Corrosion process passivation

In most corrosion processes passivity is desirable because the rate of electrode dissolution is significantly reduced. The rate of aluminum corrosion in fresh water is relatively low because of the adherent oxide film that forms on the metal surface. A thicker film can be formed on the surface by subjecting it to an anodic current in a process known as anodizing. In most electrochemical conversion processes passive films reduce the reaction rate and are, therefore, undesirable. 

Tantalum is not resistant to substances that can react with the protective oxide layer. The most aggressive chemicals are hydrofluoric acid and acidic solutions containing fluoride. Fuming sulfuric acid, concentrated sulfuric acid above 175°C, and hot concentrated aLkaU solutions destroy the oxide layer and, therefore, cause the metal to corrode. In these cases, the corrosion process occurs because the passivating oxide layer is destroyed and the underlying tantalum reacts with even mild oxidising agents present in the system. 

Passive corrosion caused by chemically inert substances is the same whether the substance is living or dead. The substance acts as an occluding medium, changes heat conduction, and/or influences flow. Concentration cell corrosion, increased corrosion reaction kinetics, and erosion-corrosion can he caused by biological masses whose metabolic processes do not materially influence corrosion processes. Among these masses are slime layers. 

Corrosion protection measures are divided into active and passive processes. Electrochemical corrosion protection plays an active part in the corrosion process by changing the potential. Coatings on the object to be protected keep the aggressive medium at a distance. Both protection measures are theoretically applicable on their own. However, a combination of both is requisite and beneficial for the following reasons ... 

The examples already discussed lead to the conclusion that any reaction of a metal with its environment must be regarded as a corrosion process irrespective of the extent of the reaction or of the rates of the initial and subsequent stages of the reaction. It is not illogical, therefore, to regard passivity, in which the reaction product forms a very thin protective film that controls rate of the reaction at an acceptable level, as a limiting case of a corrosion reaction. Thus both the rapid dissolution of active titanium in 40% H2SO4 and the slow dissolution of passive titanium in that acid must be... 

The determination of polarisation curves of metals by means of constant potential devices has contributed greatly to the knowledge of corrosion processes and passivity. In addition to the use of the potentiostat in studying a variety of mechanisms involved in corrosion and passivity, it has been applied to alloy development, since it is an important tool in the accelerated testing of corrosion resistance. Dissolution under controlled potentials can also be a precise method for metallographic etching or in studies of the selective corrosion of various phases. The technique can be used for establishing optimum conditions of anodic and cathodic protection. Two of the more recent papers have touched on limitations in its application and differences between potentiostatic tests and exposure to chemical solutions. ... 

Passivation is a necessary and natural initial corrosion process that occurs on all hot waterside surfaces. It is the conversion of a reactive metal surface into a lower energy state that does not readily further react or corrode, and it involves the development of a passive oxide film on a clean surface. 

The concepts and basic approach used in studies of electrical fluctuations in corrosion processes proved to be very successful as well in mechanistic studies of electrode reactions taking place at materials covered by passivating films. A typical example is the electrochemical dissolution of silicon. From an analysis of the noise characteristics of this process, it has been possible to identify many features as well as the conductivity of the nanostructures of porous silicon being formed on the original silicon surface. 

The deposition of contaminants in the surface usually causes an acceleration of the corrosion process however, there should not be excluded the possibility that a given contaminant could diminish corrosion rate, as it could be the case of ammonia and its influence on steel (due to its alkaline properties, it could induce the passivation of steel). 

A bare surface of silicon can only exist in fluoride containing solutions. In reality, in these media, the electrode is considered to be passive due to the coverage by Si— terminal bonds. Nevertheless, the interface Si/HF electrolyte constitutes a basic example for the study of electrochemical processes at the Si electrode. In this system, the silicon must be considered both as a charge carrier reservoir in cathodic reactions, and as an electrochemical reactant under anodic polarization. Moreover, one must keep in mind that, according to the standard potential of the element, both anodic and cathodic charge transfers are involved simultaneously (corrosion process) in a wide range of potentials. 

Pioneering work was done in this field by Schwabe [34, 35]. Substantial and very informative radiotracer adsorption studies carried out by him and his coworkers using Pt, Ni, and Fe sheets and evaporated films, using labeled anions in order to interpret the role of anions in the corrosion and passivation processes [34, 35]. 

The corrosion process can be inhibited by the addition of phosphate or polyphosphate ions [344], inorganic inhibitors as, for example, chromate ions [336], adsorbed alcohols [345], adsorbed amines, competing with anions for adsorption sites [339,] as well as saturated linear aliphatic mono-carboxylate anions, CH3(CH2)n-2COO , n = 7 — 11, [24]. In the latter case, the formation of the passive layer requires Pb oxidation to Pb + by dissolved oxygen and then precipitation of hardly soluble lead carboxylate on the metal surface. The corrosion protection can also be related to the hydrophobic character of carboxylate anions, which reduce the wetting of the metal surface. 

Anodizing employs electrochemical means to develop a surface oxide film on the workpiece, enhancing its corrosion resistance. Passivation is a process by which protective films are formed through immersion in an acid solution. In stainless steel passivation, embedded ion particles are dissolved and a thin oxide coat is formed by immersion in nitric acid, sometimes containing sodium dichromate. 

Stainless steel 316L material used for piping and equipment shows considerable corrosion resistance because of the beneficial effect of molybdenum on the surface properties. It is also observed that the surface treatment (pre-reduced, polished, passivated and chemically treated surfaces) of stainless steel equipment and piping reduces the corrosion process in seawater applications. The corrosion resistance of stainless steel in seawater applications can also be enhanced by bulk alloying the stainless steel with nitrogen, chromium, molybdenum and nickel by converting the stainless steel into super austenitic stainless steel. From leaching studies it is also observed that the release of iron, chromium and nickel from the super austenitic stainless steel to seawater is considerably... 

In the previous analysis, homogeneous current distribution has been assumed but, on many occasions, corrosion occurs with localized attack, pitting, crevice, stress corrosion cracking, etc., due to heterogeneities at the electrode surface and failure of the passivating films to protect the metal. In these types of corrosion processes with very high local current densities in small areas of attack, anodic and cathodic reactions may occur in different areas of disparate dimensions. 

This is a general name for a wide variety of corrosion processes that may be actively or passively influenced, or induced, by an even wider variety of microbiological organisms. The electrochemical reactions that occur always result in metal wastage, as with all other forms of corrosion the most active biocorrosion processes primarily involve sessile bacteria rather than planktonic bacteria, algae, or fungi. 

Most usually, a preoperational cleaning (POC) process/passivation program uses a chemical cleaner formulation based on a polyphosphate such as SHMP or STTP, together with various dispersants and surfactants. Where polyphosphate is not permitted to be discharged to sewer, silicates can often be used. Formulations may also include NaEDTA and sometimes specific corrosion inhibitors such as tolyltriazole (TTA). 

In potassium carbonate processes, arsenic and vanadium salts are used to suppress corrosion. A passive layer of magnetite on steel surfaces is maintained by adding a small amount of air88. 

Electrodes of many metals can undergo corrosion or passivation— formation of a salt film on the surface—and other reactions, depending on the medium and experimental conditions. Electrochemical techniques can be used to investigate the mechanisms of these processes. 

Whether a particular corrosion process is possible is determined by whether the line for hydrogen evolution or for oxygen reduction lies above (at a more positive potential than) the boundary for the oxidation half-reaction. This corresponds to a total negative free energy change. Nevertheless passivation often occurs, blocking further corrosion. In Fig. 16.1 a an example would be the zone where Fe203 is formed. 

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. 

Electrochemical noise consists of low-frequency, low-amplitude fluctuations of current and potential due to electrochemical activity associated with corrosion processes. ECN occurs primarily at frequencies less than 10 Hz. Current noise is associated with discrete dissolution events that occur on a metal surface, while potential noise is produced by the action of current noise on an interfacial impedance (140). To evaluate corrosion processes, potential noise, current noise, or both may be monitored. No external electrical signal need be applied to the electrode under study. As a result, ECN measurements are essentially passive, and the experimenter need only listen to the noise to gather information. 

Corrosion inhibitor - corrosion inhibitors are chemicals which are added to the electrolyte or a gas phase (gas phase inhibitors) which slow down the - kinetics of the corrosion process. Both partial reactions of the corrosion process may be inhibited, the anodic metal dissolution and/or the cathodic reduction of a redox-system [i]. In many cases organic chemicals or compounds after their reaction in solution are adsorbed at the metal surface and block the reactive centers. They may also form layers with metal cations, thus growing a protective film at the surface like anodic oxide films in case of passivity. Benzo-triazole is an example for the inhibition of copper cor-... 

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