MECHANISM AND MITIGATION OF CORROSION FATIGUE FAILURE IN AUSTENITIC STAINLESS STEELS

Introduction
The austenitic stainless steels are iron alloys with 16-26 wt. % Cr.The austenitic group contains more grades, which are used in greater quantities, than any other category of stainless steels. The wrought austenitic steels are either single or duplex phase structures. Fatigue of structural metals is often the cause of failures in service, especially in those applications where the material is in contact with an aggressive environment. In such cases, it has been long recognized that corrosion fatigue damage arises from the dynamic interaction between the corrosive media and the cyclic deformation. In the seminar the different mechanisms of corrosion fatigue failure of austenic stainless steels are discussed. The various methods to counter it are described in detail. The duplex and the super duplex stainless steels which were introduced to counter the menace of corrosion failure are studied. An experiment was conducted on super duplex stainless steel SAF 2507 which shed light on the effective use of this alloy for offshore applications.

Austenitic Stainless Steels

Austenitic stainless steels (e.g. grades 1.4301 and 1.4833) consist of chromium (16-26%), nickel (6-12%),Carbon(max 0.2%) and iron. Other alloying elements (e.g. molybdenum) may be added or modified according to the desired properties to produce derivative grades that are defined in the standards (e.g. 1.4404). The austenitic group contains more grades that are used in greater quantities, than any other category of stainless steel. Austenitic stainless steels exhibit superior corrosion resistance to both ferritic and martensitic stainless steels. Corrosion performance may be varied to suit a wide range of service environments by careful alloy adjustment e.g. by varying the carbon or molybdenum content. These materials cannot be hardened by heat treatment and are strengthened by workhardening. Unlike ferritic and martensitic stainless steels, austenitic grades do not exhibit a yield point. They offer excellent formability and their response to deformation can be controlled by chemical composition. They are not subject to an impact transition at low temperatures and possess high toughness to cryogenic temperatures. They exhibit greater thermal expansion and heat capacity, with lower thermal conductivity than other stainless or conventional steels. They are generally readily welded.

Figure 1 (Ref 8)

Effect of Alloying on Structure and properties

CHROMIUM Chromium is by far the most important alloying element in stainless steel production. A minimum of 10.5% chromium is required for the formation of a protective layer of Chromium oxide on the steel surface. The strength of this protective (passive) layer increases with increasing chromium content. Chromium prompts the formation of Ferrite within the alloy structure and is described as ferrite stabilizer. NICKEL Nickel improves general corrosion resistance and prompts the formation of austenite (i.e. it is an austenite stabilizer). Stainless steels with 8-9% nickel have a fully austenitic structure and exhibit superior welding and working characteristics to ferritic stainless steels. Increasing nickel content beyond 8-9% further improves both

corrosion resistance (especially in acid environments) and workability.

MOLYBDENUM (AND TUNGSTEN) Molybdenum increases resistance to both local (pitting, crevice corrosion, etc) and general corrosion. Molybdenum and tungsten are ferrite stabilizers which, when used in austenitic alloys, must be balanced with austenite stabilizers in order to maintain the austenitic structure. NITROGEN Nitrogen increases strength and enhances resistance to localized corrosion. It is austenite former. COPPER Copper increases general corrosion resistance to acids and reduces the rate of workhardening.It is an austenite stabilizer. CARBON Carbon enhances strength (especially, in hardenable martensitic stainless steels), but may have an adverse affect on corrosion resistance by the formation of chromium carbides. It is an austenite stabilizer. TITANIUM (AND NIOBIUM & ZIRCONIUM) Where it is not desirable or, indeed, not possible to control carbon at a low level, titanium or niobium may be used to stabilize stainless steel against intergranular corrosion. As titanium (niobium and zirconium) have greater affinity for carbon than chromium, titanium (niobium and zirconium) carbides are formed in preference to chromium carbide and thus localized depletion of chromium is prevented. These elements are ferrite stabilizers. SULPHUR Sulphur is added to improve the machinability of stainless steels. As a consequence, Sulphur-bearing stainless steels exhibit reduced corrosion resistance. CERIUM Cerium, a rare earth metal, improves the strength and adhesion of the oxide film at high temperatures. MANGANESE

Manganese is an austenite former, which increases the solubility of nitrogen in the steel and may be used to replace nickel in nitrogen-bearing grades.

SILICON Silicon improves resistance to oxidation and is also used in special stainless steels exposed to highly concentrated sulphuric and nitric acids. Silicon is a ferrite stabilizer.

Corrosion Fatigue
Stress and corrosion working together can cause failure of metals in two ways. Stress corrosion is the term used when static or stationary stresses are involved. If cyclic or alternating stresses are involved. The failure is designated corrosion fatigue.

Figure 2(Ref 6)

The graph shows the variation of number of cycles to failure with stress applied in various corrosive environments. The longest life observed is in air while the shortest is in the corrosive sodium chloride solution or sea water. The common corrosive environments are:

Acidic media like H2SO4, HNO3, HCl. Seawater. Alkalis.

Condensing steam from chloride waters. Caustic soda solutions. Lead acetate solutions.

Mechanism of Corrosion fatigue failure

The basic mechanisms of corrosion fatigue failure are described below: 1. 2. 3. 4. Active path dissolution. Hydrogen embrittlement. Film induced cleavage. Anodic dissolution.

Active path dissolution This process involves accelerated corrosion along a path of higher than normal corrosion susceptibility, with the bulk of the material typically being passive. The most common active path is the grain boundary, where segregation of impurity elements can make it marginally more difficult for passivation to occur. For example, when an austenitic stainless steel has been sensitized by precipitation of chromium carbide along the grain boundary, the local chromium concentration at the grain boundary will be reduced, and this region will be slightly less easily passivated. Consequently, a form of crevice corrosion can occur, whereby the grain boundary corrodes, with the specimen surface and the crack walls remaining passive. This process can occur in the absence of stress, giving rise to intergranular corrosion that is uniformly distributed over the specimen. The effect of the applied stress is probably mainly to open up the cracks, thereby allowing easier diffusion of corrosion products away from the crack tip and allowing the crack tip to corrode faster. Active path corrosion processes are inherently limited by the rate of corrosion of the metal at the crack tip, which limits the maximum crack growth rate to around 10-2mm/s, and crack growth rates are often much lower, down to around 10-8 mm/s (about 1 mm in 3 years) or less.

Figure 3(Ref 9)

Figure 4(Ref 9)

Hydrogen Blistering and Hydrogen Embrittlement Hydrogen dissolves in all metals to a moderate extent. It is a very small atom, and fits in between the metal atoms in the crystals of the metal. Consequently it can diffuse much more rapidly than larger atoms. For example, the diffusion coefficient for hydrogen in ferritic steel at room temperature is similar to the diffusion coefficient for salt in water. Hydrogen tends to be attracted to regions of high triaxial tensile stress where the metal structure is dilated. Thus, it is drawn to the regions ahead of cracks or notches that are under stress. Hydrogen blistering is the phenomenon in which the concentration of hydrogen in the voids increases which in turn increases the pressure leading to cracking.

The dissolved hydrogen assists in the fracture of the metal, possibly by making cleavage easier or possibly by assisting in the development of intense local plastic deformation. These effects lead to embrittlement of the metal; cracking may be either inter- or transgranular. Crack growth rates are typically relatively rapid, up to 1 mm/s in the most extreme cases. The bcc (body-centered cubic) crystal structure of ferritic iron has relatively small holes between the metal atoms, but the channels between these holes are relatively wide. Consequently, hydrogen has a relatively low solubility in ferritic iron, but a relatively high diffusion coefficient. In contrast the holes in the fcc (face-centered cubic) austenite lattice are larger, but the channels between them are smaller, so materials such as austenitic stainless steel have a higher hydrogen solubility and a lower diffusion coefficient. Consequently, it usually takes very much longer (years rather than days) for austenitic materials to become embrittled by hydrogen diffusing in from the surface than it does for ferritic materials, and austenitic alloys are often regarded as immune from the effects of hydrogen.

Figure 5(Ref 7)

Film induced cleavage If a normally ductile material is coated with a brittle film, then a crack initiated in that film can propagate into the ductile material for a small distance (around 1m) before being arrested by ductile blunting. If the brittle film has been formed by a corrosion process then it can reform on the blunted crack tip and the process can be repeated. The brittle films that are best-established as causing film-induced cleavage are de-alloyed layers

(e.g. in brass). The film-induced cleavage process would normally be expected to give a transgranular fracture. Anodic dissolution According to this mechanism cracks initiate at the surface sites of localized concentration of tensile strength (trenches, pits). The stress corrosion crack propagates by the following steps: Brittle passive oxide film is ruptured at the crack tip under tensile stress resulting in exposure of fresh metal. The bare metal surface undergoes anodic dissolution. As a result of the corrosion process the crack tip surface is re-passivated forming a new protective oxide film. This passivation and rupturing of oxide film weakens the metal and finally leads to failure.

Surface Modification for Corrosion protection

Generally austenitic stainless steels find wide applications in engineering industries, by virtue of their good mechanical and corrosion resistance properties. It may be difficult to comprehend as to why austenitic stainless steels need surface modification. This is because they suffer from the following considerations :(i) poor wear resistance and risk of galling (ii) susceptibility to sensitization (iii) inferior cavitation erosion resistance (iv) sensitivity towards localized corrosion attack. Hence in applications requiring improved wear resistance, cavitation erosion resistance, resistance to sensitization etc., suitable surface modification techniques are necessary for improved service performance. One of the most commonly used techniques for improved wear resistance is thermo chemical treatment like carburizing, nitriding,and boriding.More recent developments for modifying austenitic stainless steel surfaces using lasers, ion implantation and coatings are also discussed. Thermo chemical Methods Thermo chemical methods involve a change in both the surface chemistry as well as the microstructure by thermal treatments. The most common thermo chemical surface hardening methods involve diffusion of interstitials like carbon, nitrogen or boron on the

surface. Hard case results from the formation of carbides, nitrides or borides respectively. Carburizing Carburizing is a heat treatment process in which iron or steel is heated in the presence of another material (but below the metal's melting point) which liberates carbon as it decomposes. The outer surface or case will have higher carbon content than the original material. When the iron or steel is cooled rapidly by quenching, the higher carbon content on the outer surface becomes hard, while the core remains soft and tough. This manufacturing process can be characterized by the following key points: It is applied to low-carbon work pieces; work pieces are in contact with a high-carbon gas, liquid or solid; it produces a hard work piece surface; work piece cores largely retain their toughness and ductility; and it produces case hardness depths of up to 0.25 inches (6.4 mm). There are different types of elements or materials that can be used to perform this process, but these mainly consist of high carbon content material. A few typical hardening agents include carbon monoxide gas (CO), sodium cyanide and barium chloride, or hardwood charcoal. Nitriding Nitriding is a heat treating process that alloys nitrogen onto the surface of a metal to create a case hardened surface. The processes are named after the medium used to donate nitrogen. The three main methods used are: gas nitriding, salt bath nitriding, and plasma nitriding (ion nitriding). Ion implantation Ion implantation is a materials engineering process by which ions of a material can be implanted into another solid, thereby changing the physical properties of the solid. The ions introduce both a chemical change in the target, in that they can be a different element than the target or induce a nuclear transmutation, and a structural change, in that the crystal structure of the target can be damaged or even destroyed by the energetic collision cascades.

Many surface properties can be improved with ion implantation including hardness and wear resistance, resistance to chemical attack, and reduced friction. The ion implantation process is conducted in a vacuum chamber at very low pressure (10-4 to 10-5 torr). Large numbers of ions (typically 1016 to 1017 ions/cm2) bombard and penetrate a surface, interacting with the substrate atoms immediately beneath the surface. Typical depth of ion penetration is a fraction of a micron (or a few millionths of an inch). The interactions of the energetic ions with the material modify the surface, providing it with significantly different properties than the remainder of the material. Specific property changes depend on the selected ion beam treatment parameters, for instance the particular ion species, energy, and total number of ions that impact the surface. Ion implantation offers numerous advantages for treating component surfaces. A primary benefit is the ability to selectively modify the surface without detrimentally affecting bulk properties, largely because the process is carried out at low substrate temperatures. The process is also extremely controllable and reproducible and can be tailored to modify different surfaces in desired ways..

Figure 6(Ref 10)

Laser Surface Modification The advantage of using lasers for surface treatments is that the entire energy is absorbed within the first atomic layers of opaque materials, such as metals. Further, it can be focused precisely to the specific surface needed only. This makes lasers an

ideal tool for surface engineering. It is chemically clean, remote and non-contact process with feasibility of automation. Also the thermal profile and the distortion and shape and location of the heat affected zone can be controlled very effectively. Laser peening Laser peening, or laser shock peening (LSP), is the process of hardening or peening metal using a powerful laser. Laser peening can impart a layer of residual compressive stress on a surface that is four times deeper than that attainable from conventional shot peening treatments. A coating, usually black tape or paint, is applied to absorb the energy. Short energy pulses are then focused to explode the ablative coating, producing a shock wave. The beam is then repositioned and the process is repeated, creating an array of slight indents of compression and depth with about 5-7% cold work. A translucent layer, usually consisting of water, is required over the coating and acts as a tamp, directing the shock wave into the treated material. This computer-controlled process is then repeated, often as many as three times, until the desired compression level is reached, producing a compressive layer as deep as 1-2mm average.

Laser surface alloying Laser alloying is a material processing method which utilizes the high power density available from focused laser sources to melt metal coatings and a portion of the underlying substrate. Since the melting occurs in a very short time and only at the surface, the bulk of the material remains cool, thus serving as an intimate heat sink. Large temperature gradients exist across the boundary between the melted surface region and the underlying solid substrate. The result is rapid self-quenching and re solidification. Laser Cladding Laser cladding is a method of depositing material by which a powdered or wire feedstock material is melted and consolidated by use of a laser in order to coat part of a substrate or fabricate a near-net shape part. The powder used in laser cladding is normally of a metallic nature, and is injected into the system by either coaxial or lateral nozzles. The interaction of the metallic powder stream and the laser causes melting to occur, and is known as the melt pool. This is deposited onto a substrate; moving the substrate allows the melt pool to solidify and

thus produces a track of solid metal. This is the most common technique; however some processes involve moving the laser/nozzle assembly over a stationary substrate to produce solidified tracks. The motion of the substrate is guided by a CAD system which interpolates solid objects into a set of tracks, thus producing the desired part at the end of the trajectory.

Figure 7(Ref 11)

Surface Coating for Austenitic stainless steels For certain applications it may be necessary to develop overlay of a completely different phase like ceramics, intermetallics etc., on the base material. Coating techniques like thermal spraying, chemical vapor deposition, physical vapor deposition etc are useful in this regard.

Duplex Stainless Steels

A significant contribution to the fight against chloride corrosion has been the introduction of duplex stainless steels as structural materials. DSS combine the basic toughness of the more common austenitic stainless steels with the higher strength and improved corrosion resistance to chlorides of ferritic stainless. As a result, DSS have found widespread use in offshore oil and gas industry in preference to carbon steel or other stainless alloys. In 1986, a new DSS grade called super duplex stainless steels began to be applied in seawater systems. Since then, SDSS have been successful both in cast form and as wrought products .SDSS have higher nitrogen content than standard DSS, i.e., between

0.20% and 0.30%. This nitrogen concentrates mostly in the austenite and exerts a beneficial effect in terms of improved mechanical and corrosion resistance As a consequence, CF performance of SDSS is superior to that of conventional DSS. Classification 1. Lean Duplex such as 2304, which contains no deliberate Mo addition. 2. 2205, grade accounting for more than 80% of duplex usage. 3. 25 Cr Duplex such as Alloy 255 and DP-3. 4. Super Duplex; with 25-26 Cr and increased Mo and N compared with 25 Cr grades, including grades such as SAF2507, Zeron 100, UR 52N+, and DP-3W. SAF 2507 Chemical Composition C - 0.011% Cr - 25% Ni - 7% Mo 3.8% The micro structure consists of 54% austenite and 46% ferrite. The pitting resistance equivalent number (PREN = %Cr+3.3x%Mo+16x%N) is greater than 40. Processing of SAF 2507 Hot forming SAF 2507 should be hot worked between 1875F and 2250F. This should be followed by a solution anneal at 1925F minimum and a rapid air or water quench. Cold Forming Most of the common stainless steel forming methods can be used for cold working SAF 2507. The alloy has a higher yield strength and lower ductility than the austenitic steels so fabricators may find that higher forming forces, increased radius of bending, and increased allowance for spring back are necessary. Deep drawing, stretch forming, and similar processes are more difficult to perform on SAF 2507 than on an austenitic stainless steel. When forming requires more than 10% cold deformation, a solution anneal and quench are recommended. N - 0.24% S - 0.001%

Heat Treatment SAF 2507 should be solution annealed and quenched after either hot or cold forming. Solution annealing should be done at a minimum of 1925F. Annealing should be followed immediately by a rapid air or water quench. To obtain maximum corrosion resistance, heat treated products should be pickled and rinsed. Characteristic properties High strength High resistance to pitting and crevice corrosion High resistance to stress corrosion cracking and corrosion fatigue High resistance to uniform corrosion Good erosion resistance Good fatigue resistance High energy absorption Low thermal expansion Good weldability

Experimental study on SAF2507 Cylindrical specimens with a gauge length of 10 mm and 8 mm dia were machined from the bars. All specimens were mechanically polished with emery paper with increasingly finer grit up to 7.5 m and after with diamond paste up to 1 m. Cyclic deformation tests up to fracture were carried out in a servo hydraulic machine using a clip-on axial extensometer to measure and control strain. All tests were conducted under fully reversed total strain control, at a constant total strain rate of 102 s1 and at room temperature. Three different plastic strain amplitudes (epl/2=6x103, 2x103, and 6x10-4), were chosen for this study. Two different aqueous sodium chloride solutions: one with 30 g/ l NaCl, which is close to the usual seawater content, and another with a higher chloride content (60 g/ l NaCl). In both cases, the pH was 6.5 and the test solutions were at room temperature and open to the environment, i.e., aerated. CF tests were performed at free corrosion potential and, in order to attain potential stabilization, a time of 90 min was left before

beginning to cycle. Moreover, a peristaltic pump was used to ensure a constant-through flow during the whole test. For comparison purposes, tests were also run in air. Damage features in the lateral surfaces of the tested specimens were investigated through scanning electron microscopy. Particular attention was paid to the fatigue damage mechanisms leading to crack nucleation and growth in each environment and in the two constitutive phases. Result

At low strain amplitudes (epl/2=2x103 ) slip bands formed in austenite seem to be the main feature capable of locally destroying the passive film and, therefore, nucleation of fatigue cracks is concentrated on the phase. When fatigue lives for (epl/2=6x104) in air and in seawater are compared a relatively small influence of the corrosive media, i.e., 22% life reduction, is noted. At small plastic strain amplitudes the height of formed extrusions increases quite slowly. Therefore, a high number of cycles are needed to initiate passive film breakdown and then expose the material surface to the corrosive environment. Tests in 60 g/ l NaCl solution led to an important increase in fatigue life, i.e., 60% longer than in air and more than double as compared to seawater. A critical dissolution rate of slip bands by the highly chloride media, which would act as a polishing effect, is proposed as the mechanism responsible for the longer fatigue lives attained in this environment. At high strain amplitudes both phases sustain the plastic deformation. As a consequence, crack nucleation rates are higher and crossing through micro structural barriers becomes easier, leading to short fatigue lives. The participation of both phases in passive film breakdown leads to a more significant influence of the environment with regard to lower amplitudes. After seawater tests, fewer but more intense slip bands are observed in both phases leading to enhanced micro crack initiation Again lives in the 60 g/ l NaCl solution were longer than in air, although this favorable effect was less marked than for low strain amplitudes. Cl ions produce a layer weakening, reducing its thickness and thus promoting an easier breakdown by the emerging extrusions formed during the fatigue process. Therefore, crack nucleation is enhanced and, as a consequence, fatigue life would be reduced.

Table 1(Ref 1)

Figure 8 (Ref1)

Figure 9 (Ref1)

Figure 10 (Ref1)

Figure 11 (Ref1)

Conclusion
The corrosion fatigue mechanisms in austenitic stainless steels were studied in detail. The various surface treatment techniques employed to counter it were also discussed. Austenitic steels fail in the presence of corrosive media like sea water. Super duplex stainless steels perform well even under extreme conditions and hence find use in offshore applications. The reason behind the corrosion resistant property of super

duplex steel was found to be anodic dissolution of the surface roughness generated by cyclic deformation.

References
1. Girons A, Anglada M. and Mateo A. Chloride Content Effect on the Corrosion

Fatigue Properties of Super duplex Stainless Steels J. Eng. Mater. Technol -October 2007 -- Volume 129, Issue 4, 588-593

2. Krishnan K.N. Mechanism of corrosion fatigue in super duplex stainless steel in 3.5 percent NaCl solution, International Journal of Fracture ,88: 205213
3. Girone`s.A., Llanes L., Anglada M.,, Mateo A.,Influence of artificial seawater on

the cyclic response of super duplex stainless steels, International Journal of Fatigue 27 2005,197202. 4. Khatak H.S,Raj B.,Corrosion of Austenitic Stainless Steels,2002. 5. Bosich F.J.,Corrosion prevention for practicing engineers,1970. 6. http://en.wikipedia.org/wiki/Corrosion_fatigue 7. http://www.machinerylubrication.com/Read/573/moisture-contamination-targets 8. http://www.calphad.com/iron-chromium.html 9. http://www.npl.co.uk/upload/pdf/stress.pdf 10. http://www.spirecorp.com/spire-biomedical/surface-modification-technology/ionimplantation.php 11. http://www.thermalspraydepot.com/Laser-Cladding.html