Stress corrosion cracking

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Wet corrosion Stress corrosion cracking

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Stress corrosion cracking of a tube.

STRESS CORROSION CRACKING

Cracks across the grains (transgranular SCC) or along the grain boundaries (intergranular SCC). Stress corrosion cracking (SCC) results from the combined action of three factors: Tensile stresses in the material, a corrosive medium (esp. chloride-bearing or hydrogen-sulphide environment) and elevated temperature (normally above 60C for chloride-induced SCC). Cases where chloride induced SCC has occurred at lower temperatures than 60C exist. The most common media where stress corrosion cracking occurs are chloride containing solutions, but in other environments, such as caustics and polythionic acid, problems with SCC may also appear. Some enviroments that may cause stress corrosion cracking of stainless steels are listed below. Some environments where stainless steels are prone to stress corrosion cracking: Acid chloride solutions Seawater Condensing steam from chloride waters H 2 S + chlorides Polythionic acid (sensitised material) NaCl-H 2 O 2 NaOH-H 2 S The mechanism of stress corrosion cracking is not well understood. This is mainly due to the specific features of SCC being the result of a complex interplay of metal, interface and environment properties. As a result of this different combinations of solution and stress are seldom comparable and the most reliable information is obtained from empirical experiments. During SCC the material does not undergo general corrosion and the phenomenon is sometimes considered to be one of activation/passivation interaction. It has been found that cracks often initiate in trenches or pits on the surface, which can act as stress raisers. The isolated times for pit initiation, pit growth, crack initiation and fracture may, however, differ considerably between different materials. In some cases crack initiation has been associated with the formation of a brittle film at the surface. The film developed at grain boundaries might, for instance, have lower ductility due to a different metal composition than the bulk material. At a certain film thickness and under stress this brittle film will crack and expose the underlying metal. New film growth will proceed with subsequent continued crack growth and so forth. The developed crack tip has a small radius and will develop a very high stress concentration. Even so, the stress condition alone is not sufficient for crack growth, but corrosion still plays a very large part. It has been shown experimentally that stress corrosion cracking can be stopped when applying cathodic protection, i.e. when corrosion is stopped but the stress conditions remain unchanged. Cracking may be either transgranular (TGSCC) or intergranular (IGSCC) or, perhaps most usual, a combination of both. The material microstructure and alloying components are of major importance for crack paths as well as for SCC resistance. Alloying with Ni can make materials less prone to SCC and the duplex microstructure of the austenitic-ferritic grades is also beneficial. Standard austenitic stainless steels, like AISI 304 and AISI 316, are generally prone to SCC in chloide containing environments at temperatures above 60C, except at very low chloride contents, and therefore higher alloyed austenitics or duplex stainless steels should be used.

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Stress corrosion cracking

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Transgranular stress corrosion crack in Sandvik grade 2RE69 after autoclave testing in 1000 ppm chloride at 250C.

HYDROGEN EMBRITTLEMENT
Hydrogen embrittlement (HE) is sometimes stated to be a kind of SCC. This might, however, lead to serious misunderstandings as many discrepancies exist. Perhaps most important is that HE cannot be reduced by cathodic protection, but might instead increase under such circumstances. The reason for this is that HE is caused by the penetration of atomic hydrogen into the metal structure. This, in turn, might occur when reduction of H + is taking place on the metal surface, e.g. during cathodic protection in acidic environments. Several deposition techniques, such as electroplating, also involve reduction processes at the metal surface with the following risk of hydrogen penetration and embrittlement. To avoid this, treated articles are often baked before use to remove the hydrogen. The risk for HE is increased for harder metals, but the tendency to hydrogen cracking decreases with increasing temperature. Some differences between HE and SCC are illustrated in figure 14.

SULPHIDE STRESS CRACKING

Sulphide stress cracking (SSC) might be defined as a variant of HE, but is sometimes treated as a special corrosion type. Sulphides are hydrogenevolution poisons and as such prevent the hydrogen atoms formed on the metal surface from pairing up and dissolving as H2 into the surrounding solution. SSC has been found to cause severe problems especially in the oil and gas industry. A standard for material requirements in so-called sour environments has therefore been developed: NACE MR0175. Among the acceptable steel grades are SAF 2205, SAF 2507 and Sanicro 28. New grades can be accepted in NACE MR0175 after successful testing according to one of four methods described in NACE TM 0177. Chloride-induced SCC The best way of solving the problem of SCC is by selecting a suitable material. Type 304L and 316L austenitic steels have limited resistance to SCC, even at very low chloride contents and temperatures. The following steels, on the contrary, are highly resistant: Ferritic steels (also carbon steels) Austenitic-ferritic (duplex) steels Austenitic steels with high Ni content.

To some extent the risk of SCC can be avoided by proper design. It is especially important to avoid stress concentration, which will occur at sharp edges and notches. Testing can be carried out in e.g. 40% CaCl or in chloride-containing water. The diagram below shows results from chloride solutions 2 containing 8 ppm oxygen. Note that no cracking was observed in SAF 2507. H S-induced SCC 2 Within the oil and gas industry, the process fluids often contain a certain amount of hydrogen sulphide, H S. Applications involving 2 exposure to this type of process fluids are often referred to as sour service. When considering the corrosivity of a sour process fluid, the partial pressure of H S is to be considered besides the pH value, the temperature, the oxygen and chloride contents as well as the 2 presence of solid particles (such as sand). It has been shown that this type of corrosion attack is worst at temperatures around 80C, but cracking may occur also at temperatures below 60C.

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Stress corrosion cracking

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A high nickel content is favourable for a good resistance to this form of SCC and for most sour environments high nickel alloys are to be used. A Sandvik grade with very good resistance to sulphide-induced cracking is Sanicro 28. The duplex grades SAF 2205 and SAF 2507 have not as good resistance as the high nickel alloys, but can successfully be used at intermediate hydrogen-sulphide partial pressures. Testing can be carried out according to NACE TM0177 (5% NaCl and 0.5% acetic acid saturated with H S). The diagram below shows 2 results from this type of testing with SAF 2205 and SAF 2507. No cracking was observed on the SAF 2507 samples after the 720-hours test period. Note: Testing in NACE solution is carried out at an external laboratory, and it is both time consuming and expensive. Several of our standard grades as well as SAF 2205, SAF 2507 and Sanicro 28 are covered by the standard MR0175 and should not normally need further testing. Read more about the test in S-133.

1. SCC resistance in oxygen-bearing neutral solutions with various chloride contents. Testing time 1,000 hours. Applied stress equal to the 0.2% proof strength at testing temperature. 2. Constant-load SCC tests in NACE solution at room temperature (NACE TM0177).

Although looking as a piece of art, this SCC attack was devastating for the tube.

The photo was taken in a scanning electron microscope (SEM) and it shows a SCC crack with a magnification of 45 times.

Facts

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Stress corrosion cracking

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Three combined factors: Tensile stresses, a corrosive medium (esp. chlorides or H S), elevated temperature (normally 2 > 60C for Cl or at 80C for H S). 2 Transgranular or intergranular attacks. Materials for chloride-induced SCC: Ferritic steels (also carbon steels), duplex steels, austenitic steels with high Ni content (> 25%). Materials for H S-induced SCC: Austenitic steels with high Ni content. For less demanding environments duplex steels 2 can be used. Testing in e.g. 40% CaCl or chloride-containing water. 2 Grades with high resistance to chloride-induced SCC: SAF 2507, 254 SMO, Sanicro 28, SAF 2205. Testing in NACE solution (5% NaCl + 0.5% acetic acid, saturated with H S. 2 Grades with high resistance to H S -induced SCC: Sanicro 41, Sanicro 28 or, in some cases, SAF 2205, SAF 2507. 2 A document from the Sandvik Materials Technology web-site.

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