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How To Avoid Metal Corroding
The corrosion resistance of a stainless steel is dependent on the presence of a protective oxide layer on its surface, but it is possible under certain conditions for this oxide layer to break down, for example in reducing acids, or in some types of combustion where the atmosphere is reducing. Areas where the oxide layer can break down can also sometimes be the result of the way components are designed, for example under gaskets, in sharp re-entrant corners or associated with incomplete weld penetration or overlapping surfaces. These can all form crevices which can promote corrosion. To function as a corrosion site, a crevice has to be of sufficient width to permit entry of the corrodent, but sufficiently narrow to ensure that the corrodent remains stagnant. Accordingly crevice corrosion usually occurs in gaps a few micrometres wide, and is not found in grooves or slots in which circulation of the corrodent is possible. This problem can often be overcome by paying attention to the design of the component, in particular to avoiding formation of crevices or at least keeping them as open as possible. Crevice corrosion is a very similar mechanism to pitting corrosion; alloys resistant to one are generally resistant to both. Crevice corrosion can be viewed as a more severe form of pitting corrosion as it will occur at significantly lower temperatures than does pitting.
Stress Corrosion Cracking (SCC)
Under the combined effects of stress and certain corrosive environments stainless steels can be subject to this very rapid and severe form of corrosion. The stresses must be tensile and can result from loads applied in service, or stresses set up by the type of assembly e.g. interference fits of pins in holes, or from residual stresses resulting from the method of fabrication such as cold working. The most damaging environment is a solution of chlorides in water such as sea water, particularly at elevated temperatures. As a consequence stainless steels are limited in their application for holding hot waters (above about 50°C) containing even trace amounts of chlorides (more than a few parts per million). This form of corrosion is only applicable to the austenitic group of steels and is related to the nickel content. Grade 316 is not significantly more resistant to SCC than is 304. The duplex stainless steels are much more resistant to SCC than are the austenitic grades, with grade 2205 being virtually immune at temperatures up to about 150°C, and the super duplex grades are more resistant again. The ferritic grades do not generally suffer from this problem at all.
In some instances it has been found possible to improve resistance to SCC by applying a compressive stress to the component at risk; this can be done by shot peening the surface for instance. Another alternative is to ensure the product is free of tensile stresses by annealing as a final operation. These solutions to the problem have been successful in some cases, but need to be very carefully evaluated, as it may be very difficult to guarantee the absence of residual or applied tensile stresses.
From a practical standpoint, Grade 304 may be adequate under certain conditions. For instance, Grade 304 is being used in water containing 100 - 300 parts per million (ppm) chlorides at moderate temperatures. Trying to establish limits can be risky because wet/dry conditions can concentrate chlorides and increase the probability of stress corrosion cracking. The chloride content of seawater is about 2% (20,000 ppm). Seawater above 50°C is encountered in applications such as heat exchangers for coastal power stations.
Recently there have been a small number of instances of chloride stress corrosion failures at lower temperatures than previously thought possible. These have occurred in the warm, moist atmosphere above indoor chlorinated swimming pools where stainless steel (generally Grade 316) fixtures are often used to suspend items such as ventilation ducting. Temperatures as low as 30 to 40°C have been involved. There have also been failures due to stress corrosion at higher temperatures with chloride levels as low as 10 ppm. This very serious problem is not yet fully understood.
Sulphide Stress Corrosion Cracking (SSC)
Of greatest importance to many users in the oil and gas industry is the material's resistance to sulphide stress corrosion cracking. The mechanism of SSC has not been defined unambiguously but involves the conjoint action of chloride and hydrogen sulphide, requires the presence of a tensile stress and has a non-linear relationship with temperature.
The three main factors are Stress Level, Environment and Temperature.
Stress Level
A threshold stress can sometimes can be identified for each material - environment combination. Some published data show a continuous fall of threshold stress with increasing H2S levels. To guard against SSC NACE specification MR0175 for sulphide environments limits the common austenitic grades to 22HRC maximum hardness.
Environment
The principal agents being chloride, hydrogen sulphide and pH. There is synergism between these effects, with an apparently inhibiting effect of sulphide at high H2S levels.
Temperature
With increasing temperature, the contribution of chloride increases but the effect of hydrogen decreases due to its increased mobility in the ferrite matrix. The net result is a maximum susceptibility in the region 60-100°C. A number of secondary factors have also been identified, including amount of ferrite, surface condition, presence of cold work and heat tint at welds.
Intergranular Corrosion
Intergranular corrosion is a form of relatively rapid and localised corrosion associated with a defective microstructure known as carbide precipitation. When austenitic steels have been exposed for a period of time in the range of approximately 425 to 850°C, or when the steel has been heated to higher temperatures and allowed to cool through that temperature range at a relatively slow rate (such as occurs after welding or air cooling after annealing), the chromium and carbon in the steel combine to form chromium carbide particles along the grain boundaries throughout the steel. Formation of these carbide particles in the grain boundaries depletes the surrounding metal of chromium and reduces its corrosion resistance, allowing the steel to corrode preferentially along the grain boundaries. Steel in this condition is said to be "sensitised".
It should be noted that carbide precipitation depends upon carbon content, temperature and time at temperature. The most critical temperature range is around 700°C, at which 0.06% carbon steels will precipitate carbides in about 2 minutes, whereas 0.02% carbon steels are effectively immune from this problem.
It is possible to reclaim steel which suffers from carbide precipitation by heating it above 1000°C, followed by water quenching to retain the carbon and chromium in solution and so prevent the formation of carbides. Most structures which are welded or heated cannot be given this heat treatment and therefore special grades of steel have been designed to avoid this problem. These are the stabilised grades 321 (stabilised with titanium) and 347 (stabilised with niobium). Titanium and niobium each have much higher affinities for carbon than chromium and therefore titanium carbides, niobium carbides and tantalum carbides form instead of chromium carbides, leaving the chromium in solution and ensuring full corrosion resistance.
Another method used to overcome intergranular corrosion is to use the extra low carbon grades such as Grades 316L and 304L; these have extremely low carbon levels (generally less than 0.03%) and are therefore considerably more resistant to the precipitation of carbide.
Many environments do not cause intergranular corrosion in sensitised austenitic stainless steels, for example, glacial acetic acid at room temperature, alkaline salt solution such as sodium carbonate, potable water and most inland bodies of fresh water. For such environments, it would not be necessary to be concerned about sensitisation. There is also generally no problem in light gauge steel since it usually cools very quickly following welding or other exposure to high temperatures.
It is also the case that the presence of grain boundary carbides is not harmful to the high temperature strength of stainless steels. Grades which are specifically intended for these applications often intentionally have high carbon contents as this increases their high temperature strength and creep resistance. These are the "H" variants such as grades 304H, 316H, 321H and 347H, and also 310. All of these have carbon contents deliberately in the range in which precipitation will occur.