Temperature The rate of corrosion tends to increase with rising temperature. Temperature also has a secondary effect through its influence on the solubility of air (oxygen), which is the most common oxidizing substance influencing corrosion. In addition, temperature has specific effects when a temperature change causes phase changes which introduce a corrosive second phase. Examples include condensation systems and systems involving organics saturated with water.Velocity Most metals and alloys are protected from corrosion, not by nobility [a metal’s inherent resistance to enter into an electrochemical reaction with that environment, e.g., the (intrinsic) inertness of gold to (almost) everything but aqua regia], but by the formation of a protective film on the surface. In the examples of film-forming protective cases, the film has similar, but more limiting, specific assignment of that exemplary-type resistance to the exposed environment (not nearly so broad-based as noted in the case of gold). Velocity-accelerated corrosion is the accelerated or increased rate of deterioration or attack on a metal surface because of relative movement between a corrosive fluid and the metal surface, i.e., the instability (velocity sensitivity) of that protective film.
An increase in the velocity of relative movement between a corrosive solution and a metallic surface frequently tends to accelerate corrosion. This effect is due to the higher rate at which the corrosive chemicals, including oxidizing substances (air), are brought to the corroding surface and to the higher rate at which corrosion products, which might otherwise accumulate and stifle corrosion, are carried away. The higher the velocity, the thinner will be the films which corroding substances must penetrate and through which soluble corrosion products must diffuse.
Whenever corrosion resistance results from the formation of layers of insoluble corrosion products on the metallic surface, the effect of high velocity may be to prevent their normal formation, to remove them after they have been formed, and/or to preclude their reformation. All metals that are protected by a film are sensitive to what is referred to as its critical velocity; i.e., the velocity at which those conditions occur is referred to as the critical velocity of that chemistry/temperature/velocity environmental corrosion mechanism. When the critical velocity of that specific system is exceeded, that effect allows corrosion to proceed unhindered. This occurs frequently in small-diameter tubes or pipes through which corrosive liquids may be circulated at high velocities(e.g., condenser and evaporator tubes), in the vicinity of bends in pipelines, and on propellers, agitators, and centrifugal pumps. Similar effects are associated with cavitation and mechanical erosion.
Films Once corrosion has started, its further progress very often is controlled by the nature of films, such as passive films, that may form or accumulate on the metallic surface. The classical example is the thin oxide film that forms on stainless steels.
Insoluble corrosion products may be completely impervious to the corroding liquid and, therefore, completely protective; or they may be quite permeable and allow local or general corrosion to proceed unhindered. Films that are nonuniform or discontinuous may tend to localize corrosion in particular areas or to induce accelerated corrosion at certain points by initiating electrolytic effects of the concentration-cell type. Films may tend to retain or absorb moisture and thus, by delaying the time of drying, increase the extent of corrosion resulting from
exposure to the atmosphere or to corrosive vapors.
It is agreed generally that the characteristics of the rust films that form on steels determine their resistance to atmospheric corrosion. The rust films that form on low-alloy steels are more protective than those that form on unalloyed steel.
In addition to films that originate at least in part in the corroding metal, there are others that originate in the corrosive solution. These include various salts, such as carbonates and sulfates, which may be precipitated from heated solutions, and insoluble compounds, such as “beer stone,” which form on metal surfaces in contact with certain specific products. In addition, there are films of oil and grease that may protect a material from direct contact with corrosive substances. Such oil films may be applied intentionally or may occur naturally, as in the case of metals submerged in sewage or equipment used for the processing of oily substances.
Other Effects Stream concentration can have important effects on corrosion rates. Unfortunately, corrosion rates are seldom linear with concentration over wide ranges. In equipment such as distillation columns, reactors, and evaporators, concentration can change continuously, making prediction of corrosion rates rather difficult. Concentration is important during plant shutdown; presence of moisture
that collects during cooling can turn innocuous chemicals into
dangerous corrosives.
As to the effect of time, there is no universal law that governs the reaction for all metals. Some corrosion rates remain constant with time over wide ranges, others slow down with time, and some alloys have increased corrosion rates with respect to time. Situations in which the corrosion rate follows a combination of these paths can
develop. Therefore, extrapolation of corrosion data and corrosion rates should be done with utmost caution.
Impurities in a corrodent can be good or bad from a corrosion standpoint. An impurity in a stream may act as an inhibitor and actually retard corrosion. However, if this impurity is removed by some process change or improvement, a marked rise in corrosion rates can result. Other impurities, of course, can have very deleterious effects on materials. The chloride ion is a good example; small amounts of chlorides in a process stream can break down the passive oxide film on stainless steels. The effects of impurities are varied and complex. One must be aware of what they are, how much is present, and where they come from before attempting to recommend a particular material of construction.
Whenever corrosion resistance results from the formation of layers of insoluble corrosion products on the metallic surface, the effect of high velocity may be to prevent their normal formation, to remove them after they have been formed, and/or to preclude their reformation. All metals that are protected by a film are sensitive to what is referred to as its critical velocity; i.e., the velocity at which those conditions occur is referred to as the critical velocity of that chemistry/temperature/velocity environmental corrosion mechanism. When the critical velocity of that specific system is exceeded, that effect allows corrosion to proceed unhindered. This occurs frequently in small-diameter tubes or pipes through which corrosive liquids may be circulated at high velocities(e.g., condenser and evaporator tubes), in the vicinity of bends in pipelines, and on propellers, agitators, and centrifugal pumps. Similar effects are associated with cavitation and mechanical erosion.
Films Once corrosion has started, its further progress very often is controlled by the nature of films, such as passive films, that may form or accumulate on the metallic surface. The classical example is the thin oxide film that forms on stainless steels.
Insoluble corrosion products may be completely impervious to the corroding liquid and, therefore, completely protective; or they may be quite permeable and allow local or general corrosion to proceed unhindered. Films that are nonuniform or discontinuous may tend to localize corrosion in particular areas or to induce accelerated corrosion at certain points by initiating electrolytic effects of the concentration-cell type. Films may tend to retain or absorb moisture and thus, by delaying the time of drying, increase the extent of corrosion resulting from
exposure to the atmosphere or to corrosive vapors.
It is agreed generally that the characteristics of the rust films that form on steels determine their resistance to atmospheric corrosion. The rust films that form on low-alloy steels are more protective than those that form on unalloyed steel.
In addition to films that originate at least in part in the corroding metal, there are others that originate in the corrosive solution. These include various salts, such as carbonates and sulfates, which may be precipitated from heated solutions, and insoluble compounds, such as “beer stone,” which form on metal surfaces in contact with certain specific products. In addition, there are films of oil and grease that may protect a material from direct contact with corrosive substances. Such oil films may be applied intentionally or may occur naturally, as in the case of metals submerged in sewage or equipment used for the processing of oily substances.
Other Effects Stream concentration can have important effects on corrosion rates. Unfortunately, corrosion rates are seldom linear with concentration over wide ranges. In equipment such as distillation columns, reactors, and evaporators, concentration can change continuously, making prediction of corrosion rates rather difficult. Concentration is important during plant shutdown; presence of moisture
that collects during cooling can turn innocuous chemicals into
dangerous corrosives.
As to the effect of time, there is no universal law that governs the reaction for all metals. Some corrosion rates remain constant with time over wide ranges, others slow down with time, and some alloys have increased corrosion rates with respect to time. Situations in which the corrosion rate follows a combination of these paths can
develop. Therefore, extrapolation of corrosion data and corrosion rates should be done with utmost caution.
Impurities in a corrodent can be good or bad from a corrosion standpoint. An impurity in a stream may act as an inhibitor and actually retard corrosion. However, if this impurity is removed by some process change or improvement, a marked rise in corrosion rates can result. Other impurities, of course, can have very deleterious effects on materials. The chloride ion is a good example; small amounts of chlorides in a process stream can break down the passive oxide film on stainless steels. The effects of impurities are varied and complex. One must be aware of what they are, how much is present, and where they come from before attempting to recommend a particular material of construction.
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