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Although stainless steels are often chosen because of their resistance to corrosion, they are not immune to it. Whether a stainless steel is corrosion resistant in a specific environment depends on a combination of its chemical composition and the aggressiveness of the environment.
The corrosion resistance of stainless steel is attributed to the thin passive film that forms spontaneously on its surface in oxidizing environments if the steel has a minimum chromium content of approximately 10.5%.
All types of corrosion affecting stainless steel are related to permanent damage of the passive film, through either complete or local breakdown. Factors such as the chemical environment, pH, temperature, surface finish, product design, fabrication method, contamination, and maintenance procedures can all affect the corrosion behavior of steel and the type of corrosion that may occur.
Typically, stainless steel does not corrode in the same manner as carbon or low-alloy steel, which rust due to constantly changing anodes and cathodes on the whole surface. In order for this process to occur on stainless steel, the passive film needs to be completely broken down in environments such as non-oxidizing acids like hydrochloric acid. More commonly, the passive film is attacked at certain points, causing various types of localized corrosion.
This type of corrosion is highly localized, with discrete pits on the free surface of stainless steels. If the passive layer is damaged or locally weak, pitting corrosion can initiate, and the small area that is unprotected by the passive film becomes the anode. As this anodic area is very small compared to the large cathode area of the undamaged passive film, the corrosion rate is high and a pit is formed.
The Pitting Resistance Equivalent (PRE), often also given as PREN to indicate the influence of nitrogen in the steel, can be used in order to rank and compare the resistance of different stainless steels in terms of their resistance to pitting corrosion. It takes into account the effect of the most important alloying elements. One frequently used equation for stainless steels is PRE = % Cr + 3.3 × %Mo + 16 × %N.
It is important to remember that the calculated PRE only gives an indication of the resistance of stainless steels and gives no information on their behavior in real environments. Therefore, it should only be used for roughly comparing the pitting corrosion resistance of different grades.
Uniform corrosion occurs when the passive layer is destroyed on the whole, or a large part, of the steel surface. This means the anodic and cathodic reactions occur on the same surface at constantly changing locations, much like corrosion on carbon steel. The result is more or less uniform removal of metal from the unprotected surface. Uniform corrosion can occur on stainless steels in acids or hot alkaline solutions.
Like pitting and crevice corrosion, stress corrosion cracking (SCC) most frequently occurs in chloride-containing environments. Elevated temperatures (> 60 °C for chloride environments and > 100 °C for alkaline environments) are normally required for SCC to occur in stainless steel. Nevertheless, there are cases where cracking can occur at temperatures as low as 30 °C, for example in swimming pool environments.
A common cause of SCC is evaporation on hot stainless steel surfaces. Liquids with low chloride content that would normally be considered harmless can cause chloride concentrations high enough to cause SCC. One example of where this can occur is underneath thermal insulation on piping.
Standard austenitic grades, such as 4307 and 4404, are generally sensitive to chloride-induced stress corrosion cracking. High nickel and molybdenum content increases the resistance of austenitic stainless steels, which is why the high alloyed austenitic grades 904L, 254 SMO®, and 654 SMO® show excellent resistance to chloride-induced SCC. Stainless steels with a duplex microstructure generally have high resistance to SCC, as have ferritic grades.
Another hydrogen embrittlement failure mode that can be a concern in the oil and gas industry is hydrogen-induced stress cracking (HISC), where hydrogen is introduced when the material is under cathodic protection in seawater. The hydrogen is a result of the increased cathodic reaction, hydrogen ion reduction, on the stainless steel surface.
Even high-alloyed stainless steels can be subjected to full cathodic protection in offshore applications, as these steels are typically connected to carbon steel and other low-alloyed steels already under protection. Ferritic, martensitic, and duplex stainless steels are generally more susceptible than the austenitic grades to hydrogen embrittlement.
As with stress corrosion cracking, residual stresses from manufacturing processes can adversely affect resistance to corrosion fatigue. Increasing the mechanical strength of stainless steels also increases their resistance to corrosion fatigue so duplex stainless steels are often superior to conventional austenitic grades.
Stainless steel that is exposed to an aggressive atmospheric environment is primarily affected by staining, sometimes referred to as tea staining. However, not all discoloration is necessarily the result of corrosion. It can also be discoloration from dirt or extraneous rust caused, for example, by iron particles on the surface. However, if the chloride level is high enough, stainless steel can, over time, also be attacked by localized corrosion such as pitting and crevice corrosion.
However, with their passive layer, stainless steels exhibit a totally different corrosion mechanism. This means it is not easy to apply the corrosivity classes in ISO 9223 to stainless steels, and they are therefore not the best tool for selecting stainless steels for atmospheric conditions. The higher the corrosion class, the higher alloyed stainless steel needs to be used, with the range going from ferritic grades up to superaustenitic and superduplex grades.
How the stainless steel is exposed to the atmosphere is also of great importance. In areas with rainfall, sheltered conditions prevent rinsing, and corrosivity is increased. In dry areas with little or no rainfall, sheltering will protect steel from aggressive pollutants and thus decrease corrosivity.
Surface condition and surface roughness can affect the performance of stainless steels. On a coarse surface, dirt, particles, and corrosive chemicals are easily retained, increasing the susceptibility to atmospheric corrosion. A smooth surface will facilitate rinse-off and is therefore less susceptible. Rinse-off is also facilitated if a ground or polished surface is vertically orientated. The lower the alloying levels of the stainless steel, the greater the impact of the surface finish on the resistance to atmospheric corrosion.
Galvanic corrosion can take place if two dissimilar metals are electrically connected and exposed to a corrosive environment. Galvanic corrosion, is usually not a problem for stainless steels but can affect other metals in contact with them.
In their passive state, stainless steels are nobler than the majority of other metallic construction materials in most environments. Galvanic coupling to metals such as carbon steel, galvanized steel, copper, and brass can therefore increase the corrosion rate of these metals. Galvanic corrosion between different stainless steel grades is generally not a problem providing that each grade remains passive in the environment in question.
If the surface of the less noble metal is small relative to the nobler metal, the corrosion rate can become very high. This is the case if carbon steel bolts are used to fasten stainless steel sheets, which can lead to severe galvanic corrosion on the bolts. Similarly, defects in coating or paint on a less noble material can result in a small anodic area and lead to high corrosion rates. It is therefore preferable to coat or paint the nobler metal in a galvanic couple in order to reduce the risk of galvanic corrosion.
In addition to the electrochemically based wet corrosion, stainless steels can suffer high temperature corrosion and oxidation. This can occur when a metal is exposed to a hot atmosphere containing oxygen, sulfur, halogens, or other compounds able to react with the material.
As with wet corrosion, stainless steel used for high-temperature applications must rely on the formation of a protective oxide layer at the surface. The environment must be oxidizing in order to form the protective layer, which consists of oxides of one or several of the alloying elements. An environment is often termed oxidizing or reducing as meaning "with respect to iron", since a so-called reducing atmosphere can oxidize elements such as aluminum and silicon, and often even chromium.
When stainless steels are exposed to an oxidizing environment at elevated temperatures, an oxide layer is formed on the surface, acting as a barrier between the metal and the gas. Chromium increases the oxidation resistance of stainless steels by the formation of a chromia (Cr2O3) scale on the surface. 2b1af7f3a8