All rights reserved. Comments and correspondence can be directed to Sten von Matérn, Technical Editor, Avesta AB, oO §-77480 Avesta, Sweden, Tel. +46(0)226-81800. ~ - Telex 40976 AVESTA S, telefax +46(0)226-54507. CONTROL DOCUMENT CODE Ka Some Factors Affecting Stainless Steel Corrosion in Seawater by Bengt Wallén, Avesta AB, S-77480 AVESTA, Sweden Abstract Introduction This paper summarizes data from the literature and From corrosion point of view, seawater may be looked from Avesta’s own investigations illustrating the effects _upon as a neutral chioride solution, ie. an environment of different factors on the corrosivity of seawater. The promoting localized corrosion in stainless steels. At the main emphasis is placed on crevice corrosion of stain- moderate temperatures existing in most seawater less steels and on galvanic corrosion in elements systems, crevice corrosion, and sometimes pitting cor- containing stainless steel cathodes. It is established _rosion, are the main hazards. that the microbial activity existing in natural seawater, lays a decisive role and that it explains why a living water is more corrosive than sterile chloride solution. Measures affecting the microbiology, e.g. chlorination or heating, may have considerable influence on the ccorrosivity of the water. The corrosion conditions exist- ing in an anaerobic environment and under cathodic protection are also discussed. ‘Two water types may soem to have the same composi tion but their corroswvity can stil be very different. The reason for this can be attributed to the microorganisms in the water having different effects on the electro- ‘chemical properties of a stainless stee!surtace. The aim of this paper is to illustrate how these microorganisms influence the risks ofcrevice end pitting corrosion under different conditions. Much of the information presented has been produced in Norwegian studies sponsored by Avesta AB and others. FP avesia—Seawater resistant stainless steels Practical experience and numerous corrosion tests have shown that conventional stainless steels are prone to localized corrosion in seawater. Over the last 10-15 years a number of highly-alloyed steels with excellent Corrosion resistance fave been introduced onto the market. Some of the new steels are being used exten- sively in seawater applications, especialy in the sea~ water systems on offshore platforms ‘A common factor of the new steels is a high content of the alloying elements chromium, molybdenum and, in most casos, nitrogen. Attompts have been made to establish a measure of the pitting and crevice corrosion resistance by calculating the sum of the most important alloying elements in a weighed form. This sum is called PRE (pitting resistance equivalent) and a common. ‘expression for austenitic steels is shown below (1). PRE = %Cr + 3.3 x %Mo + 30 x SGN It should be remembered however, that PRE express~ ions are based on accelerated laboratory tests per- formed on perfectly heat treated base material. The effect of various production processes and of welding may completely overshadow the effect of small, or sometimes even larger, differences in the steel compo- sition. A waming for uncritical use ot PRE values, especially for materials selection, is certainly justified (2), The composition of the stainless stee's determines their microstructure which, in turn, affects other prop- erties such as corrosion resistance, mechenical strongth and woldability. Examples of ssawateresis~ tant steels with different structures are shown in table 1 ‘These steels have varying corrosion resistance in many chemicals but their resistance to crevice and pitting corrosion is much the same. The lower part of table 1 shows some conventional steels which, in the following study, are used as reference materials. Welding may have a great impact on corrosion resis~ tance and this is especially true for the resistance to crevice and pitting corrosion of highly-alloyed steels (3, 4), By following the steel producers’ advice regarding welding methods and filler material, satisfactory cor- rosion resistance will be obtained even if the level of the base material is seldom reached. Natural seawater The effects of the biofilm Itwas observed quite early that when astainless steel is exposed in seawater the corrosion potential quickly rises in the noble direction (5, 6). As the example in figure 1 shows, the potential is low at the start of the exposure but ‘reaches a seemingly constant level around 300 mV SCE after a few weeks. After very long exposure times potentials around 450 mV SCE have been measured (5, 8,9). Thisis not far fromthe stan¢ard potential for oxygen evolution which ie around 500 mV SCE at pH 8, Figure 1 also shows that the corrosion potential is inde- pendent of the composition of the stainless steel and, furthermore, that the potential is much lower in a sterile chloride solution like artificial seawater. The same potential increase in natural seawater as with stainless, steels has also been observed with other passive ma- terials such as titanium and NiCrMo-alloys (10, 11). The phencmenon is not restricted to full strength seawater bul has also been established in brackish water (12) and, even river water (13). It has been clearly shown that the potential increase is, connected with the thin microbial slime layer, the so- calledbiofilm, that quickly forms on an inertsurface, and that the biofilm has a strong catalytic effect on the cathodic reaction of the corrosion process, ie. oxygen reduction (5, 6). The anodic reaction, however, seems not to be influenced by the presence of a biofilm (14). ) 256 suo 7 0 SAF 205 100 eS ee ‘Sxposure pond ays) Figure 4 Corrosion potential versus time for stainless steels in natural ‘and artificial seawater at &°C, After Johnsen and Bardal (7) Table 1: Chemical composition and mechanical strength (min. values) of some seawater resistant and conventional stainless steels. Mech. prop. Steel grade Typical composition, % Nimm? @0°C) | Structure Avesta SS UNS |Gnx Cr Ni Mo Cu N Others | Rp0.2 Rm 254SMO 2378 $31254 |.020 20 18 61 O7 02 300650 ‘| Austenite Monit - sagea5 |.020 25 4 4 TH @0 730 _—| Ferrite SAF 2507 2328 $32750 |.030 25 7 4 - 03 550800 _| Duplex 171225 2343 316 050 175 11 26 - — 20-510 __| Austenite 904-2562 NO8904 | 020 20 45 15 - 220 500 _—_—| Austenite 2205-2377 s31803 |.030 22 55 3 - 0.15 480680 __| Duplex ‘COM No. 4-90It a stainless steel is attacked by crevice corrosion, the corrosion potential quickly decreases to -100 to -200 mV SCE and the propagation rate of the attack is determined by the rate of the cathodic reaction oc- curing on intact surfaces of the steel. Figure 2 shows how the cathodic current changes with time when a stainless steel is polarized to potentials lving between 200 and -600 mV SCE (15), Analogous to the rise in the corrosion potential, the current at constant potential increases after a couple of days and reaches a constant level of around 10-20 uAlcm? after a few weeks. If a comparison is made with figure 3 it is evident that the cathodic current density (imAlm? = 0.1 A/cm?) is about two orders of mag nitude greater than that in a sterile chloride solution (7,16). The curvesin figure 2 were determined for specimens that were polarized from the start of the exposure. In practice, this corresponds toa situation where the steel has been galvanicaly coupled to a less noble metal or where crevice cortsion hes occurred very quickly. Normally, however, crevice corrosion is not initiated Until the corrosion potential has risen appreciably, ie when a biofilm has already formed. Such a film does not seem to have ful catalytic activity since a certain time is nevertheless needed before the cathodic current reaches its constant value after the steel surface has been polarized (10) (of. figure 5) The great difference in cathodic efficiency of steel surfaces exposed to natural and artificial seawateris no doubt due to the catalytic action of the biofilm. A generally accepted model of the mechanism involved dozs not however seem to exist (6, 13, 17). Factors affecting the biofilm Ofthe factors investigated, just a few will influence the catalytic activity of the biofim (14) and the greatest effect is no doubt exerted by the temperature (18), Figures 4 and 5 show that if cold seawater (Trondheim) is heated, the bioflm loses its activity somewhere between 24 and 32°C. In water from the Norwegian south coast (Sandefjord) high corrosion potentials, indicating an active biofilm, have been recorded at 30°C (19). In warmer water (Genua) the activity is not completely lost until the temperature reaches 40°C (17). tis quite clear that there is a critical temperature or temperature range but thet this is dependent on the microbiology of the seawater. ‘The other factor that might have an effect on the biofilm is the flow rate of the water. In this case, however, dif- ferent investigations arrive at different results. In one study it is stated that no active biofilm develops if the flow rate exceeds 2 m/sec (5) while another finds that 46 m/sec does not reduce the activty (7). Practical consequences It has been shown that in natural seawater stainless steels have more noble corrosion potentials and higher Current densities at cathodic polarisation than in corre~ sponding sterile water. A high corrosion potential in- creases the risk for initiation of crevice and pitting corrosion while a faster cathodic reaction means higher propagation rate of the attack. Consequently, natural living seawater is considerably more corrosive than artificial seawater of sodium chloride solutions, coe Time tay) Cathodic current density versus time for 254 SMO in natural seawater at 9°C, After Holthe et al (18). mm wm 2 Figure 3 posure period (days) Cathodic current density versus time for 254 SMO in 3% Sodium chloride at 20°C. Polarization to ~300 mV SCE. After Jonnsen and Bardal (7) 350 180 Figure 4 me (sys) Cerrosion potential versus time for 254 SMO in natural sea weter at different temperatures. After Holthe et al (18). VaESNEGTesy tate Scene) ress Time days) Cathodic current density versus time for 254 SMO in natural seawater at different temperatures. Polatization to +100 mV SCE. The specimens were pre-exposed at the corrosion potential for 14 days. After Holthe et al (15). com No. 4-90The fact that the activity of the biofilm ceases at a certain temperature means that the corrosion risks should be greater in cold water than if the same water has been heated to a temperature exceeding the citi- cal one. A crevice corrosion test illustrating this stu- ation is shown in table 2 (19).Itis true that the conven- tional steels 316 and S04L are attacked at both 25 and 70°C but the attack is much deeper at the lower tem- perature in spite of the exposure time having been halved. Table 2: Crevice corrosion (MCA washers) in natural seawater at two temperatures. 25°C, 8 months 70°C, 6 months Max, Max. Steel! | Attacked | depth | attacked | deptn grade | specimens [mm — | specimens | mm 2343 | Soutot 3 [1 Soutof 8 | 008 eos | outof 3|15 |3outof 3 | 003 254 smo | O out of 15 | = Tout or 15 | 10, 30 min/d. 40 continuous | 1.5-2 45 continuous | 05 ‘As mentioned in the previous section the galvanic cor- rosion of a less noble metal coupled to stainless steel is very much influenced by chlorination. Figure 12 shows that the corrosion rate of 90-10 copper-nickel, coupled to 254 SMO, is much higher in unchlorinated water (32). Intermittent chiorination reduces the galvanic corrosion rate considerably so that this is of the same magnitude as the free corrosion rate of copper-nickel even at a high area ratio, When 316 was used instead of 254 SMO {at 6:1 area ratio) the galvanic corrosion rate was not changed significantly. Polluted water Cleanseawater contains many kinds of microorganisms which, under special conditions, may cause corrosion on metallic materials (33). In practice the organisms most dangerous to stainless steels are the sulphate- reducing bacteria which receive their energy by re~ ducing sulphate ions to hydrogen sulphide while simul- taneously oxidzing organic substances. The growth of these bacteria is promoted by anacrobic conditions which, for instance, exist in bottom sediments contain- ing decomposing organic matter. In severely polluted harbour or estuarine water the hydrogen sulphide level ‘can reach 50 ppm or more (20) and in bottom sediments 200-300 ppm have been measured (34). Several investigations show that hydrogen sulphide stimulates the anodic reaction in the corrosion process of stainless steels. The active corrosion rate of 304 is increased and the active corrosion peak in the polariz~ ation curve becomes broader when a strongly acid sulphate solution is saturated (750 ppm) with hydrogen sulphide at 60°C (35). Pitting corrosion in chloride solutions is also affected and the pitting potential of 304 decreases continuously when the hydrogen sulphide concentration increases from 170 to 3400 ppm (36). Furthermore, stainless steels containing up to 42% molybdenum have much lower pitting potentials in a chloride solution if this is acid (pHi 4) and saturated with hydrogen sulphide (3000 ppm) than if itis neutral and saturated with nitrogen (1). Accordingly, very high levels of hydrogen sulphide lower the pitting potential of a stainless steel and increase the rate of the active corrosion existing in tho pit. However, hydrogen sulphide is a strong reductant ‘which lowers the corrosion potential so potentials inthe region ~400 to ~480 mV SCE have been measured on com No. 4-0 ‘rea ratio, 258 SMO: 90-10 CUNI Figure 12 Corrosion rate of 90-10 CuNi versus area ratio in the galvanic ‘element 254 SMO/copper nickel. Natural seawater with differ- ‘ent chlorine concentrations. 90 days at 35°C. stainless steel specimens buried in bottom sediment (20, 34), These low potentials mean that the risk of initi- ation of crevice and pitting corrosion will decrease. The question is which effect will dominate for seawater resistant steels in neutral water containing moderate amounts of hydrogen sulphide. In our laboratory the risk of crevice corrosion on the grade 254 SMO has been investigated in a neutral Chloride solution (2.2% Cr) containing 90 ppm hydro- gen sulphide at ambient temperature (19). The cor- rosion potential was around 430 mV SCE and no corrosion could be detected. When investigating the Corrosion conditions in sour oil and gas wells, tests have also been performed at higher temperatures (19). Ina slightly acid chloride solution (2% Cl-) the effect of hydrogen sulphide was investigated at 150°C. When the hydrogen sulphide partial pressure was 045 bar no corrosion occurred on 254 SMO and only sight pitting was observed at 1 bar partial pressure. Against these positive results stands the fact that pitting corrosion has been noticed on 904L in harbour water containing large amounts of sulphate-reducing bacteria (37) Thus, there are strong indications that the most highly- alloyed stainless steels are resistant in seawater evenif this contains high levels of hydrogen sulphide. However. no confirming investigation, carried out in the natural environment, seems to have been reported. Cathodic protection and hydrogen embrittlement Naturally, cathodic protection of seawater-resistant stainless steels is not necessary. However, such stees might be included in a protection system if they are parts ofa construction in which other components have to be protected. One example of this is the subsea templates in the offshore industry. Another example exists in power plant condensers when stainless steel tubes have been rolier-expanded into tube sheets made of bronze and brass. Intentional protection of the stainless steel does exist however. In the offshore industry ‘lowlines, placed on ‘the bottom of tho soa, transport corrosive oil and gas from satellite platforms to the main platform. in this case the choice of material is determined by the environ ‘ment inside the fiowline and this seldom justifies a sea~water-resistant steel. Therefore, cathodic protection of the outside of the fiowline is often necessary in spite of an extensive passive corrosion protection, In cathodic protection with sacrificial anodes, there are always parts of the object where the potential is more negative than the reversible potential of hydrogen evolution, 80 significant hydrogen evolution always takes place. Under such circumstances certain alloys may pick up hydrogen and thus suffer embrittlement and cracking, The risks particulary creat ifthe material is cold worked and subject to high mechanical stresses and fatigue loading It has been reported thatin the off- shore industry, cracking has occurred in bolts made of Monel K-500 and inconel 625 (wrongly heat treated) (G8). Cracking due to hydrogen embrittlement has also ‘occurred in power plant condensers in tubes made of ferritic stainless steels, which have been roller-ex- panded into less noble, cathodicaly protected tube sheets (39). Quite recently an investigation of the sensitivity to hy- drogen embrittlement of three bolt materials of current interest for the offshore industry has been reported (40). In this investigation the slow strain rate technique was used in two environments, air and artificialseawater with cathodic protection at -1030 mV SCE. The alloys tested were two seawater-resistant steels, one austen- Itlc (284 SMO) and one duplex (SAF 2507), together with Monel K-50. The results are shown in table 4. ‘The austenitic steel is not influenced by seawater and cathodic protection in spite of being cold worked to 30%. However, a clear embrittling effect is observed on the duplex steel and especially on Monel K-500. The conclusions concerning the austenitic and the duplex steels have been confirmed by other investigations (41). The phenomenon needs further investigations but a certain cautiousness is recommended if severely Cold-worked duplex stainless steels are used in sea- water constructions equipped with cathodic protection. Table 4: Results from slow strain rate testing of poton- tial bolt materials inair and in artificialseawater with cathodic protection. Temperature 11°C. After Bardal et al (40) Max. sitess, | Elongation, | Reduction MPa % in 22mm | of area Alloy Air Sea- | Air Sea | Ar Sea- water water | water +0P +P OP 254smo_— | 1163 1167 | 159 158 | 65 70 ‘SAF 2507, 952 950 | 40.0 36.2 | 70 54 Monel k-500 | 1097 1034 | 289 20.3 | 35 17 Conclusions The biofilm that is quickly formed on stainless stee! sur- faces exposed to natural seawater has a catalytic effect on the oxygen reduction reaction. This results in more noble corrosion potentials and an increased cathodic efficiency at cathodic polarization. This explains why crevice and galvanic corresion is more vigorous in natural water than in a corresponding sterile water. The biofilm loses its catalytic effect if the water is heated to a critical temperature which, depending on the microbiology of the water, lies in the region 30- 40°C. If this temperature is exceeded, the corrosivity of the water is considerably reduced, In chlorinated water the corrosion potential is higher than in unchlorinated water, at least if the residual chlorine concentration exceeds 0.1-0.2 ppm. Therefore the tisk of crevice corrosion initiation is groater in chlorinated water and the risk increases with ncreasing temperature. However, chlorination prevents the formation of en active biofilm so the cathodic efficiency is considerably less than in unchlorinated water. Therefore the propa- gation rate of crevice attack and the rate of galvanic corrosion is much lower than in unchlorinated water. Hydrogen sulphide, which may be produced by su- phate-reducing bacteria under anserobic conditions, stimulates the anodic reaction in the corrosion process, On the other hand, the corrosion potential becomes very low in the presence of hydrogen sulphide and ths reduces the risk of crevice corrosioninitiation The most highly-alloyed stainless steels should be resistant to seawater even at higher hydrogen sulphide concentra- tions. Cathodic protection introduces a risk of hydrogen embrittlement of certain types of stainless steels. However, seawalerresistant, austenilic steels seem immune to embrittiement even in a highly cold-worked condition References 1. Herbsleb G Werksioffe und Korrosion, 33 (1982), p 334-40 2, Shone E B, Malpas RE, Gallagher P Trans.IMar. E 100 (1988), p 183-206 3. Gamer A, Welding Journal 62 (1989): 1, p 27-34 4, Lillas M, Holmberg B, Ulander A Proceedings Stainless Steels ‘84, Gothenburg, Sweden, Sept 3-4, 1984, p 323-29 5, Mollice A, Trevis A Proceedings 4th International Congress on Marine Cor rosion and Fouling, Antibes, France, June 14-16, 1976, 951-65 8. Johnsen R, Bardal E, Drugli J M Proceedings 9t1 Scandinavian Corrosion Congress, Copenhagen, Denmark, Sept 12-14, 1983, Vol 1, p 371-82 7, Johnsen R, Bardal E Corrosion/86, Peper No 227 8, Holthe R, Gartland P ©, Bardal E Proceedings 7th Intemational Congress on Narine Cor rosion and Fouling, Valencia, Spain, Nov 1988 9. Gallagher P, Malpas R E Corrosion/89, Peper No 113 10, Bardal €, Johnsen Proceedings UK Corrosion/86, Birmingham, UK, 1986, p 287-299 11, Mollica A et al Int Biodeterior, 24 (1988): 4-5, p 221-30 12. Vatjonen O et al Proceedings 11th Scandinavian Corrosion Congress, Stavanger, Norway, Juno 19-21 1989, Papor no F-67 18, Dexter$ ©, Zhang Hod Proceedings 11th International Corrosion Congress, Florence, italy, April 2-6, 1990, Vol. 4, p 4.339-4.340 14, Holthe R ‘Thesis, Norwegian Institute of Technology, Trondheim, Norway, Oct 1988 acom No. 4-9015. Holthe R, Bardal E, Gartland P.O Materials Pertormance 28 (1989): 6, p 16-23, 16, Mollica A et al Proceedings @th International Congress on Marine Cor rosien and Fouling, Athens, Groccs, 1964, p 269-81 17. Mollica A et al Corrosion 45 (1989): 1, p 48-56 18, Holthe R, Gartiand P O, Bardal E Proceedings Eurocorr 7, Karlsruhe, Germany, Apri, 1987, p 617-23 19. Wallén B, Abrehamsen T Proceedings Highly Resistant Stainless Steo's and Metal Alloys at Sea, Oslo, Norway, Jan S0-Feb 1, 1984, NITO, Oslo, 1984 20. LaQue, F Marine Corrosion, John Wiley & Sons, New York, 1975 21. 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Malpas R E, Gallagher P, Shone EB Proceedings Chlorination of Seawater Systems and its effect on corrosion, Birmingham, UK, Mar 4, 1986, Paper ‘TRCP.2919R, Soc of Chem Ind, 1986 acom js distributed free of charge to persons actively involved in the development of the processing industry and other areas where stainloss stools are important. 28, Wallén B, Abrahamsen T Proceedings Stainless Steels ’84, Gothenburg, Sweden, ‘Sop 3-4, 1984, p 463-70 29. Johansen B et al Proceedings 10th Scandinavian Corrosion Congress, ‘Stockholm, Sweden, Jun 2-4, 1986, p 135-142 30. Malpas R E, Galagher P, Shone EB Proceedings Stainless Steels '87, York. UK. Sep 14-16 1987 31, Ventura G, Traverso E, Mollica A Corrosion 45 (1989): 4, p 319-25 82 Wallén B, Henrikson S Werkstoffe und Korrosion 40 (1989), p 602-15 38, Schumacher M (e d) Seawater Corrosion Handbook, Noyes Data Corporation, New Jersey, 1979 34, Mollica A et al Corrosion 44 (1988): 4, p 194-98 35, Herbsleb G, Schwenk W Werkstoffe und Korrosion 17 (1966), p 745-50 36, Newman R C, Isaacs HS, Alman B Corrosion/89, Paper No 186 37. Scott P J B, Davies M Corrosion 38 (1882): 5, p 261-65 38. Johnsen R Proceedings 11th Scandinavian Corrosion Congress, Stavanger, Norway, Jun 19-21, 1989, Paper No F-52 39. Grubb JF, Maurer J R Corrosion/84, Paper No 28 40, Bardal E et al Proceedings Fetigue 90, Honolulu, Hawai, Jul, 1990, p 1875-80 44, Henrikson Swedish Thermal Engineering Research Association, Report No 339, 1989 (in Swedish) acom appears four times ayear, and we welcome your application, as well as additional applications from your friends and colleagues. 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