Corrosion processes

Maintenance costs depend on whether processing fluids are solids on the one hand or gas and liquid on the other. Solids handling tends to increase maintenance costs. Highly corrosive process fluids increase maintenance costs. Average maintenance costs tend to be around 6 percent of the flxed capital investment. ... 

Figure A3.10.1 (a) A schematic illustration of the corrosion process for an oxygen-rich water droplet on an iron surface, (b) The process can be viewed as a short-circuited electrochemical cell [4],...

Parkins R N 1982 Corrosion Processes (London Applied Soienoe)... 

Congleton J and Craig I H 1982 Corrosion Processes ed R N Parkins (London Applied Science) p 209... 

Conserva.tlon, Because the most common conservation problem with metal objects occurs when corrosion processes form a threat to the safety of the object or disfigure its appearance to an unacceptable degree (130,131), many conservation treatments are intended to stabilize the corrosion processes and to remove aesthetically displeasing corrosion cmsts. The latter requkes a great deal of thought and discussion as to when a corrosion layer ceases to be a deskable patina and becomes unacceptable. 

Cobalt aHoys may find appHcation ia a fluidized-bed process for the direct combustion of coal (qv). CoCrAlY-coated Haynes 188 has proven to be one of the most resistant materials to a fireside corrosion process encountered ia tubes coimected the fluidized-bed combustor to a steam turbiae. 

The Nonzero Minimum-Life Case. In many situations, no failures are observed during an initial period of time. For example, when testing engine bearings for fatigue life no failures are expected for a long initial period. Some corrosion processes also have this characteristic. In the foUowing it is assumed that the failure pattern can be reasonably weU approximated by an exponential distribution. 

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. 

Foulants enter a cooling system with makeup water, airborne contamination, process leaks, and corrosion. Most potential foulants enter with makeup water as particulate matter, such as clay, sdt, and iron oxides. Insoluble aluminum and iron hydroxides enter a system from makeup water pretreatment operations. Some well waters contain high levels of soluble ferrous iron that is later oxidized to ferric iron by dissolved oxygen in the recirculating cooling water. Because it is insoluble, the ferric iron precipitates. The steel corrosion process is also a source of ferrous iron and, consequendy, contributes to fouling. 

The mechanisms of lead corrosion in sulfuric acid have been studied and good reviews of the Hterature are available (27—30). The main techniques used in lead corrosion studies have been electrochemical measurements, x-ray diffraction, and electron microscopy. More recendy, laser Raman spectroscopy and photoelectrochemistry have been used to gain new insight into the corrosion process (30,31). 

Biological Corrosion The metabohc activity of microorganisms can either directly or indirectly cause deterioration of a metal by corrosion processes. Such activity can (1) produce a corrosive environment, (2) create electrolytic-concentration cells on the metal surface, (3) alter the resistance of surface films, (4) have an influence on the rate of anodic or cathodic reaction, and (5) alter the environment composition. 

Electrochemical Impedance Spectroscopy (EIS) and AC Impedance Many direct-current test techniques assess the overall corrosion process occurring at a metal surface, but treat the metal/ solution interface as if it were a pure resistor. Problems of accuracy and reproducibility frequently encountered in the application of direct-current methods have led to increasing use of electrochemical impedance spectroscopy (EIS). 

In maldug electrochemical impedance measurements, one vec tor is examined, using the others as the frame of reference. The voltage vector is divided by the current vec tor, as in Ohm s law. Electrochemical impedance measures the impedance of an electrochemical system and then mathematically models the response using simple circuit elements such as resistors, capacitors, and inductors. In some cases, the circuit elements are used to yield information about the kinetics of the corrosion process. 

Making use of the information from monitoring probes, combined with the storage and analysis capabilities of portable computers and microprocessors, seems the best method for understanding corrosion processes. Commercial setups can be assembled from standard probes, cables, readout devices, and storage systems. When these are coupled with analysis by corrosion engineers, the system can lead to better a understanding of in-plant corrosion processes. 

Thiobacillus thiooxidans is an aerobic organism that oxidizes various sulfur-containing compounds to form sulfuric acid. These bacteria are sometimes found near the tops of tubercles (see Chap. 3, Tubercu-lation ). There is a symbiotic relationship between Thiobacillus and sulfate reducers Thiobacillus oxidizes sulfide to sulfate, whereas the sulfate reducers convert sulfide to sulfate. It is unclear to what extent Thiobacillus directly influences corrosion processes inside tubercles. It is more likely that they indirectly increase corrosion by accelerating sulfate-reducer activity deep in the tubercles. 

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. 

Sulfides are intermixed with iron oxides and hydroxides on carbon steels and cast irons. The oxides are also produced in the corrosion process (Reaction 6.6). Although theoretical stoichiometry of 1 to 3 is often suggested between sulfide and ferrous hydroxide, empirically the ratio of iron sulfide to ferrous hydroxide is highly variable. Sulfide decomposes spontaneously upon exposure to moist air. Additionally, corrosion-product stratification is marked, with sulfide concentration being highest near metal surfaces. 

Perhaps the most important stress factor affecting corrosion fatigue is the frequency of the cyclic stress. Since corrosion is an essential component of the failure mechanism and since corrosion processes typically require time for the interaction between the metal and its environment, the corrosion-fatigue life of a metal depends on the frequency of the cyclic stress. Relatively low-stress frequencies permit adequate time for corrosion to occur high-stress frequencies may not allow sufficient time for the corrosion processes necessary for corrosion... 

The protective coating reforms on the metal surface via a corrosion process. 

In addition to fluid velocity, other characteristics of the eroding fluid can exert a marked influence on the erosion-corrosion process. Among the important factors are the following ... 

Impediments to water flow resulting from inadequate equipment design or lodgement of foreign objects in the tubes can exercise a dramatic effect on the erosion-corrosion process. Much of this influence is linked to the creation of turbulence and the simple increase in fluid velocity past obstructions. The importance of these factors is quickly recognized when the phenomenon of threshold velocity is considered. 

Due to the numerous factors that can contribute to an erosion-corrosion process, numerous approaches can mitigate or eliminate the problem. 

Use of inhibitors. Because corrosion is such a vital aspect of the erosion-corrosion process, inhibitors that will reduce corrosion under conditions of high fluid velocity have been a cost-effective method of dealing with erosion-corrosion. For example, injection of ferrous sulfate either intermittently or continuously has been successful in inhibiting erosion-corrosion, especially with copper-base alloys. 

Chemical removal of deposits and corrosion products revealed the appearance of the groove (Fig. 14.5). The crevice formed by the incompletely fused weld seam fostered the establishment of differential concentration cells (see Chap. 2). This resulted in localized corrosion and eventual perforation through the greatly thinned tube wall at the bottom of the crevice. The tubercle, which is composed of corrosion products, is a simple result of the corrosion process occurring locally within the crevice. 

The triggering mechanism for the corrosion process was localized depassivation of the weld-metal surface. Depassivation (loss of the thin film of chromium oxides that protect stainless steels) can be caused by deposits or by microbial masses that cover the surface (see Chap. 4, Underdeposit Corrosion and Chap. 6, Biologically Influenced Corrosion ). Once depassivation occurred, the critical features in this case were the continuity, size, and orientation of the noble phase. The massive, uninterrupted network of the second phase (Figs. 15.2 and 15.21), coupled... 

Galvanic corrosion in typical industrial cooling water systems is the net result of the interplay of these factors. Some factors may accelerate the corrosion process others may retard it. In their approximate order of importance, the more influential factors are discussed below. 

Most galvanic corrosion processes are sensitive to the relatively exposed areas of the noble (cathode) and active (anode) metals. The corrosion rate of the active metal is proportional to the area of exposed noble metal divided by the area of exposed active metal. A favorable area ratio (large anode, small cathode) can permit the coupling of dissimilar metals. An unfavorable area ratio (large cathode, small anode) of the same two metals in the same environment can be costly. 

Consideration of the basic elements characteristic of the galvanic corrosion process, as discussed above, points to the principles of sound preventive techniques. Since a galvanic potential difference is the driving force for corrosion reducing the magnitude of this difference can reduce or prevent galvanic corrosion. 

Graphitic corrosion is a slow corrosion process, typically requiring many years to effect significant damage. Complete penetration of thick cross sections has, however, occurred in as little as 2 years in adverse environments. On the other hand, cast iron components can be found in use in Europe after 160 years of service. Although graphitic corrosion causes a substantial reduction in mechanical strength, it is well known that corroded cast iron, when sufficiently supported, may remain serviceable when internal pressure is low and shock loads are not applied. 

All areas of the cooling water system where a specific form of damage is likely to be found are described. The corrosion or failure causes and mechanisms are also described. Especially important factors influencing the corrosion process are listed. Detailed descriptions of each failure mode are given, along with many common, and some not-so-common, case histories. Descriptions of closely related and similarly appearing damage mechanisms allow discrimination between failure modes and avoidance of common mistakes and misconceptions. 

Many sources contain scattered information concerning cooling water system corrosion and defects, and many literature studies describe corrosion processes and mechanisms from a predominantly theoretical viewpoint. Until now, however, no source discusses cooling water system corrosion with emphasis on identification and elimination of specific problems. Much of the information in this book is unique every significant form of attack is thoroughly detailed. Color photos illustrate each failure mechanism, and case histories further describe industrial problems. 

We can aggravate the corrosion effect if misiiligned parts have relative movement, sueh as loose fit bearings or rapid changes in the system. Cavitation, erosion and high fluid velocity advance the corrosion process. 

The concept of the corrosion process, derived from the Latin corrodere (to eat away, to destroy), first appeared in the Philosophical Transactions in 1667 [2]. It was discussed in a German translation from the French on the manufacture of white lead in 1785 and was mentioned in 1836 in the translation of an English paper by Davy on the cathodic protection of iron in seawater [3]. However, almost until the present day, the term was used indiscriminately for corrosion reaction, corrosion effects, and corrosion damage. Only in DIN 50900, Part I, were these terms distinguished and defined [4] (see Section 2.1). 

Corrosion Processes, Corrosion Damage, and Protective Countermeasures... 

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