IBP1265_12 RELATIVE MERITS OF DUPLEX AND AUSTENITIC STAINLESS STEELS FOR APPLICATIONS IN THE OIL & GAS INDUSTRY

Elisabeth Johansson1, Lena Wegrelius2, Rachel Pettersson3

Copyright 2012, Brazilian Petroleum, Gas and Biofuels Institute - IBP

This Technical Paper was prepared for presentation at the Rio Oi & Gas Expo and Conference 2012, held between September, 1720, 2012, in Rio de Janeiro. This Technical Paper was selected for presentation by the Technical Committee of the event according to the information contained in the final paper submitted by the author(s). The organizers are not supposed to translate or correct the submitted papers. The material as it is presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute opinion, or that of its Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Oil & Gas Expo and Conference 2012 Proceedings.

Abstract
The broad range of available stainless steel grades means that these materials can fulfil a wide variety of requirements within the oil and gas industry. The duplex grades have the advantage of higher strength than standard austenitic grades, while the superaustenitic grades provide a cost-effective alternative to nickel-base alloys in a number of cases. The paper presents the results of various types of laboratory testing to rank the grades in terms of resistance to pitting, crevice corrosion and stress corrosion cracking. Results from field testing in actual or simulated service conditions are discussed and a number of application examples, including process piping flexibles, heat exchangers and topside equipment are presented.

1. Introduction
The entire spectrum of stainless steels is used in oil and gas production. The range extends from the lowestalloyed lean grades to the high-alloyed high performance stainless steels which are often an attractive alternative to nickel base alloys. This extensive range exists both for alloys with austenitic microstructure and alloys with duplex microstructure. As this paper will show, each category has characteristic strong points that should be considered when specifying stainless steel for oil and gas production. Results from laboratory corrosion test will be presented together with corrosion tests in seawater and sour service conditions. Finally, a number of application examples will discuss the merits of austenitic and duplex grades in the oil and gas industry. Austenitic stainless steels include standard austenitic grades such as 316L as well as superaustenitic grades. In the 1970s, 6Mo grades such as 254 SMO was introduced (Fredriksson et al., 1985). The high molybdenum content together with increased levels of chromium (20%) and nitrogen (0.20%) gave this grade excellent corrosion resistance and improved mechanical properties. Other alloys with even higher alloying contents were later developed such as 4565 (Guempel et al., 1988). Despite the lower level of molybdenum (4.5%) this grade exhibits increased corrosion resistance because of the higher levels of chromium (24%) and nitrogen (0.45%). The high nitrogen solubility for 4565 is achieved by alloying with manganese (5.5%). To overcome limitations under very harsh conditions, the second generation superaustenitic stainless steel 654 SMO was developed by further increasing the levels of chromium (24%) and molybdenum (7.3%) which made it possible to reach an even higher nitrogen content (0.5%) (Walln et al., 1992). 654 SMO is still one of the highest alloyed austenitic stainless steel grades produced to date. The duplex grades have a two-phase structure comprising both austenite and ferrite. The 2205 grade can be considered the modern prototype of duplex stainless steels and contains 22% chromium, 5.7% nickel and 3.1% molybdenum. From this grade, both leaner and more highly alloyed grades have been developed. In the higher alloyed grade 2507, molybdenum (7%) and nitrogen (0.3%) were the main elements used to increase corrosion performance (Berhardsson et al., 1985). The leaner grade 2304 has low content of molybdenum (0.3%) and nitrogen (0.1%), resulting in a lower corrosion resistance (Berhardsson et al., 1984). More recently even leaner grades such as LDX 2101 have been developed with a very low nickel content (1.5%) (Alfonsson et al., 2000). Instead, manganese (5%) is

______________________________ 1 Ph.D. Outokumpu Stainless AB 2 Ph.D. Outokumpu Stainless AB 3 Ph.D Outokumpu Stainless AB

Rio Oil & Gas Expo and Conference 2012 used to balance the duplex microstructure and the nitrogen content (0.2%) ensures that the corrosion resistance is sufficient. The stainless steel grades described and evaluated in this paper are shown Table 1 with their chemical compositions and some properties. As seen in the table, the duplex grades generally have a much lower nickel content compared to the austenitic grades. Moreover, duplex grades have higher yield strength than the austenitic grades, while the elongation is higher for the austenitic grades. For stainless steels the most important alloying elements for corrosion resistance, and particularly localized corrosion resistance, are chromium, molybdenum and nitrogen. In order to obtain a rough ranking of stainless steels with regards to their corrosion performance the Pitting Resistance Equivalent (PREN) can be used. As defined by the ISO 15156-3 standard the PREN is calculated according to Equation1 (ISO, 2009): PREN = %Cr + 3.3 (%Mo + 0.5 %W) + 16 %N (1)

As shown in Table 1 the range of PREN values, and thus the corrosion resistance, cover a wide range for both austenitic and duplex grades. Table 1. Stainless steel grades Grade 316L LDX 2101 2304 2205 2507 254 SMO 4565 654 SMO
# ##

UNS S31603 S32101 S32304 S32205 S23750 S31254 S34565 S32654

EN 1.4404 1.4162 1.4362 1.4462 1.4410 1.4547 1.4565 1.4652

Typical chemical composition[wt%] Cr Ni Mo N C Others 17.2 21.5 23 22 25 20 24 24 10.1 1.5 4.8 5.7 7 18 17 22 2.1 0.3 0.3 3.1 4 6.1 4.5 7.3 0.22 0.10 0.17 0.27 0.2 0.45 0.5 0.02 0.03 0.02 0.02 0.02 0.01 0.02 0.01 5Mn Cu 5.5Mn 3Mn, Cu

Microstructure Austenitic Duplex Duplex Duplex Duplex Austenitic Austenitic Austenitic

PREN 24 26 26 35 43 43 46 56

YS# 170 530 400 450 550 310 415 430

El## 40 30 25 25 15 35 35 40

ASTM, minimum yield strength, Rp0.2 [MPa], given for LDX2101for <5mm thickness ASTM min elongation, A50, [%]

In Figure 1 the correlation between corrosion resistance, as PREN, and mechanical strength, as minimum yield strength, is illustrated. The wide range of corrosion properties is clearly illustrated as is the high mechanical strength of the duplex stainless steel grades.
700 Austenitic 600 Duplex

Min. yield strength [MPa]

500

LDX 2101 2205

2507

400

2304

4565 254 SMO

654 SMO

300

200

316L

100

0 0 10 20 30 40 50 60 70 PREN = %Cr + 3.3 x (%Mo + 0.5 x %W) + 16 x %N

Figure 1. Correlation between corrosion resistance (as PREN) and mechanical strength ( as min. yield strength) for austenitic and duplex stainless steel grades.

Rio Oil & Gas Expo and Conference 2012

2. Laboratory corrosion tests

Localized corrosion such as pitting corrosion, crevice corrosion and stress corrosion cracking is the main concern when using stainless steel in oil & gas applications. Results from laboratory corrosion test in various chloride environments are presented below. As these laboratory tests are often performed under very severe conditions (e.g. high potentials and high chloride concentrations), their main use is for ranking stainless steels according to their resistance to localized corrosion. 2.1. ASTM G150 The relative resistance to pitting corrosion can be evaluated by determining the critical pitting temperature (CPT) according to ASTM G150 (ASTM, 2010). This potentiostatic technique uses a temperature scan and a flushed port cell that eliminates the occurrence of crevice corrosion. From an initial temperature of 0C, the test solution is heated at 1C/min while the potential is held at 700 mV SCE which is close to the potential reached when seawater in chlorinated seawater. The current is monitored and the CPT is defined as the temperature at which the current density exceeds 100 A/cm2 for 60 seconds. Pitting on the surface of the specimen is confirmed visually. In the present case the surface area tested was 10 cm2 and 60x60 mm specimens were wet ground 320-grit and left to passivate in air for a minimum of 24 hours before being tested. The standard test solution according to ASTM G150 is 1 M NaCl but as the maximum test temperature is 90C some of the highest alloyed stainless steels does not exhibit pitting under these conditions. Therefore, a 3 M NaBr solution can be used which lowers the recorded CPT for the tested materials. In Figure 2 the CPT results for both 1 M NaCl and 3 M NaBr are presented. Results shows that LDX 2101 has the lowest CPT value in 1 M NaCl while for the highest alloyed grades 4565 and 654 SMO it is not possible to determine the CPT as it exceeds 90C. Conversely, it is not possible to determine the CPT for lower alloyed grades 316L, LDX 2101 and 2304 as in 3M NaBr as it is below 10C. The CPT for 654 SMO in 3 M NaBr still exceeds 90C while for 4565 it is well below 90C. Ranking of the tested materials according to their CPT measured using the ASTM G150 method is thus: LDX 2101 < 316L 2304 < 2205 < 2507 254 SMO < 4565 < 654 SMO Furthermore, it has been shown that 654 SMO has higher CPT in 3 M NaBr than some nickel-base alloys such as Alloys 625, C276 and C22 (Johansson et al., 2012).
110
100 90 1 M NaCl 3 M NaBr > 90

> 90

Critical temperature [ C]

80 70 60 50 40 30

20
10 <10 <10 <10

Figure 2. Typical CPT values measured using the ASTM G150 method in 1 M NaCl and 3 M NaBr. 2.2 ASTM G48 The standard ASTM G48 Methods E and F can be used for determining the critical pitting temperature (CPT) and critical crevice corrosion temperature (CCT) respectively in acidified ferric chloride solution (ASTM, 2009). The tests use 25x50 mm specimens and for CCT measurements (Method F) a hole is drilled for the bolt that fastens the crevice washers. Specimens are dry ground 120-grit on all surfaces and left to passivate in air for a minimum of 24 3

Rio Oil & Gas Expo and Conference 2012 hours. On CCT specimens two MTI-type PTFE crevice washers with 12 slots are applied and fastened with Hastelloy bolts, nuts and washers with a torque of 1.58 Nm. The specimens are immersed in the 6% FeCl 3 + 1% HCl test solution at the desired temperature. The duration of tests is 24 hours, and at the end of the test period specimens are inspected and the weight loss determined. Pitting or crevice corrosion is considered to be present if the local attack is 0.025 mm or greater. The CPT and CCT are defined as the lowest test-temperature that initiates pitting or crevice corrosion with 2.5C increments. The result shown in Figure 3 shows that LDX 2101 has the lowest CPT value while for 654 SMO it is not possible to determine the CPT as it exceeds the boiling point of the test solution. Conversely, it is not possible to determine the CCT for lower alloyed grades 316L, LDX 2101 and 2304 as it is below 0C. It is however possible to determine the CCT for 654 SMO. The ranking of the materials is the same for both CPT and CCT and is: LDX 2101 < 316L < 2304 < 2205 < 2507 254 SMO < 4565 < 654 SMO A study has also shown that using ASTM G48 Method F the CCT for 654 SMO is higher than for nickel-base Alloys 625 and C276, an on a par with Alloy C22 (Johansson et al., 2012).
110
100 90 CPT ASTM G48 E CCT ASTM G48 F

> 102

Critical temperature [ C]

80 70 60 50 40 30

20
10 <0 <0 <0

Figure 3. Typical critical pitting and crevice corrosion temperatures using ASTM G48 Methods E and F. 2.3 Chloride stress corrosion cracking Stress corrosion cracking (SCC) can occur if stainless steel is exposed to the combination of elevated temperature (> 60C), chloride containing environment and mechanical tensile stress. One of the most severe conditions for chloride induced stress corrosion cracking (SSC) in stainless steels is when chlorides accumulate on hot surfaces by evaporation. The drop evaporations test (DET) simulates evaporative conditions with a dilute sodium chloride solution and constant load specimens. This test is based on the procedure in MTI-5 Test Method (Treseder and Degnan, 1995), but the drop frequency is lower. Electropolished tensile specimens with a diameter of 1.8 mm are resistance heated to approximately 300C and a 0.1 M NaCl solution dripped on the surface at a frequency of 6 drops per minute. The specimen temperature is adjusted so that any remaining liquid on the specimen fully evaporates before the next drop reaches the surface. This results in a temperature variation (80-120C) that adds a certain fatigue factor to the test as the relative load on the specimen is effectively varied together with a small variation in length due to thermal expansion all resulting in a very aggressive test. The test is terminated after 500 hours if complete failure has not occurred by then. The load level is calculated as per cent of the measured yield strength at 200C and the load level is increased until the minimum stress level for failure is established. In Table 2, the DET results for the different stainless steel grades are presented as the minimum stress for failure (% of Rp0.2). It is well know that standard austenitic grades such as 316L are particularly susceptible to SCC, and this is confirmed as in the DET the threshold for cracking is 10%. The leaner duplex grades LDX 2101 and 2304 both show a fairly high threshold for cracking of 50%, which is larger than for 2205. However, both lean duplex grades actually fail at stress levels < 50% due to selective dissolution of the ferritic phase, so the results can be considered to be misleadingly good. The superaustenitic grades 254 SMO and 654 SMO has a very high threshold to SCC, for 654 SMO the threshold is above the yield strength at 200C. 4

Rio Oil & Gas Expo and Conference 2012 If instead the threshold for SCC is expressed as the absolute minimum stress for failure, the ranking of the materials will change. For example, the minimum stress for failure for 2507 will be higher than for 254 SMO. This is a result of the higher yield strength of 2507 compared to 254 SMO. Nevertheless, both methods of evaluation shows the superior resistance to stress corrosion cracking of super duplex and super austenitic grades, especially compared to standard austenitic grades such as 316L. Table 2. DET results as minimum stress for failure by stress corrosion cracking. LDX2101 and 2304 can fail by selective corrosion at lower stresses. Minimum stress for failure [MPa] [% of Rp0.2 at 200C] 10 50 50 40 70 90 90 > 100 20 193 178 172 297 232 276 333

Grade 316L LDX 2101 2304 2205 2507 254 SMO 4565 654 SMO

3. Tests for seawater applications and sour service

When stainless steels are used in oil & gas application they are most often exposed to seawater in some form or to sour conditions containing H2S. The seawater conditions can often become very harsh by elevated temperatures and chlorination that has an oxidizing effect. Sour environments can be more aggressive due to the presence of high chloride contents, low pH and high temperatures. Some results from studies in sweater and sour service conditions are presented below. 3.1 Field tests in natural seawater A study was performed in natural seawater of crevice corrosion on both duplex and austenitic stainless steels (Larch et al., 2011). Depending on the steel grade, welded specimens were exposed at 5-50C and under both nonchlorinated and chlorinated (0.5 ppm) conditions. The results confirms the limited resistance of the lower alloyed grades, 316L, LDX 2101 and 2304, that all showed crevice corrosion at 20C, even under stagnant conditions. At 30C 2205 showed crevice corrosion in non-chlorinated conditions, while 2507 and 254 SMO showed no sign of corrosion even at 50C in non-chlorinated conditions, but crevice corrosion occurred in chlorinated conditions. The study also show the importance of crevice geometry, since grades 2507 and 254 SMO suffered crevice corrosion at 30C under chlorinated conditions if the applied pressure was increased from 3 to 20 N/mm 2. Ranking of the material with regard to their resistance to crevice corrosion in natural seawater was as follows: LDX 2101 < 316L ~ 2304 < 2205 < 254 SMO ~ 2507 These results are in agreement with practical experience from the offshore industry that indicates that austenitic stainless steels with a minimum of 6% molybdenum, such as 254 SMO, can be used in seawater handling systems up to 30C with 1 ppm residual chlorine level (Johnsen and Olsen, 1992). As 654 SMO has even higher PREN than 2507 and 254 SMO it is expected to withstand even harsher seawater conditions. A field test was performed in chlorinated (10 ppm residual chlorine) natural seawater of welded specimens with crevice formers applied with a torque of 40 Nm at a temperature of 45C for 95 days (Fron and Walln, 1990). The test conditions were very severe as 10 ppm residual chlorine far exceeds the levels found in most seawater systems. The results showed that 654 SMO was completely resistant to crevice corrosion while 254 SMO, as well as the nickel-base materials Alloys 625 and C22, all suffered crevice corrosion. The configuration of a plate heat exchanger (PHE) represents a very severe crevice configuration. Also, as the demanding forming operation requires high elongation values, austenitic grades are often used in PHEs. A study was performed in chlorinated sea water (North Sea, salinity 3.3 -3.6%) where PHEs with nitrile rubber sealing were used (Walln and Wegrelius, 2000). The seawater temperature was 45-70C and there was continuous chlorination with 2 ppm residual chlorine. The duration of this test was 3 months and results revealed that bright annealed 654 SMO 5

Rio Oil & Gas Expo and Conference 2012 showed no signs of crevice corrosion even at the highest temperature of 70C while 254 SMO and even nickel-base Alloy C276 both suffered crevice corrosion at 45C and 50C. 654 SMO is thus much more resistant to crevice corrosion in seawater than 2507 and 254 SMO, and on a par with or better than some nickel base alloys. 3.2 Sour service testing In Table 3 a summary of test for LDX 2101, 2205, 2507, 254 SMO and 654 SMO in the standard NACE environment (5% NaCl + 0.5 CH3COOH) at 25 and 90C and for 254 SMO and 654 SMO in autoclave environment at 150C (Wolfe et al., 1997; Johansson and Pettersson, 2010). The superaustenitic grades were also cold worked up to 80% reduction, resulting in hardness up to 47 HRC. For the lean duplex grade no cracking was observed up to 0.15 bar H 2S at 90C, but preferential attack on the ferritic phase occurred at 0.1 and 0.15 bar H 2S. As was the case for the DET tests, this selective corrosion can suppress environmentally-induced cracking. This is more evident when comparing with results for 2205 where cracking occurs at 0.1 bar H2S.It is also shown that super duplex grade 2507 cracks under conditions (0.9 bar H2S, 150C) which the superaustenitic grade 254 SMO does not crack. Thus, the superaustenitic stainless steel displays superior performance in sour environments even though cold worked superaustenitics have a higher strength level. No cracking was observed for 654 SMO under any of these test conditions while 254 SMO failed at the highest temperature (150C). Also the high strength level achieved from cold working seems to have no adverse effect on the cracking resistance on 654 SMO under these conditions. As no cracking was observed for 654 SMO, the upper limit for sour service has yet to be established. Table 3. Summary of testing under sour conditions (Wolfe et al., 1997; Johansson and Pettersson, 2010) Grade Cold work [%] LDX 2101 0 0 0 0 0 0 0 0-80 0 0-80 0 0 0-80 0 0-80 Stress [% of Y.S.] 90 90 90 70, 100 70, 100 95 70-100 70-90 100 83-100 70-100 90 90, 100 100 90 Temp. [C ] 90 90 90 90 90 90 150 25 90 150 150 150 25 90 150 NaCl [%] 5 5 5 5 5 5 2 5 5 2 2 2 5 5 2 pH2S [bar] 0.05 0.10 0.15 0.01 0.1 0.1 0.9 1 1 0.4 0.9 1.4 1 1 1.4 3.5 3.5 3.5 3 3 2.7 5.8 3 3 4.7 5.8 5 3 3 5 pH pCO2 [bar] 6.7 2.7 6.7 7 7 No No# No# No Yes No Yes No No No No Yes No No No Cracking

2205 2507

254 SMO

654 SMO
#

Preferential attack on the ferritic phase

Some testing on LDX 2101 in H2S environments has been reported in the literature. Welded LDX 2101 was included in a test where it was compared to 13Cr supermartensitic stainless steel (Outokumpu Corrosion Handbook, 2009). The result is shown in Table 4 and while the 13Cr grade cracks at 0.01 bar H 2S none of the LDX 2101 samples cracked at 0.1 bar H2S. Compared to the previous results this study was performed at ambient and at a higher pH of 4.7, while the chloride content was higher at 16.5%. A qualifications test of LDX 2101 for use as carcass material in flexible pipes has been reported where carcass specimens of LDX 2101 and 316L were tested (Gudme and Nielsen, 2009). The test environment was designed to be close to the limit for cracking/no-cracking at 0.1 bar H2S, 500 mg/l Cl-, pH 4 and 130C. The results showed that there were no signs of cracking on any of the specimens. No signs of preferential attack were found on the LDX 2101 samples.

Rio Oil & Gas Expo and Conference 2012 Table 4. Results from testing of welded LDX 2101 and 13Cr supermartensitic stainless steel, 4-PB at 100% of proof strength (Outokumpu Corrosion Handbook, 2009) Grade 13Cr LDX 2101 SMSS LDSS pH2S [bar] 0.01 0.1 Cl[%] 16.5 16.5 CO2 Bal. Bal. pH 4.7 4.7 Temp. R.T. R.T Results* 6/6 0/3

*Number of cracked specimens/total number of specimens.

Coudreuse et. al. (2003) have reported tests on 2304 specimens at a constant load of 90-100% of the yield strength for 720 hours and under test conditions according to Table 5. No failure or cracking was observed in any of the test conditions. However, some selective corrosion of the ferritic phase was found, with more severe attack found on specimens exposed with 0.5 and 1 bar H2S. It was suggested that 2304 could be used up to at least 0.05 bar H 2S and probably also at higher H2S levels. This should be compared to the limit of 0.1 bar H 2S in ISO 15156-3 (ISO, 2009) for 2205 (see Table 6). Table 5. Test conditions for 2304 (Coudreuse et al., 2003) NACE TM0177 Temperature [C] pH2S [bar] pCO2 [bar] NaCl [%] pH 25 1 5 2.7 EFC 17 formation water 80 0.05, 05 and 1 16.5 4.5 Field formation water 25 and 80 0.04 20 16.5 4.5 - 5 Formation water 25 and 80 0.01 1 25 4

Table 6. ISO 15156-3 environmental limits for austenitic and duplex stainless steels used for any equipment or components (ISO, 2009) Max. temp [C] 60
2)

Material type/individual alloy Austenitic stainless steels AUSTENITIC STAINLESS STEELS S31600 S31603 (%Cr + 2 %Mo) > 30 or PREN > 40 PREN > 40 30 < PREN 40, Mo 1.5% 40 < PREN 45

Max. pH2S [bar] 1

2)

Max. Cl- conc. [mg/l]

1)

pH
1) 2)

93 149 60
2)

0.102 0.102 1
2)

50 5 000 1 000
1)

5.0 4.0
1) 2) 3) 3) 3) 1) 2) 1) 2)

DUPLEX STAINLE SS STEELS

121 149 171 232

2)

7 3.1 1 0.1
2)

50 5000 5000 5000

1)

50
1)

232
2)

0.2
2)

50

1)

2)
3)

Any combination of chloride concentration and in situ pH occurring in production environments These materials have been used without restrictions on temperature, pH2S or in situ pH in production environments. The in situ pH values occurring in productions environments are acceptable.

Table 6 shows the current ISO 15156-3 (ISO, 2009) environmental limits for austenitic and duplex stainless steels used for any equipment or components. It is seen that duplex stainless steels are possible to use at higher temperatures than austenitic stainless steels, while austenitic stainless steels are possible to use at higher partial pressures H2S than duplex stainless steels. However, these limits are under continual revision as more data becomes available. Two particular points from the table are worth noticing. Firstly, the highest alloyed austenitic stainless steels 7

Rio Oil & Gas Expo and Conference 2012 are required to have PREN > 40 and thus 654 SMO with a PREN of 56 is included in a group of materials with considerably lower PREN values. However, as shown above the upper limit for 654 SMO has not yet been defined and this grade should rightly be compared with some nickel-base grades. Also, duplex grades are required to have (%Cr + 2 %Mo) > 30 which excludes leaner duplex grades such as LDX 2101 and 2304. But, as discussed above these grades can be used in less harsh environments and can be an attractive alternative to supermartensitic grades. It may therefore be argued that a new higher class is required for austenitic stainless steels with PREN > 50 and a new lower class required for duplex stainless steels with PREN < 30.

4. Application examples
4.1 Process piping In offshore wells, production can be complicated. In addition to the incoming mixtures of oil, gas and sand, the main process piping has to withstand seawater, hydrogen sulphide and carbon dioxide. Extreme conditions, at elevated temperatures and under high pressure with often highly corrosive process fluids, require extreme measures. Due to their excellence corrosion resistance, 6Mo superaustenitic grades such as 254 SMO as well as grade 4565 are used in both process streams and in seawater handling in the offshore industry. Large quantities of pipes and fittings in 254 SMO are installed in a variety of platforms and sites in the North Sea and the Arabian Gulf region with very good results. 4.2 Flexible pipes and flow lines The manufacturing of a flexible pipe requires wrapping of many intertwining layers of high strength stainless steel carcass and special leak-proof polymer barriers. The high strength of duplex stainless steels together with their high resistance to chloride induced stress corrosion cracking (SCC) are important reasons why LDX 2101, 2304 and 2205 are all used as carcass material. In fact duplex stainless steel is today considered as the standard material for carcasses in subsea applications. Due to the presence of CO2, chlorides, H2S and the formation of water condensate caused by reduced pressure, corrosion is a very real risk in flowlines. Adding the factors of high flow rates and temperatures, it is easy to see why the material used for flowlines and piping systems has to be very resistant indeed. Thanks to their superior mechanical strength and good corrosion resistance, grades LDX 2101 and 2205 are excellent choices. They have cost advantages and for some dimensions installation costs for duplex are lower than for clad steel. 4.3 Seawater systems The up and downside of chlorination is well known when it comes to seawater piping. Without it, heat exchangers lose their effectiveness. With it, corrosiveness increases dramatically. Superaustenitic 254 SMO has enjoyed widespread success in chlorinated systems operating at up to 30C. By combining 254 SMO piping with 4565 or 654 SMO for flanges or other parts with crevices, service temperatures can be further increased. A plate heat exchanger is, from a corrosion point of view, one of the most demanding applications for stainless steels and other alloys whose corrosion resistance depends on a protective passive film. The construction involves two types of crevices: those between the rubber sealing gaskets and the plates and those formed in the contact points between the plates. There are appreciable risks for crevice corrosion in seawater when such crevices are present. According to practical experience, even 6Mo superaustenitic stainless steels can hardly be used in continuously chlorinated ocean water even at low temperatures. Seawater cooled plate heat exchanges are normally made of titanium, which can be used up to high temperatures. In those cases where the product to be cooled is corrosive to titanium, a Nibase alloy is often used. However, 654 SMO has proven superior to the 6Mo steels, in laboratory as well as in field tests, and may be an alternative to some nickel-base alloys. It has been shown that 654 SMO, in the bright annealed condition, is resistant to crevice corrosion at 70C and at least up to 60C in the polished condition (Walln and Wegrelius, 2000). 4.4. Topside construction On an offshore platform it is not only the process fluids and seawater that are corrosive but also the atmosphere itself. Secondary structural components such as pipe supports, cable trays, stairs, walkways, and blast and fire walls are all exposed to the harsh offshore atmospheric environment. When choosing materials for these applications, mechanical properties, safety and corrosion resistance must be considered for the lowest overall lifecycle cost. The atmospheric corrosion resistance of stainless steel in offshore environments mean that they can be an attractive alternative to painted carbon steel due to the reduction in the required maintenance. Choosing a duplex stainless steel can provide weight savings due to the increased strength compared to austenitic stainless steels. Blast walls need to absorb energy and provide good resistance to buckling, and thus duplex grades with their higher strength levels can be used. Fire walls, cable trays, stairs and walkways must maintain their structural integrity in the case of fire. Austenitic grades such as 316L can be used in such applications but there is also a potential of utilising duplex stainless steel when fire resistance 8

Rio Oil & Gas Expo and Conference 2012 must be considered (Schedin et al. 2011). Despite duplex grades having somewhat lower strength retention than austenitic grades at the higher temperatures their absolute strength level is similar to the austenitic grades. 4.5 Refineries The duplex grade 2205, with its high strength and good corrosion resistance, is an attractive alternative as a replacement for austenitic 316L in plate air-cooled and refinery plate shell heat exchangers. This application of duplex stainless steel in the plates of these types of heat exchangers has previously been considered as impossible because of their lower ductility. However, after some development work involving new design and pressing technique, conventional austenitic stainless steel 316L could be replaced with duplex grade 2205 (Duplex 2205 for plate heat exchangers, 2012). By doing this, the service life was extended from 1- 3 months to 2 years and beyond.

5. Conclusions
Stainless steels have long been established as reliable materials for demanding applications within the oil and gas industry. A very wide range of grades is available in terms of chemical composition, strength and corrosion resistance. The key to successful use lies in identification of critical requirements and matching these against the available grade property profiles. Application examples range from storage tanks and topside construction equipment, where the lean duplex grades provide cost-efficient solutions by virtue of their low maintenance costs, to systems for handling chlorinated seawater and sour process streams, where the high performance of the superaustenitic grades is required.

6. References
ALFONSSON, E., WANG, J., LILJAS, M.,JOHANSSON, P. Ferrit-austenitiskt rostfritt stl. Swedish patent SE0003448 L, 2000. ASTM G48 - 03 Standard Test Methods for Pitting and Crevice Corrosion Resistance of Stainless Steels and Related Alloys by Use of Ferric Chloride Solution, ASTM International, 2009. ASTM G150 - 99 Standard Test Method for Electrochemical Critical Pitting Temperature Testing of Stainless Steels, ASTM International, 2010. BERHARDSSON, S.-O., ERIKSSON, H. F., NORBERG, S. P., FORSELL, L. O. H.,LINDQVIST, N. L. Ferritaustenitiskt rostfritt stl mikrolegerat med molybden och koppar och anvndning av stlet. Swedish patent SE0003448 L, 1984. BERHARDSSON, S.-O., HAGENFELD, P.,LAGERBERG, S. Hgkvvhaltigt ferrit-austenitiskt rostfritt stl. Swedish patent SE8504131 L, 1985. COUDREUSE, L., LIGIER, V., AUDOUARD, J. P.,SOULIGNAC, P. Lean duplex stainless steel for oil and gas applications. In: CORROSION 2003, San Diego, CA: NACE International, 16-20 March, 2003. Duplex 2205 for plate heat exchangers. Retrieved 15 May, 2012, from http://www.outokumpu.com/en/ CustomerIndustries/Project-and-Process-Industries/Heat-Exchangers/Pages/Heat-Exchangers.aspx. FRON, D.,WALLN, B. Effect of high concentrations of chlorince and sulfide on stainless alloys in seawater. In: CORROSION 93, New Orleans, LA: NACE International, March 12-14, 1990. FREDRIKSSON, H., FRIDBERG, J.,LILJAS, M. Austenitiskt rostfritt stl med hg Mo-halt. Swedish patent SE7601070 L, 1985. GUDME, J.,NIELSEN, T. S. Qualification of Lean Duplex Grade LDX 2101 (UNS32101) for Carcass Material in Flexible Pipes. In: Corrosion 2009, Atlanta, GA: NACE International, 22-26 March, 2009. GUEMPEL, P., EMIL, M.,GRUNDMANN, R. Use of a steel in the construction of tankers for chemicals. German patent DE 3729577 (C1), 1988. NACE MR0175-2003 Standard Material Requirements Metals for Sulfide Stress-Cracking and Stress Corrosion Cracking Resistance in Sour Oilfield Environments, NACE International, 2003. ISO 15156-3:2009 Petroleum and natural gas industries - Materials for use in H2S-containing environments in oil and gas production - Part 3: Cracking resistant CRAs (corrosion-resistant) and other alloys, International Organization of Standardization, 2009. JOHANSSON, E., MAMENG, S., PETTERSSON, R.,ALFONSSON, E. UNS S32654 Superaustenitic Stainless Steel for Demanding Offshore Applications. Acom, n. 2, 2012. JOHANSSON, E.,PETTERSSON, R. Lean duplex stainless steel within the oil and gas industry. In: EUROCORR 2010, Moscow, Russia: European Federation of Corroison, 13-17 September, 2010. JOHNSEN, R.,OLSEN, S. Experience with the use of UNS S 31254 in seawater systems--case histories from the field. In: CORROSION/92 Nashville, TN: NACE International, 26 April - 1 May, 1992. LARCH, N., THIERRY, D., DEBOUT, V., BLANC, J., CASSAGNE, T., PEULTIER, J., JOHANSSON, E., TARAVEL-CONDAT, C. Crevice corrosion of duplex stainless steels in natural and chlorinated seawater. Rev. Metall., v. 108, n. 7-8, p. 451-463, 2011. 9

Rio Oil & Gas Expo and Conference 2012 Outokumpu Corrosion Handbook, Outokumpu Oyj, 2009. TRESEDER, R. S., DEGNAN, T. F. Corroison Testing of Iron- and Nickel-Based Alloys - Part 1: Test Methods, Materials Technology Institute of the Chemical Process Industries, 1995. WALLN, B., LILJAS, M.,STENWALL, P. Austenitiskt rostfritt stl. Swedish patent SE465373 B, 1992. WALLN, B.,WEGRELIUS, L. Performance of a Highly Alloyed Stainless Steel in Seawater Cooled Plate Heat Exchanger. In: EUROCORR 2000, London: The European Federation of Corrosion, September 10-14, 2000. WOLFE, C., ARNVIG, P.-E., WASIELEWSKA, W.,JARGELIUS-PETTERSSON, R. F. A. Hydrogen Sulphide Resistance of Highly Alloyed Austenitic Stainless Steels. Acom, n. 2, p. 1-7, 1997.

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