Factors Influencing Corrosion (Part 2)

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.

Factors Influencing Corrosion (Part 1)

Solution pH The corrosion rate of most metals is affected by pH. The relationship tends to follow one of three general patterns:

1. Acid-soluble metals such as iron have a relationship as shown in Fig. a below. In the middle pH range (≈4 to 10), the corrosion rate is controlled by the rate of transport of oxidizer (usually dissolved O2) to the metal surface. Iron is weakly amphoteric. At very high temperatures such as those encountered in boilers, the corrosion rate increases with increasing basicity, as shown by the dashed line.
   
   
2. Amphoteric metals such as aluminum and zinc have a relationship as shown in Fig. b. These metals dissolve rapidly in either acidic or basic solutions.
   
   
3. Noble metals such as gold and platinum are not appreciably affected by pH, as shown in Fig. c.

Please click at picture to enlarge size

Oxidizing Agents In some corrosion processes, such as the solution of zinc in hydrochloric acid, hydrogen may evolve as a gas. In others, such as the relatively slow solution of copper in sodium chloride, the removal of hydrogen, which must occur so that corrosion may proceed, is effected by a reaction between hydrogen and some oxidizing chemical such as oxygen to form water. Because of the high rates of corrosion which usually accompany hydrogen evolution, metals are rarely used in solutions from which they evolve hydrogen at an appreciable rate. As a result, most of the corrosion observed in practice occurs under conditions in which the oxidation of hydrogen to form water is a necessary part of the corrosion process. For this reason, oxidizing agents are often powerful accelerators of corrosion, and in many cases the oxidizing power of a solution is its most important single property insofar as corrosion is concerned.

Oxidizing agents that accelerate the corrosion of some materials may also retard corrosion of others through the formation on their surface of oxides or layers of adsorbed oxygen which make them more resistant to chemical attack. This property of chromium is responsible for the principal corrosion-resisting characteristics of the stainless steels.

It follows, then, that oxidizing substances, such as dissolved air, may accelerate the corrosion of one class of materials and retard the corrosion of another class. In the latter case, the behavior of the material usually represents a balance between the power of oxidizing compounds to preserve a protective film and their tendency to accelerate corrosion when the agencies responsible for protective-film breakdown are able to destroy the films.

Fluid Corrosion : General

Corrosion is the destructive attack upon a metal by its environment or with sufficient damage to its properties, such that it can no longer meet the design criteria specified. Not all metals and their alloys react in a consistent manner when in contact with corrosive fluids. One of the common intermediate reactions of a metal surface is achieved with oxygen, and those reactions are variable and complex. Oxygen can sometimes function as an electron acceptor and cause cathodic depolarization by removing the “protective” film of hydrogen from the cathodic area. In other cases, oxygen can form protective oxide films. The long-term stability of these films also varies: some are soluble in the environment, others form more stable and inert passive films. Electrochemically, a metal surface is in the active state (the anode), i.e., in which the metal tends to corrode, or is being corroded. When a metal is passive, it is in the cathodic state, i.e., the state of a metal when its behavior is much more noble (resists corrosion) than its position in the emf series would predict. Passivity is the phenomenon of an (electrochemically) unstable metal in a given electrolyte remaining observably unchanged for an extended period of time.

Metallic Materials Pure metals and their alloys tend to enter into chemical union with the elements of a corrosive medium to form stable compounds similar to those found in nature. When metal loss occurs in this way, the compound formed is referred to as the corrosion product and the metal surface is spoken of as being corroded.

Corrosion is a complex phenomenon that may take any one or more of several forms. It is usually confined to the metal surface, and this is called general corrosion. But it sometimes occurs along defective and/or weak grain boundaries or other lines of weakness because of a difference in resistance to attack or local electrolytic action.

In most aqueous systems, the corrosion reaction is divided into an anodic portion and a cathodic portion, occurring simultaneously at discrete points on metallic surfaces. Flow of electricity from the anodic to the cathodic areas may be generated by local cells set up either on a single metallic surface (because of local point-to-point differences on the surface) or between dissimilar metals.

Nonmetallics As stated, corrosion of metals applies specifically to chemical or electrochemical attack. The deterioration of plastics and other nonmetallic materials, which are susceptible to swelling, crazing, cracking, softening, and so on, is essentially physiochemical rather than electrochemical in nature. Nonmetallic materials can either be rapidly deteriorated when exposed to a particular environment or, at the other extreme, be practically unaffected. Under some conditions, a nonmetallic may show evidence of gradual deterioration. However, it is seldom possible to evaluate its chemical resistance by measurements of weight loss alone, as is most generally done for metals.

Introduction of Fluid Corrosion

In the selection of materials of construction for a particular fluid system, it is important first to take into consideration the characteristics of the system, giving special attention to all factors that may influence corrosion. Since these factors would be peculiar to a particular system, it is impractical to attempt to offer a set of hard and fast rules that would cover all situations.

The materials from which the system is to be fabricated are the second important consideration; therefore, knowledge of the characteristics and general behavior of materials when exposed to certain environments is essential.

In the absence of factual corrosion information for a particular set of fluid conditions, a reasonably good selection would be possible from data based on the resistance of materials to a very similar environment. These data, however, should be used with considerable reservations. Good practice calls for applying such data for preliminary screening. Materials selected thereby would require further study in the fluid system under consideration.