Stainless Europe

Stainless Steel and Corrosion
What is corrosion?
Metals, with the exception of the precious metals such as gold and platinum, that are found in their natural state are always extracted from ores; metals have therefore a tendency to revert to their stable state, which corresponds to their original state, that is to say their oxide form. Metal corrosion is essentially an electro-chemical reaction at the interface between metal and surrounding environment . Stainless Steel and the passive layer Steel is an alloy of iron and carbon. Contrary to carbon steel, the presence of a minimum of 10.5 % chromium in the stainless steel gives it the property of corrosion resistance.
The Composition of Stainless Steel It is the chromium which gives the stainless quality to our steels.

What are the major factors of corrosion?
MediuM
Chemical nature Concentration Oxidising power pH (acidity) Temperature Pressure Viscosity Solid deposits Agitation Composition Manufacturing Metallurgical state (thermal or mechanical treatment) Additives Impurities

design
Surface state Shape Assembly (welds, rivets) Mechanical stresses Proximity to other metals Contact with a medium (partial or total immersion) Methods of protection

Corrosion
Ageing of the structure Evolution of stresses Temperature variability Modification of coatings Maintenance frequency
faCtors

Material

tiMe

Chromium >10,5% Iron Carbon <1,2% Fe+C=steel Fe+C+Cr=stainless steel

What are the 5 principal types of corrosion linked with the surrounding environment ?
generalised loCalised

Indeed, on contact with oxygen, a chromium oxide layer is formed on the surface of the material. This passive layer protects it and has the particular ability to self repair.
Reaction of steel and stainless steel in contact with moisture in the air or water. Steel Formation of iron oxide (rust) Stainless Steel
neutral Chloride environMent

Pitting

CreviCe

O2

Formation of chromium oxide

under
stress

Fe + C

Fe + C + Cr > 10,5 %

Rust Passive layer

generalised
aCid MediuM

intergranular

However if this protective layer is damaged, the start of corrosion can appear

400 K03 K09 K10 Martensitic K30-K31 300 To simulate this type of corrosion under laboratory circumstances.4509 1.4521 1. Passive layer Metal If the potential of the stainless steel in the given medium is superior to the pitting potential =>the stainless steel corrodes Note: the higher the pitting potential.4016 .1 301 301LN 304L 316 .Generalised corrosion is noticed when stainless steel is in contact with an acid medium and localised corrosion is seen in the majority of cases when stainless steel is placed in a neutral chloride environment In the document which follows we describe the 5 principal types of corrosion and we rank the majority of Stainless Europe grades from standard laboratory tests However.4318 1. corrosion will develop if the pit does not re-passivate. It shows the influence on the resistance to pitting corrosion with the content of chromium and molybdenum for the ferritics.2 201LN 201.4512 1. a sample is immersed in a corrosive electrolyte to which an increasing potential is applied until the passive layer is broken.4618 1.4003 1.4404 1. Figure 1 shows pitting potentials obtained for different stainless steels in water containing 0. where the metal is unprotected. Pitting Corrosion To understand the phenomenon Pitting corrosion is a local break in the passive layer of the stainless steel provoked by an electrolyte rich in chloride and or sulphides. and chromium. the data described does not exclude extra trials to choose the optimal material.3%Mo+16%N) Commercial designations Martensitic K09 K03 K10 K30-K31 K39 K41 K36 K45 K44 16-4Mn 16-5Mn 17-4Mn 17-7A/C/E 18-7L 18-9L 18-11 ML 17-11MT Norms ASTM Type Standards EN 1.4510 1.4310 1. At the site of the pitting. Outside the pits. the phenomena of corrosion in real life are always specific. better shall be the corrosion resistance of the grade.4371 1. molybdenum and nitrogen content for the austenitics.1.4307 1. the passive layer is always present to protect the stainless steel.02MNaCI pH=6. During this dynamic potential (intensity/potential) scan the sudden increase in intensity corresponds to the pitting potential Epitting INTENSITy I =50µA/cm2 200 10 12 14 16 18 20 22 24 26 PREN (%Cr+3. If the potential of the stainless steel in the given medium is inferior to the pitting potential => pitting does not start .4401 .4372 1.4021 1. mV/SCE METAL ATTACK Chlorides Passive layer Metal Figure 1 K44 800 Pitting potential in water containing 0.4000 1.6 at 23°C (mV/SCE ) 2nd case 700 17-11MT 18-11ML The metal re-passivates passive layer Metal Corrosion of the base metal 600 18-9E/L 18-10T 17-7A/C/E K41 K39 K45 K36 18-7L 17-4Mn 16-4Mn 16-5MnL 500 This dissolution gives rise to metal ions and electrons and thus the passage of current (of dissolution) which gives rise to an electrical potential difference between the anodic zone (pitting) and the cathodic zone (the rest of the metal).4571 420 409 410S 430 439 441 436 445 444 201.4526 1.1.4621 1. in other words if the speed of metal dissolution enables to maintain a sufficiently aggressive environment to prevent its re-passivation.4017 1.02M NaCl (710mg/l Cl-) at 23°C.316 L 316Ti Epitting Passive field POTENTIAL The pitting potential corresponds to the potential necessary to initiate stable pits.

As figures 2 and 3 show.5M NaCI pH=6. at 23°C and 50°C (mV/SCE) Normes Appellations commerciales ASTM Designation Type DX2202 DX2304 DX2205 2202 2304 2205 UNS UNS 32202 UNS 32304 UNS 32205 1. this pitting potential can only be used to rank the grades in a given medium.6 at 23°C (mV/SCE) Pitting potential in water containing 0. a confined (occluded) zone linked for example to bad design. limiting contact time. tests in the most severe medium. The PREN. Pitting potential in water containing 0.6 at 50°C (mV/SCE) 500 K44 600 500 400 K39 18-9E/L 450 400 350 300 250 200 150 100 50 0 K03-K09-K10 K30 K41 K39 18-9E/L K36 18-11ML K44 18-11ML K41 K36 300 K30 200 100 0 K03-K09-K10 10 12 14 Figure 2 PREN (%Cr+3. The results obtained are shown below. Crevice Corrosion To understand the phenomenon A/ Initiation of corrosion In an electrolyte high in chloride.75g/l Cl-) at 50°C. demonstrates the major influence of these alloy elements.02M NaCI pH=6. favours the accumulation of chloride ions. %Cr+3. 0.4362 1. We would choose a grade high in chromium or containing molybdenum. WHy? Confined zone (acidification) HOW? Break in the passive layer and metal attack .5M NaCl.3%Mo+16%N) 16 18 20 22 24 26 In order to map the duplex range.4462 EN Figure 4 Usually we use the PREN (Pitting Resistance Equivalent Number) of the grades to rank their general piting behaviour. It diminishes notedly when the temperature (figure 2) or the concentration of chlorides in the medium increases. When the pH in this zone reaches a critical value called « depassivation pH ».5M NaCl (17. were carried out. avoiding stagnant areas and reducing the concentration of halogens and the presence of oxidants.3%Mo+16%N . Our Recommendation To avoid pitting corrosion: We would look to see if it is possible to lower the corrosiveness by lowering the temperature of the medium.corrosion starts.4062 1. The depassivation pH or pHd is used to characterize the resistance to crevice corrosion initiation. The progressive acidification of the medium in this zone facilitates the de-stabilisation of the passive layer. (figure 3) 700 Pitting potential in water containing 0.3%Mo+16%N) 16 18 20 22 24 26 10 12 14 Figure 3 PREN (%Cr+3.

gaps between two plates etc. deposits. . Consequently.5 1 2500 K03/K09/K10 Martensitic 2000 K30/K31 K41 0. For unstabilized ferritic stainless steels. its propagation occurs by active dissolution of the material in the crevice. the sensitisation temperature is greater than 900°C. nickel and chromium (see figure 6 ).5 10 15 PREN (%Cr+3. These carbides have a higher chromium content in comparison to the matrix. 1. An artificial crevice can be created by a badly made joint.4%Ni Our Recommendation Our first recommendation to avoid crevice corrosion is to optimise the design of the piece to avoid all artificial crevices. a rough or bad weld. The sensitisation state takes place in a lot of environments by privileged initiation and the rapid propagation of corrosion on the de-chromed sites.Some pHd values for our stainless steels are given in figure 5. crevice corrosion is starting . we simulate this type of corrosion by recording the potentiodynamic scans in chloride mediums of increasing acidity. The speed of propagation is also a function of local aggressiveness and temperature of the medium. If the confined zone is unavoidable. If the design of the pièce is not modifiable or if the fabrication process makes difficult to avoid confined zones. choosing an appropriate grade. Critical current «icrit» at the peak of activity for various stainless steels in NaCl 2M (71g/l de Cl-) de-aerated and acidified with HCl at 23°C. it is preferable to enlarge this zone and not to make it smaller. This value is sensitive to the alloy elements which improve the passivity and limit active dissolution. We recommend. principally molybdenum. when these materials are cooled slowly from these temperatures or even heated between 425 and 815 °C. Intergranular corrosion To understand the phenomenon At temperatures greater than 1035°C . in this case. Activity peak measurement for a pH lower to the depassivation pH can then be considered to quantitatively compare the speed of crevice corrosion propagation for different grades. in particular a stainless steel austenitic or duplex when the product will be in contact with corrosive media or part of the process equipment. the zone directly adjacent to the grain boundaries is greatly impoverished. The lower the value pHd the better the resistance to crevice corrosion.3%Mo+16%N) K39 20 25 30 35 1500 K45 1000 B/Propagation of corrosion Once corrosion is initiated. If on a recording we detect a current peak (activity).5 3 2. the carbon is in solid solution in the matrix of the austenitic stainless steels. However.5 2 Figure 6: Critical current «icrit» at the peak of activity for various stainless steels in NaCl 2M (71g/l de Cl-) deaerated and acidified with HCl at 23°C. Figure 5: Depassivation pH of various stainless steels in NaCl 2M (71g/l Cl-) de-aerated and acidified with HCl at 23°C 4 Depassivation pH of various stainless steels in NaCl 2M ( 71g/l Cl-) de-aerated and acidified with HCl at 23°C 3. chromium carbides precipitate at the grain boundaries.2%Cr+%Mo+0.. 500 164Mn 165MnL 174Mn K44 DX2202 187L DX2304 177A 1898 1810T 1810L 1811L 1711MT 1812MS 1813MS DX2205 0 1 3 5 7 9 11 13 0. the risk of crevice corrosion is very high . In the laboratory. in the opposite case repassivation takes place.

The austeno-ferritic structure of the duplex gives them an intermediate behaviour. As shows the graph below. their body cubic centred structure rarely renders them subject to this type of phenomena in practice . and the titanium or niobium stabilized ferritic grades.the applied or residual stresses . the austenitic stainless steels with manganese perform worse. favouring as a solution a ferritic or duplex but bearing in mind the other corrosion problems encountered . Interscience.% 60 80 Our recommendation To avoid this type of corrosion : Suppress the stresses or have a better redistribution. choose the grade most adapted. since stress corrosion rarely develops under 50°C . New York.] . The solution for the austenitic consists of using a low carbon grade called « L » (Low C%<0.temperature.Our recommendation In practice . H2S or caustic media NaOH Although stress corrosion of ferritics can be provoked by particularly aggressive tests in the laboratory . by optimising the design or by a stress relieving treatment after forming and welding of the pieces concerned. The volume of the piece permiting a thermal treatment of the quenching type (rapid cooling) at 1050/1100°C or a tempering of the welded piece can be done. wt. 1000 Aggressive medium PASSIVE LAyER Chlorides Temperature effects Cracking No cracking STAINLESS STEEL STRESS STAINLESS 100 Time to crack (hours) PASSIVE LAyER STAINLESS CRACKS 10 The metallurgical structure of stainless steels influences their behaviour in this type of configuration 1 0 20 40 Nickel content. In effect . 247 (1959). The face cubic centred structure of austenitic stainless steels can present a risk. In austenitic stainless steels. this case of corrosion can be encountered in the welded zones .the corrosiveness of the medium : presence of Cl-. This particularly dangerous phenomenon is the result of the combined effects of 3 parameters: . an increase in nickel above 10% is beneficial . it favours a mode of planar deformation which can generate very strong stress concentrations locally. Stress Corrosion To understand the phenomenon We mean by « stress corrosion » the formation of cracks which start after a period of long incubation and which afterwards can propagate very rapidly and provoke downtime of the equipment by cracking .03%) or a stabilized grade. very close to the ferritics in the chloride medium and even better in the H2S medium . lower the temperature if possible If not practicable. Effect of nickel content on the resistance to stress corrosion of Stainless steel containing from 18-20% chromium in magnesium chloride at 154°C [ From a study by Copson [ref] . this is particularly true for classic austenitic stainless steels with 8% nickel. Physical Metallurgy of Stress Corrosion Cracking.

ArcelorMittal .agencembcom.01 K09 K03 K30 K41 K39 K45 K44 16-4 18-9E 17-4 18-11 Mn Mn ML Pre-passivity Up Activity Immunity M Figure 7: Critical current «icrit» at the peak maximum in H2SO4 2M de-aerated at 23°C B Current density (I) UP = Cathodic curve Anodic curve Pitting potential In a low oxidising medium.1 Passivity 0. ArcelorMittal . Our recommendation To avoid this type of corrosion.Stainless Europe. 100 10 Polarization curve in an acidic medium 1 Potential U Transpassivity 0.Stainless Europe. While everycare has been taken to ensure that the information contained in this publication is as accurate as possible. the cathodic curve (B) cuts the anodic curve above the pitting potential: pits appear on the surface of metal. An increasing potential scan is imposed on the metal and the corresponding intensity is recorded. choose the appropriate grade in regard to the acid medium used.Stainless Europe. :+33 1 71 92 06 52 Fax : +33 1 71 92 07 97 www.Uniform corrosion To understand the phenomenon This is the dissolution of all the affected points on the surface of the material which are attacked by the corrosive medium. Indeed.com/stainlesseurope © March 2010. Design and conception: www. In a strong oxidising medium. We note the favourable impact of chromium and molybdenum which reinforce the existing passive film but also the combined effect of noble alloys (nickel. Generally. registered in numerous countries. In the laboratory. in common with all ArcelorMittal Group companies. below a critical pH value.eng. thus the less the grade will be resistant. KARA™ is a trademark of ArcelorMittal . the faster and greater the dissolution.com . the higher the current. we measure this speed of corrosion in an acid medium by graphing the polarisation curve (see below). the cathodic curve (M) cuts the anodic curve below the pitting potential: metal remains intact. The more acid the medium. the faster the corrosion and the loss of thickness of the stainless steel. Fiche Corrosion.arcelormittal. molybdenum and copper) which slow down the dissolution of the material when the stability of its passive layer is broken. the passive layer protecting the stainless steel is no longer stable and the material suffers a generalised active dissolution.this corresponds to a regular uniform loss of thickness or loss of weight (uniform or generalised corrosion as opposed to localised corrosion). We see this corrosion in acid mediums. The maximum current reading of the activity peak allows us to classify the resistance of different grades to this type of corrosion (see figure 7). On the micrographic scale. cannot guarantee that it is complete nor that it is free from error. Head office ArcelorMittal Paris Stainless Europe 1-5 rue Luigi Cherubini FR-93212 La Plaine Saint Denis Cedex Information Tel.

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