemistry finds wide application. In addition to industrial electrolytic processes, electroplating, and the manufacture and use of batteries already mentioned, the principles of electrochemistry are used in chemical analysis, e.g.. polarography, and electrometric or conductometric titrations in chemical synthesis, e.g., dyestuffs, fertilizers, plastics, insecticides in biolugy and medicine, e g., electrophoretic separation of proteins, membrane potentials in metallurgy, e.g.. corrosion prevention, eleclrorefining and in electricity, e.g., electrolytic rectifiers, electrolytic capacitors. 

A general scheme for the development of corrosion models based on electrochemical principles has been described, and a number of examples for active, passive, and localized corrosion has been given. This chapter is by no means comprehensive, and a search of the scientific and technical literature will unearth many additional examples. The value in using electrochemical methods both to develop understanding of the corrosion process and to measure the values of specific modeling parameters is obvious. However, their application alone would not provide all the elements and parameter values required for the development of corrosion models, so the use of supplementary techniques is necessary. It is necessary also to keep in mind that electrochemical techniques inevitably accelerate the corrosion process one is interested in. Consequently, the scaling of electrochemi-cally determined parameter values to the rates and time periods of interest in the corrosion process to be modeled should be undertaken carefully and with a full knowledge of the limitations involved. 

A corrosion inhibitor is a chemical substance that, upon addition to a corrosive environment, results in reduction of corrosion rate to an acceptable level. Corrosion inhibitors are generally used in small concentrations. The principles and applications of corrosion inhibitors are discussed at great length in a recent monograph.47 A corrosion inhibitor should not only mitigate the corrosion, but also be compatible with the environment in the sense that it should not cause any complications. Usually the corrosion inhibitor is rated in terms of inhibition efficiency I and is given by the relationship. 

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