Corrosion products environment

Manning, B.A., Hunt, M.L., Amrhein, C., and Yarmoff, J.A., Arsenic(III) and ar-senic(V) reactions with zero-valent iron corrosion products, Environ. Sci. Technol., 36(24), 5455-5461, 2002. 

In the outdoor environment, the high concentrations of sulfur and nitrogen oxides from automotive and industrial emissions result in a corrosion having both soluble and insoluble corrosion products and no pacification. The results are clearly visible on outdoor bronze sculpture (see Airpollution Exhaust CONTROL, automotive Exhaust conthol, industrial). 

Stress corrosion cracking, prevalent where boiling occurs, concentrates corrosion products and impurity chemicals, namely in the deep tubesheet crevices on the hot side of the steam generator and under deposits above the tubesheet. The cracking growth rates increase rapidly at both high and low pH. Either of these environments can exist depending on the type of chemical species present. 

Cooling System Corrosion Corrosion can be defined as the destmction of a metal by chemical or electrochemical reaction with its environment. In cooling systems, corrosion causes two basic problems. The first and most obvious is the failure of equipment with the resultant cost of replacement and plant downtime. The second is decreased plant efficiency to loss of heat transfer, the result of heat exchanger fouling caused by the accumulation of corrosion products. 

The most common form of corrosion is uniform corrosion, in which the entire metal surface degrades at a near uniform rate (1 3). Often the surface is covered by the corrosion products. The msting of iron (qv) in a humid atmosphere or the tarnishing of copper (qv) or silver alloys in sulfur-containing environments are examples (see also SiLVERAND SILVER ALLOYS). High temperature, or dry, oxidation, is also usually uniform in character. Uniform corrosion, the most visible form of corrosion, is the least insidious because the weight lost by metal dissolution can be monitored and predicted. 

Very often the environment is reflected in the composition of corrosion products, eg, the composition of the green patina formed on copper roofs over a period of years. The determination of the chemical composition of this green patina was one of the first systematic corrosion studies ever made (see Copper). The composition varied considerably depending on the location of the stmcture as shown in Table 2 (26,27). 

Duration of Test Although the duration of any test will be determined by the nature and purpose of the test, an excellent procedure for evaluating the effect or time on corrosion of the metal and also on the corrosiveness of the environment in laboratory tests has been presented by Wachter and Treseder [Chem. Eng. Pi og., 315-326 (June 1947)]. This technique is called the planned-interval test. Other procedures that require the removal of sohd corrosion products between exposure periods will not measure accurately the normal changes of corrosion with time. 

No common industrial metal is immune to corrosion fatigue since some reduction of the metal s resistance to cyclic stressing is observed if the metal is corroded, even mildly, by the environment in which the stressing occurs. Corrosion fatigue produces fine-to-broad cracks with little or no branching. They are typically filled with dense corrosion product. The cracks may occur singly but commonly appear as families of parallel cracks (Fig. 10.2). They are frequently associated with pits, grooves, or other forms of stress concentrators. Like other forms of... 

Metal surfaces in a well-designed, well-operated cooling water system will establish an equilibrium with the environment by forming a coating of protective corrosion product. This covering effectively isolates the metal from the environment, thereby stifling additional corrosion. Any mechanical, chemical, or chemical and mechanical condition that affects the ability of the metal to form and maintain this protective coating can lead to metal deterioration. Erosion-corrosion is a classic example of a chemical and mechanical condition of this type. A typical sequence of events is ... 

Metals that depend on a relatively thick protective coating of corrosion product for corrosion resistance are frequently subject to erosion-corrosion. This is due to the poor adherence of these coatings relative to the thin films formed by the classical passive metals, such as stainless steel and titanium. Both stainless steel and titanium are relatively immune to erosion-corrosion in most cooling water environments. 

The resistance of a metal to erosion-corrosion is based principally on the tenacity of the coating of corrosion products it forms in the environment to which it is exposed. Zinc (brasses), aluminum (aluminum brass), and nickel (cupronickel) alloyed with copper increase the coating s tenacity. An addition of V2 to 1)4% iron to cupronickel can greatly increase its erosion-corrosion resistance for the same reason. Similarly, chromium added to iron-base alloys and molybdenum added to austenitic stainless steels will increase resistance to erosion-corrosion. 

Types of damage can be classified as uniform or localized metal removal, corrosion cracking or detrimental effects to the environment from the corrosion products. Local attack can take the form of shallow pits, pitting, selective dissolution of small microstructure regions of the material or cracking. Detrimental effects are certainly not the case with buried pipelines, but have to be considered for environments in vessels and containers. It is usual, where different results of reactions lead... 

Corrosion products formed as thin layers on metal surfaces in either aqueous or gaseous environments, and the nature and stability of passive and protective films on metals and alloys, have also been major areas of XPS application. XPS has been used in two ways, one in which materials corroded or passivated in the natural environment are analyzed, and another in which well-characterized, usually pure metal surfaces are studied after exposure to controlled conditions. 

Material selection for the enclosure shell should consider the corrosiveness of the environment. Aluminized sheeting is preferred over zinc-coated material in a steel-production environment. 

This method is generally not capable of achieving a uniform standard of cleanliness on structural steel. It is not effective in removing intact mill scale or corrosion products from pitted surfaces. The durability of subsequent coats is therefore variable and unpredictable, and depends on the thoroughness of the operation and the exact nature of the contaminants left on the surface. The method should be confined to non-aggressive environments or where short-term durability is economically acceptable. 

Metal/environment interface—V ne cs of metal oxidation and dissolution, kinetics of reduction of species in solution nature and location of corrosion products him growth and him dissolution, etc. 

The study of corrosion is essentially the study of the nature of the metal reaction products (corrosion products) and of their influence on the reaction rate. It is evident that the behaviour of metals and alloys in most practical environments is highly dependent on the solubility, structure, thickness, adhesion, etc. of the solid metal compounds that form during a corrosion reaction. These may be formed naturally by reaction with their environment (during processing of the metal and/or during subsequent exposure) or as a result of some deliberate pretreatment process that is used to produce thicker films or to modify the nature of existing films. The importance of these solid reaction products is due to the fact that they frequently form a kinetic barrier that isolates the metal from its environment and thus controls the rate of the reaction the protection afforded to the metal will, of course, depend on the physical and chemical properties outlined above. 

Attack by erosion-corrosion may be uniform or localised, and in the case of the latter it is characterised by the formation of grooves or rounded depressions that are smooth and free from corrosion products. Frequently the areas of localised attack follow a pattern that is indicative of the direction of movement of the metal or the environment (Fig. 1.61). 

The corrosion products may be soluble or insoluble. If insoluble, they usually reduce the rate of corrosion by isolating the substrate from the corrosive environment. Less commonly, they may stimulate corrosion by offering little physical protection while retaining moisture in contact with the metal surface for longer periods. 

Weather conditions at the time of initial exposure of zinc and steel have a large influence on the protective nature of the initial corrosion products This can still be detected some months after initial exposure. Finally, rust on steel contains a proportion of ferrous sulphate which increases with increase in SO2 pollution of the atmosphere. The effect of this on corrosion rate is so strong that mild steel transferred from an industrial atmosphere to a rural one corrodes for some months as though it was still exposed to the industrial environment. ... 

Non-metallic impurities in liquid alkali metals play a major role in the corrosion of materials either by affecting metal solubilities, f orming spalli-ble corrosion products on the metal surface, promoting liquid metal embrittlement or bulk embrittlement of the surface or by sensitising the structure for further attack by other impurities e.g. O2. As in other corrosive environments the direction and magnitude of these impurity reactions... 

Under certain conditions, it will be impossible for the metal and the melt to come to equilibrium and continuous corrosion will occur (case 2) this is often the case when metals are in contact with molten salts in practice. There are two main possibilities first, the redox potential of the melt may be prevented from falling, either because it is in contact with an external oxidising environment (such as an air atmosphere) or because the conditions cause the products of its reduction to be continually removed (e.g. distillation of metallic sodium and condensation on to a colder part of the system) second, the electrode potential of the metal may be prevented from rising (for instance, if the corrosion product of the metal is volatile). In addition, equilibrium may not be possible when there is a temperature gradient in the system or when alloys are involved, but these cases will be considered in detail later. Rates of corrosion under conditions where equilibrium cannot be reached are controlled by diffusion and interphase mass transfer of oxidising species and/or corrosion products geometry of the system will be a determining factor. 

The atmospheric corrosion data in Table 4.34 (and also Table 13.8) is related to historic environments. Current use in the industrial areas listed with acidic pollution would show much lower corrosion rates as the corrosion of zinc in the atmosphere is essentially related to the SOj content (and the time of wetness) and in many countries the sulphurous pollution has been greatly reduced in the past 20 years. Zinc also benefits from rainwater washing to remove corrosive poultices thus, although initial corrosion rates are usually not very different on upper and lower surfaces, the latter tend —with time—to become encrusted with corrosion products and deposits and these are not always protective. 

---