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No 1-2 1986
AVESTA CORROSION MANAGMENT

All rights reserved. Comments and correspondence can be directed to Dr Sten Nordin, Avesta Projects AB, P.O. Box 557, S-651 09 Karlstad, Sweden. Tel. +46(0)54-10 27 70. Telex 66108 apab s. Telefax +46(0)54-18 82 54.

Engineering Properties of Duplex Stainless Steels

Duplex stainless steels, and in particular grade UNS S31803, are gaining importance as engineering material in various demanding industries with special emphasis on gas and oil applications. Because of their two-phase structure, duplex stainless steels are more complicated than pure one-phase stainless steels and their successful use is very much dependent on the knowledge of how they behave under various conditions. The reports published hereon aim at increasing the knowledge about metallurgical properties, fabrication properties, and applications and they were presented at the conference "Duplex Stainless Steels '86" in The Hague, October 26-28, 1986. "Influence of Nitrogen on Weldments in UNS S31803" by M Liljas and R Qvarfort Page 2-12 "Textures and Anisotropy in Duplex Stainless Steel SS 2377" by W B Hutchinson, U v Schlippenbach and J Jonson Page 13-17 "Applications and Uses of Duplex Stainless Steels" by J Olsson and S Nordin Page 18-23

Influence of Nitrogen on Weldments in UNS S31803

by
Mats Liljas and Rolf Qvarfort, Research and Development, Avesta AB, S-77401 Avesta, Sweden

Abstract
Welding has a profound influence on the structure of duplex ferritic-austenitic stainless steels. It is well established that both corrosion and mechanical properties of duplex stainless steel weldments are strongly dependent on the ferrite-austenite balance. For example, resistance to pitting and intercrystalline corrosion as well as impact strength can be impaired by high ferrite levels. Much attention has been paid to controlling the ferriteaustenite ratio in welds by restrictions of welding parameters. However, the wide limits for the alloying elements according to UNS S31803 may result in large variations of microstructure in the weld zone. Tests with laboratory heats show that the pitting resistance of both base metal and autogenous GTAW welds is greatly improved by increasing the nitrogen content in the steel. However, the weld metal has always a lower resistance than the base metal. A more austenitic composition of UNS S31803 with minimum 0.15% N has been tested. The base metal of this variant contains 5-10 % more austenite than the more conventional type with equal amounts of ferrite and austenite. After welding with normal practices the ferrite content of weld metal or HAZ does not exceed 65 %. Properties of weldments including GTAW, PAW, SAW and SMAW are presented. Due to the relatively low ferrite contents high ductility and impact strengths are obtained. Microprobe measurements of element partitioning between the two phases indicate that nitrogen has a controlling effect on the austenite reformation in welds. Pitting corrosion tests of weldments in ferric chloride show that the base metal (HAZ included) in the high nitrogen variant has a very high resistance while attacks in HAZ are quite common in heats with low nitrogen. The welding parameters as well as sample preparation appear to have a great effect on the results.

development has in general been towards higher alloyed steels which are more corrosion resistant and one trend has been to use the duplex materials in environments where pitting or crevice corrosion might occur. As these types of localized corrosion normally are initiated at the weakest point on a steel surface the individual phases in the material should have similar pitting resistance. The parent material, solution treated at about 1050C, contains typically 50 % austenite and 50 % ferrite with a higher content of austenite formers such as nickel, nitrogen and carbon in the austenite and a higher content of ferrite formers such as chromium and molybdenum in the ferrite phase. Many expressions as regards the alloy content have been proposed for guidance concerning the pitting resistance. If the pitting resistance equivalent PRE = % Cr + 3.3 x % Mo + 16 x % N is used for both phases, it can be demonstrated that a nitrogen content of 0.18 % is required in a steel of the type 22Cr 5Ni 3Mo to obtain equal pitting resistance of the two phases (1). A positive influence of nitrogen on pitting as well as intercrystalline and stress corrosion cracking resistance of the parent material has been shown by many authors (1-5). As the duplex stainless steels during welding undergo a transformation to ferrite followed by nucleation and growth of austenite, the welded joints have a different microstructure than the parent material. Normally the cooling rates are not sufficiently low to obtain an equilibrium austenite content and, with the wide compositional limits in the standard of e.g. UNS S31803, very high ferrite contents could be expected in the weld metal if too ferritic a composition is selected. Therefore, much attention has been paid to controlling the ferrite/austenite balance in welds by restrictions on the welding parameters (6, 7). However, welding with heat inputs normally used in manual welding (0.6-1.6 kJ/mm), the arc energy has a minor influence on the microstructure compared to the effect of composition (8). It is well established and understood that a high ferrite level has an adverse effect on ductility and impact toughness. As concerns pitting corrosion it is shown in many works that the weld metal has a lower resistance than the parent material (2, 9,10,11). A post weld heat treatment (PWHT) can improve the pitting resistance (11) and it has also been found that the use of a more austenitic filler metal by adding nickel or/and nitrogen gives better pitting resistance (8, 12, 13). Both the PWHT which restores a higher austenite content and use of a filler metal with increased nickel will result in a

Introduction
Although produced for approximately 50 years duplex stainless steels have experienced increased interest in recent years, due to the use in oil and gas industry. The

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3 higher austenite content which of course also improves the impact properties. The austenite level required for obtaining acceptable pitting resistance has been discussed (12, 14, 15), but there are naturally many other factors such as pitting index of the filler metal, presence of carbide or nitride precipitates and surface roughness that will influence the result (13). The pitting attacks are reported to occur in the ferrite phase of weld metals in as welded condition (14) but in the austenite phase in the PWHT condition (10). As the ferritic solidtfication results in insignificant microsegregation (16), the partitioning of the elements during the solid state transformation must play an important role. The purpose of this paper is to show the effect of nitrogen on weld metal microstructures, mechanical properties, and pitting corrosion resistance of a duplex stainless steel of the type UNS S31803.

Experimental
Materials
The duplex stainless steels used in this investigation were all of the type 22Cr5Ni3MoN (UNS S31803 or W.-Nr. 1.4462). Laboratory heats with variations in nickel and nitrogen were made into 30 kg ingots. Compositions are listed in Table 1. The ingots were hot forged and cold rolled to 1.6 mm strips which were annealed for 5 min at 1030C, water quenched and pickled. Material was also obtained from normal production heats with varying nitrogen contents. The compositions are given in Table 2. In the weld tests where filler metals were used more austenitic compositions than the base material were selected. As seen in Table 3 the filler metals had nickel contents ranging from 8 to 9.5 %.

Table 1: Composition of laboratory heats

Heat No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 C 0.020 0.024 0.021 0.024 0.024 0.023 0.027 0.023 0.022 0.025 0.026 0.022 0.022 0.022 Si 0.38 0.37 0.37 0.35 0.37 0.33 0.34 0.37 0.34 0.37 0.38 0.40 0.37 0.38 Mn 1.16 1.18 1.19 1.38 1.13 1.14 1.15 1.17 1.15 1.23 1.25 1.17 1.14 1.20 Elements, percent by weight P 0.011 0.011 0.011 0.011 0.011 0.011 0.011 0.011 0.011 0.012 0.011 0.011 0.011 0.011 S 0.015 0.013 0.011 0.015 0.013 0.013 0.015 0.013 0.014 0.015 0.014 0.012 0.012 0.015 Cr 22.4 21.8 22.4 21.9 23.6 22.1 22.0 21.8 21.8 22.2 21.6 21.9 22.2 21.7 Ni 5.1 5.1 5.2 5.1 5.4 5.6 5.6 5.6 5.5 5.6 5.9 6.0 6.0 6.0 Mo 3.03 3.02 3.16 3.03 2.98 3.13 3.04 2.95 3.08 3.03 2.81 2.93 3,02 3.01 N 0.127 0.168 0.214 0.217 0.095 0.130 0.144 0.149 0.181 0.236 0.122 0.141 0.157 0.179

Table 2: Composition of parent materials, production heats Code I II III IV v Thickness mm 3-12.5 2-5 3 6 3 C 0.021 0.018 0.020 0.014 0.017 Si 0.40 0.42 0.40 0.42 0.48 Mn 1.50 1.45 1.52 1.41 1.71 Elements, percent by weight P 0.024 0.026 0.022 0.025 0.028 S 0.001 0.002 0.001 0.001 0.004 Cr 22.03 21.95 21.94 21.95 22.78 Ni 5.71 5.62 5.53 5.66 5.58 Mo 3.16 3.05 2.98 3.07 2.94 N 0.179 0.168 0.150 0.128 0.106

Table 3: Composition of filler materials

Code T1 T2 T3 T4 T5 Type Wire Diameter mm 1.2-3.0 3.0 1.2 2.5 3.25 C 0.018 0.016 0.011 0.017 0.019 Si 0.49 0.45 0.48 0.71 0.94 Mn 1.68 1.50 1.61 0.83 0.82 Elements, percent by weight P S Cr 0.018 0.003 22.57 0.018 0.003 22.41 0.016 0.003 22.50 0.019 0.023 0.020 0.015 21.47 22.08 Ni 8.04 7.94 8.00 9.61 9.49 Mo 2.99 2.99 2.95 2.90 3,35 N 0.150 0.140 0.130 0.131 0.136

"
" Rod "

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Tests with laboratory heats

The 1.6 mm strips were autogenously GTA welded (bead on plate) with arc energies of 0.05, 0.1 and 0.2 kJ/mm. Cross sections of the welds produced with an arc energy of 0.2 kJ/mm were studied metallografically and the ferrite contents were measured by point counting. For preparation see "Metallographic examination", next column. The critical pitting temperature (CPT) was determined in FeCI3 according to ASTM-G48-A on welds produced with arc energies of 0.05 and 0.1 kJ/mm. Specimens in size 25 x 50 x t mm with the weld in the centre and parallel to the shorter side were cut out from the samples. All surfaces of the corrosion specimens were wet ground to 400 mesh. The corrosion tests were made at gradually increasing temperatures in steps of 2.5C. New duplicate specimens were used at each temperature. The CPT was defined as the lowest temperature where corrosion attacks could be seen on the surface at approx. 20 x magnification. Since the attacks found in this investigation were very shallow, visible corrosion was often noticed without any significant weight loss of the specimen. Attacks on ground edges were omitted.

6 mm parent material: Weld B1U corresponds to pipes 1705-6 with no filler addition while weld B1M corresponds to 1703-4 where filler metal was used in both runs. B2 is a simulated girth weld utilizing GTAW and filler metal. 2-5 mm parent material: The welding conditions for tests with 2-5 mm material of different heats are given in Table 6. Some of the welded plates and pipes were post weld heat treated. Weld A1 was annealed for 10 min at 1080C and water quenched while welds B1U and B1M were annealed for 10 min at 1050C and air cooled. Pipes 1300,1302,1703 and 1705 were mill annealed at 1080C and quenched by water spray. Mechanical testing The welded plates were submitted to tensile and bending tests across the welds. Charpy V impact testing was performed at -40C of weld, heat affected zone and base metal. The notch was oriented perpendicular to the surface giving crack propagation in the weld direction. Three specimens were tested at each location. The tensile testing of the pipes was performed on longitudinal specimens either of the base metal or the weld metal. Impact testing and bend testing of the pipes were done in the same way as above. Metallographic examination Metallographic sections transverse to the weld were first etched electrolytically in 10% oxalic acid to reveal presence of precipitates and then etched in Murakami's etchant for staining the ferrite phase. The ferrite content was measured by point counting of the austenite phase according to ASTM E562-83 at 400 x magnification. A minimum of 30 fields were measured with a grid containing 16 points giving a maximum standard deviation of 10 % ferrite at the 50 % ferrite level. Also, the extended ferrite number (EFN) was measured using a Magne-Gage with counterweights as described by Kotecki (17). To relate the ferrite content to the annealing temperature, steels I and IV were annealed for 10 minutes between 950 and 1350C and water quenched. The resulting ferrite levels were measured as above. Electron Probe Micro Analysis (EPMA) To assess the partitioning of major alloying elements between ferrite and austenite in weldments EPMA was performed by point counting. The specimens were polished and slightly etched in Murakami's etchant prior to the analysis to facilitate positioning of the electron beam on the different phase regions. The nitrogen measurements were carried out according to a direct calibration method using a set of Fe-N alloys (0-0.435 % N) as references for the EPMA (18). The instrument was an ARL-SEMQ; 10 kV, 200 nA was used giving an accuracy of the nitrogen determinations of about 20 % and a limit of detection of about 0.02 % N. Pitting corrosion tests

Test with production heats

For documentation of the weldment properties of UNS S31803 with high nitrogen content weld tests were performed on 2-12.5 mm plate with the compositions given in Table 2. The welding procedures were selected to simulate both longitudinal and girth welding of pipes. Also fabrication of seam welded pipes was tested. Welding The welding conditions for 2-12.5 mm plate and for the pipes are listed in Tables 4-6. The used joint geometries are shown in Figure 1. 12.5 mm parent material: Weld A1 resembles the in pipes 1300-1303. However, pipes 1300-1301 welded without filler in the first two passes pipes 1302-3 had filler addition in all passes. A2 lates a girth weld with SMAW in the filler passes. welds were while simu-

Figure 1 Weld preparations a) Weld A1 and pipes 1300-3 b) Weld A2

c) Weld B1, pipes 1701-4 and 2-3 mm material d) Welds B2 and F2b

The test procedure described earlier was followed, with one exception: The edges of the specimen were ground with 120 mesh abrasive paper, but the two plate surfaces were not machined. The specimens were then pickled to remove the weld oxide from the surfaces prior to test in the FeCl3-solution.

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5 Table 4: Welding conditions for 12.5 and 6 mm plate, heat I

Weld no A1 Thickness mm 12.5 Weld run no 1 2 3-5 1 2 3-5 1 2 B1M B2 6 6 1 2 1 2 3 Process Filler heat dia no mm T1 T1 T1 T4 T5 T1 T1 T1 T1 T1 1.2 3.0 1.6 2.5 3.25 1.2 1.2 1.6 1.6 1.6 Voltage V 27.5 12 32 15.5 23 27 27.5 12 27.5 12 13 13 13 Current A 200 220 400 160 67 73 175 220 200 220 132 123 105 Travel speed mm/min 150 250 550 130 64 42 200 250 150 220 105 64 37 Arc energy kJ/mm 2.2 0.6 1.4 1.1 1.4 2.8 1.4 0.6 2.2 0.7 1.0 1.5 2.2

A2

12.5

B1U

PAW GTAW SAW GTAW SMAW SMAW PAW GTAW PAW GTAW GTAW GTAW GTAW

Table 5: Welding conditions for longitudinally welded pipes

Weld no 1300-1 O.D.x t mm 273 X 12.5 Weld run no 1 2 3-5 1 2 3-5 1 2 1 2 Process Filler heat no T2 T3 T3 T2 T3 T3 dia mm 3.0 1.2 1.2 3.0 1.2 1.2 Voltage V 27 11 32 27 11 33 28 10 26 10 Current A 210 200 400 210 200 375 210 200 190 190 Travel speed mm/min 200 180 650 200 180 650 260 200 300 230 Arc energy kJ/mm 1.7 0.7 1.2 1.7 0.7 1.1 1.4 0.6 1.0 0.5

PAW GTAW SAW PAW GTAW SAW PAW GTAW PAW GTAW

1302-3

273 X 12.5

1703-4 1705-6

168 X 6 168 X 6

Table 6: Welding conditions for tests with 2-5 mm parent material

Weld no C1B C1U C1M D1U D1M D2U D2M E1U E1M E2 F1 F2a BM heat no I I I II II II II II II II II II II II II II II II II V v V III III Thickness mm 3 3 3 2 2 2 2 3 3 3 3 5 5 5 5 5 5 5 5 3 3 3 3 3 Weld run no 1 1 1 1 1 1 1 1 1 1 2 1 2 1 2 3 1 2 3 1 1 1 1 1 Process heat no GTAW Filler dia mm 1.2 Voltage V 10 13 14 11 T1 T1 T1 T1 T1 T1 T1 T1 T1 T1 T1 T5 T5 T1 T1 T1 1.2 1.6 1.2 1.6 1.6 1.2 1.2 1.6 1.6 2.4 1.6 3.25 3.25 1.2 1.6 1.6 12 12 13 12 13 12 14 15 15 12 13 15 15 30 30 10 12 14 12 12 Current A 60 168 170 95 110 62 60 115 130 65 92 190 165 70 110 130 105 100 110 60 125 155 70 70 Travel speed mm/min 300 200 200 300 300 90 90 200 200 60 100 200 200 55 120 105 130 260 260 300 200 200 94 86 Arc energy kJ/mm 0.10 0.66 0.71 0.21 0.26 0.50 0.52 0.41 0.50 0.78 0.77 0.85 0.74 0.92 0.72 1.11 0.73 0.69 0.76 0.10 0.45 0.65 0.54 0.59 Type of joint Bead on plate Butt

"
"

T1

" " " " " "

" V-80 " V-60 " V-80 " " see Fig. 1

" " "

"

"
"

"
"

"
"

" "
" GTAW SMAW SMAW GTAW "

F2b

"
" Bead on plate Butt " Butt

K1B K1U K1M R1M R2M

"
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"

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Results
Test of laboratory heats with different nitrogen contents
The CPT data obtained for base metal and autogenous GTAW weld metal are plotted versus nitrogen content in Figure 2. For both base metal and weld metal there is an improvement when the nitrogen content is raised. The different nickel contents are not influencing the CPT of the base metal while there appears to be a beneficial effect of nickel as regards the weld metal. Figure 2 also shows that the autogenous weld metal has a 5-10C lower CPT than the base metal. The ferrite contents of the weld metal are plotted against the nitrogen content in Figure 3. An increased nitrogen content resulted in a reduced ferrite content as expected.

Tests of production heats

Mechanical tests The results of the mechanical tests are shown in Tables 7-9. All tensile tests in Tables 7 and 8 across the weld resulted in fracture of the base metal and showed high elongations of both as welded (AW) and PWHT conditions i.e. no signs of weld defects, which was confirmed by the bend tests. The impact energies of the HAZ and the weld metal (Tables 7 and 9) were in general somewhat lower than that of the base metal. It appears that the GTAW welds had the highest impact value (weld B2). Weld A1, containing PAW and SAW also had a high impact toughness. Welds B1U and B1M, produced by PAW with and without filler, gave equal impact values. The SMAW (A2) showed the lowest impact toughness. A PWHT with air cooling only gave a slight improvement whereas a PWHT with water quenching resulted in a large increase of the impact toughness. The tensile tests of welded pipes (Table 8) showed that weld metal and base metal had similar tensile properties in both as welded and PWHT condition. Also here the bending with a bend radius of 1.25 x t was performed without signs of cracks. The impact tests of the welded pipes (Table 9) showed that the welds produced by PAW without filler and SAW (1301) had a somewhat lower impact toughness than the one produced with filler (1303). PWHT resulted in a great increase and the two types of welds had equal impact strengths. The relatively low values in as welded condition for the fusion line were probably caused by crack propagation into the weld metal. The welds of pipes with 6 mm wall thickness showed high impact energies also when no filler addition was used. In fact the weld metal was slightly tougher than the base metal. The PWHT only resulted in a small increase of the impact values. Microstructures a) Base metal

Figure 2 Influence of nitrogen on CPT in FeCI3, laboratory heats.

The ferrite contents versus annealing temperature for steels I and IV are illustrated in Figure 4. Steel I had 5-10 % lower ferrite content over the entire temperature range 950-1350C. Figure 4 also shows that steel IV is fully ferritic at 1350C while steel I contains about 90 % ferrite at that temperature.

Figure 3 Ferrite content versus nitrogen concentration in autogenous GTAW welds. Arc energy 0.2 kJ/mm, laboratory heats.

Figure 4 Ferrite content versus temperature for steels I and IV.

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Table 7: Results of mechanical testing of 12.5 and 6 mm plate

Weld Condition Thickness mm 12.5 " " 6 " Tensile test, across weld Rp0.2 Rm A5 MPa MPa % 490 726 28 538 748 39 540 765 29 586 552 582 535 584 812 807 816 818 822 31 35 29 33 30 Charpy V impact energy* -40C, J Base Fusion Weld metal zone metal 161 164 113 273 227 160 70 42 133 125 133 126 60 66 61 72 130 74 78 77 82 142 Bend test Bend Bend radius angle 1.25 x t 180 1.25 x t " 2xt " 1.25 x t "

A1 A2 B1U B1M B2

AW PWHT AW AW PWHT AW PWHT AW

"
"

"
" "

"
" "

" "
"

* For 6 mm thickness half size specimens were used: AW = As welded PWHT = Post weld heat treated

Table 8: Mechanical tests of welded pipes

Pipe no Condition Dimension O.D.x t mm 273X12.5 " " " 168X6 " " Base metal Rm MPa 776 828 779 812 785 795 792 825 Tensile test Weld metal Rp0.2 Rm MPa MPa 599 758 671 822 551 667 610 674 784 840 793 859 752 771 786 807 Across weld metal Rm MPa 820 876 838 871 827 885 846 889 Bend test Bend Bend radius angle 1.25 x t " " " " " " " 180 " " "

Rp0.2 MPa 660 722 624 713 598 627 604 646

A5 % 34 29 33 30 33 31 31 30

A5 % 37 26 37 31 36 24 34 28

1300 1301 1302 1303 1703 1704 1705 1706

PWHT AW PWHT AW PWHT AW PWHT AW

"
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"
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Table 9: Impact test of longitudinally welded pipes

Pipe no 1300 1301 1302 1303 1703 1704 1705 1706 Condition PWHT AW PWHT AW PWHT* AW* PWHT* AW* Charpy V impact energy -40C, J Weld Distance from fusion line Base metal 0 mm 2 mm 5 mm metal 99 32 97 42 107 93 110 94 >147 42 114 48 91 64 94 89 >147 103 153 75 89 83 92 77 >147 83 177 116 93 85 88 81 >147 192 244 95 92 93 97

Table 10: Ferrite contents in plate welds

Weld Condi- Thick no tion ness mm A1 A1 A2 B1U B1U B1M AW PWHT AW AW PWHT AW 12.5 " " 6 " " " Ferrite content, % EFN HAZ Weld metal Weld metal Face Root Face Root Face Root 57 35 47 45 37 51 41 49 63 56 50 52 41 51 41 53 51 31 30 61 41 56 35 38 65 44 40 64 41 52 34 42 78 51 41 96 61 78 60 65 110 64 49 86 60 82 58 68

B1M PWHT B2 AW

* Reduced size 10 X 5 mm cross section of specimen

Table 11: Ferrite contents in pipe welds

Pipe no Condition Dimension O.D. x t mm 273 x 12.5 " " " 168 X 6 " " " Ferrite content, % EFN Wel metal Weld metal HAZ Face Root Face Root 32-36 44 30-33 51 31-36 48 35-39 50-51 25 45 29 48 31 53 38 61 34 45 30 56 34 56 36 63 44 80 41 73 56 81 60 98 58 75 65 77 57 72 66 84

b) Weld metal The obtained ferrite levels in the weld metals and HAZ are shown in Tables 10 and 11. The typical ferrite content in the HAZ of the as welded condition is about 50% and in the PWHT condition about 40 %. Autogenous weld metals contained maximum 65 % ferrite. After annealing these welds contain about 40 % ferrite. Due to a more austenitic composition of the filler metals, deposited weld metals had a range of 30-50 % ferrite depending on the degree of dilution from the base metal.

1300 PWHT 1301 AW

1302 PWHT 1303 AW

1703 PWHT 1704 AW

1705 PWHT 1706 AW

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8 The extended ferrite numbers (EFN) of the weld metals are also included in Tables 10-11. When correlating the obtained data the following relationship was found. Ferrite content (%) = 4.5 + 0.59 x EFN. Due to the limited width of the HAZ no measurement of the EFN could be executed. Typical microstructures of the as welded condition are shown in Figures 5-6. In the ferrite phase small precipitates can be observed in optical microscope. These precipitates appear only outside a certain distance from the austenite phase and where the distance between austenitic areas is small no such precipitates are present. Annealing resulted in complete dissolution of the precipitates. Another observation is that the weld metal microstructure varied with the distance from the surface. This is illustrated in Figures 7 and 8. Under certain conditions the surface structure was almost fully ferritic and contained precipitates while, under other conditions, the surface had a border of austenite. Electron Probe Micro Analysis (EPMA) Results of EPMA measurements in ferrite and austenite of base and weld metal in two autogenously GTA welded steels are shown in Table 12. The distribution between the two phases expressed as the partitioning coefficient content in ferrite P= content in austenite

Figure 5 Microstructure of Weld B 1 M. 6 mm plate PAW with filler metal. Arc energy 2.2 RJ/rnm, 56 % ferrite. 400 x

Figure 7 Microstructure at the root surface of weld R2M. GTAW with no root gas. 400 x

Figure 6 Microstructure of root run (GTAW with filler) weld B1M. Arc energy 0.7 kJ/mm. 52 % ferrite. 400 x

Figure 8 Microstructure at the root surface of weld R1M. GTAW with 10 l/min Ar as root gas. 400 x

Table 12: Composition (percent by weight) of ferrite (F) and austenite (A) in weld and base metal of two welds
Sample no C1U Condition AW AW PWHT PWHT K1U AW AW PWHT PWHT Area BM WM BM WM BM WM BM WM Ferrite % 40 64 40 49 59 89 57 56 F 23.3 21.8 23.6 23.2 23.5 22.6 23.8 24.0 Cr A 20.7 21.8 20.9 21.7 20.2 22.2 20.5 21.3 Ni F 4.7 6.1 4.6 4.8 4.9 6.0 4.9 5.0 A 7.3 6.4 7.3 6.4 7.4 6.3 7.7 7.1 F 4.03 3.22 3.81 3.76 3.34 2.95 3.40 3.43 Mo A 2.66 3.11 2.52 2.88 2.17 2.73 2.18 2.40 F 0.02 0.04 0.06 0.05 0.01 0.04 0.03 0.04 N A 0.29 0.42 0.30 0.30 0.21 0.45 0.21 0.23

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9 are shown for the both conditions in Figure 9. The partitioning for Cr, Ni and Mo in the base metal is in good agreement with results from other investigations (19). The nitrogen content is 5 to 10 times higher in the austenite than in the ferrite. However, due to the low nitrogen level, there is a comparatively large scatter in the values for the ferrite phase. Assuming that the nitrogen concentration of the ferrite in samples C1U and K1U is 0.04 and 0.03 % respectively, the P-values as shown in Figure 9 are obtained. In as welded condition the contents of the substitutional elements were about the same in austenite and ferrite and thus the P-values are close to unity. Nitrogen on the other hand was strongly concentrated to the austenite. After annealing at 1050C the P-values in the weld metal were approaching those of the base metal. No principal difference between the two heats with different nitrogen contents could be observed. Due to the high ferrite content in weld K1U the nitrogen content in the austenite was higher than in weld C1U although total nitrogen was lower in K1U. Pitting corrosion tests All corrosion tests were made according to ASTMG48-A on as welded specimens. As mentioned earlier, the microstructure at the weld surface was often different from that within the weld. This is the reason why the weld surfaces were not ground, but only pickled to remove weld oxide prior to test, although it will limit the possibility to compare these results with other investigations. In most published investigations the surface of the weld metal has been removed by grinding. The CPT-values measured for flat welded specimens and welded pipes and the corresponding ferrite content are given in Table 13 and Figure 10. The CPT-value for the base metal varied between 35C and 40C for different plate thicknesses of heat I. The CPT-values plotted versus the ferrite content in Figure 10 are the values measured at the sites where the corrosion attacks started i.e. root or top side respectively, as specified in Table 13. Table 13 a, b: CPT values, location of attack and microstructure at weld surface for the different welds Table 13 a: Plate welds
Weld no A1 A1 A2 B1U B1U B1M B1M B2 C1B C1U C1M Figure 9 Partitioning of Cr, Ni, Mo and N in base metal and weld metal of welds K1U and C1U. D1U D1M D2U D2M E1U E1M E2 F1 F2a F2b K1B K1U K1M Condition AW PWHT AW AW PWHT AW PWHT AW " " " " " " " " " " " " " " " Microstucture* at weld surface Root Top 0.9FN A 0.5F 0.7FN 0.5F 0.5F 0.5F 0.5F 0.9FN 0.9F 0.7FN 0.9FN 0.9FN 0.8FN 0.9FN 0.7FN 0.9FN 0.9FN 0.5F 0.3F FN 0.9FN Heat I Heat II Heat V 0.5F 0.1 F 0.5F 0.7FN 0.5F 0.4F 0.5F 0.6F 0.9F 0.4FN 0.4F 0.9FN 0.4FN 0.2F 0.9FN 0.8FN 0.8FN 0.9FN 0.8FN 0.8F 0.4F FN FN 0.9FN CPT in FeCI3 25 30 25 22.5 27.5 30 25 22.5 7.5 15 15 15 15 22.5 22.5 12.5 15 17.5 20 30 27.5 7.5 12.5 15 Location* of attack at CPT RW TW RW TW RTW TW TW RW TW RW RW TW RW RW RTW RW TW RW RTW RW TW TW RTW RTW

Weld A1-C1M: Weld D1U-K1B: Weld K1U, K1M:

Table 13b: Pipe welds

Weld no 1300 1301 1302 1303 1703 1704 1705 1706 Figure 10 CPT in FeCI3 versus ferrite content in weld metals. Welds according to Table 13. Condition PWHT AW PWHT AW PWHT AW PWHT AW Microstructure* at weld surface Root Top 0.5F 0.5FN 0.5F 0.8FN 0.5F 0.9FN 0.5F 0.7FN 0.5F 0.2F 0.5F 0.2F 0.5F 0.4FN 0.5F 0.8FN CPT in FeCI3 <20 >17.5 <20 22.5 25 22.5 30 20 Location* of attack at CPT RW RW RW TW RW RW RW

* Symbols: Microstructure: austenite (A), ferrite (F) and ferrite with nitride precipitates (FN). 0.5F denotes a fraction of 50% ferrite. Location; weld metal (W), root (R) and top side (T) respectively.

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10 The CPT value is a measure of the material's ability to resist initiation of pitting corrosion. In order to measure the effect of different parameters on the propagation, the weight loss of the specimens at temperatures above CPT was determined. Some examples are given in Figures 11 and 12. The difference between the high and a low nitrogen materials is obvious, also when the low nitrogen material has been welded with a filler metal with nitrogen addition, Fig. 12. At a temperature of 10C over the CPT the weight loss of the high nitrogen material steel was about one fifth of that of the low nitrogen material, although the CPT value was almost equal for the different welds, 12.5-15C.

Discussion
Effect of nitrogen and nickel on pitting resistance and microstructure (laboratory heats)
The tests with the laboratory heats showed that nitrogen had a clearly beneficial influence on the pitting resistance of both base and weld metal, see Figure 2. A similar influence has been found for base metal and simulated heat affected zones (1). The effect of nitrogen in the weld metal was at least as high as in the base metal. However, the weld metal appeared to have a lower pitting resistance than the base metal. A certain positive influence of nickel could also be observed for the weld metal while nickel seemed to have no effect for the base metal. Therefore, as nickel normally is considered to have a negligible influence on the pitting resistance in stainless steels the observed positive effect should be related to the role of nickel in controlling the weld microstructure. The ferrite contents obtained in the weld metal with an arc energy of about 0.2 kJ/mm were in the range 7090%. A multiple regression analysis on the influence of chromium, nickel and nitrogen on ferrite content only gave a statistically significant correlation for nitrogen having a clearly negative effect. As both the fraction of austenite and CPT of the weld metal were increased by nitrogen addition one conclusion could be that the major contribution of nitrogen to increased pitting resistance is its effect on microstructure.
figure 11 Weight loss in FeCI 3 versus temperature for autogenous GTA welds in 3 mm material. Further data: Weld C1U D1U E1U K1U %N 0.179 0.168 0.168 0.106 % ferrite 65 70 68 81 Arc energy 0.66 0.21 0.41 0.45 15 15 12.5 12.5 CPT

Test with production heats

Mechanical properties The mechanical tests of welded plates as well as welded pipes showed that the strength and ductility of base and weld metal were similar both in as welded and PWHT condition. The impact tests were performed at -40C, a temperature specified in many pipe-line projects. Both GTAW and PAW processes gave high impact toughnesses of weld metals in as welded and PWHT condition also when no filler metal was used. The ferrite contents ranged from 30 to 60% but appeared to have no significant influence on the impact toughness. This could be concluded from Tables 9 and 11 where it is shown that the PWHT of pipes 1703 and 1705 has not resulted in any great improvement of the impact energy although the ferrite content decreased with more than 20 %.

Figure 12 Weight loss in FeCI 3 versus temperature for 3 mm GTA welds with filler. Further data: Weld C1M D1M E1M K1M %N 0.179 0.168 0.168 0.106 % ferrite 60 71 58 81 Arc energy 0.71 0.26 0.50 0.65 CPT 15 15 15 15

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11 The SMAW and SAW weld metals had impact toughnesses of 30-40 J. Here, the PWHT resulted in a substantial improvement of the impact energy with the same decrease in ferrite level as for PAW weld metals. As the microstructure in the SAW weld metal was free from precipitates it is suggested that a coarser ferrite grain size and an unfavourable grain orientation caused this difference in behaviour. In general the impact energies noted for the fusion line are on the same level as those of the weld metal. Due to the weld geometry the crack propagation was partly in the weld metal. Also the values 2 and 5 mm from the fusion line are in some cases influenced by weld metal which partly explains the lower values than for the base metal. Microstructure and composition Autogenous GTAW and PAW weld metals of the high nitrogen steels, made with arc energies of 0.5-0.7 kJ/mm contained 60-65 % ferrite. This could be compared with the heat with low nitrogen content where ferrite levels up to 90% was measured. However, when very low arc energies were used, as in the examples with GTAW bead on plate resulting in 0.1 kJ/mm, the ferrite content was about 90% also in the high nitrogen material. When using low arc energies precipitation of fine particles can occur within the ferrite in both weld metal and HAZ. Normally there is a precipitate free zone immediately adjacent to the austenite and in welds with sufficiently high austenite contents the distance between the austenitic areas appears to be small enough to prevent the precipitation. The precipitates were in a limited number of samples identified by electron diffraction as Cr2N. In general a higher nitrogen content in the steel appeared to reduce the occurrence of Cr2N by increasing the amount of austenite. However, at low arc energies resulting in ferrite contents above 60% some nitrides could be observed. Despite the presence of nitrides in GTAW root welds the ductility and bendability was very high. The occurrence of a surface zone with higher ferrite content than the bulk of the weld probably is the result of different cooling conditions at the surface. This phenomenon has to be studied in more detail to be fully understood. When the weld metal microstructure is developed from a fairly homogeneous ferrite to a duplex ferritic-austenitic structure, EPMA showed that only a very limited migration of substitutional elements is involved. On the other hand, nitrogen, being an interstitial with high diffusivity, appears to participate to a very large extent in the reformation of austenite. The nitrogen levels reported for the austenite in Table 12 were measured on the coarser austenite areas along the ferrite grain boundaries. Limited measurements in smaller austenite particles within the ferrite grains indicated even higher nitrogen contents. Thus, nitrogen, and most likely also carbon, plays an important role in controlling the austenite formation. As a consequence, substituting nickel with nitrogen could increase the austenite content of the weld metal without altering the austenite content in the base metal. (13). The metallographic examination of the structure at the weld surface confirmed the detrimental effect of very high ferrite levels. In some cases extremely low CPT values were correlated to very high ferrite levels, often with nitride precipitates also at the surface. The specimens with the highest CPT values had less ferrite in the weld surface, sometimes even pure austenite, and no nitrides. The EPMA of the weld metal showed that the alloy contents in the two phases were almost equal, the higher nitrogen content of the austenite being the only difference. This will have the effect that the PRE number (defined as PRE = Cr + 3.3 Mo + 16 N) for the ferrite is lower than for the austenite. Nitride precipitates make the ferrite in the weld even more susceptible to pitting corrosion, and could therefore enhance the effect of a low PRE number. As the addition of nitrogen does not change the composition of the ferrite in the weld metal to any large extent the effect of nitrogen on pitting resistance should be through its influence on the phase balance. The tests with production heats which were performed on pickled surfaces generally resulted in lower CPT than the tests with laboratory heats which were performed on ground surfaces. Apparently the weld surface has an unfavourable microstructure as regards the initiation of pitting. The observed beneficial effect of nitrogen in the laboratory heats was therefore not so evident on the production heats although a favourable effect of nitrogen on the resistance to pit propagation at temperatures slightly above CPT was observed. As all tests showed a lower CPT in the weld metal than in the base metal (both with pickled and ground surfaces) filler metals overalloyed in chromium and molybdenum should be considered for applications where a slight decrease of the pitting resistance in the weld metal cannot be accepted. However, steels with low nitrogen content often are attacked in the HAZ which would then be the weakest point. In the material with high nitrogen content, on the other hand, no attacks have occurred in the HAZ.

Conclusions
The present investigation on duplex stainless steels of type 22Cr 5Ni 3Mo N (UNS S31803) with variation in nitrogen has shown that - High nitrogen content gives high ductility and impact toughness in the weld metal and heat affected zone in the as welded condition irrespective of if filler is used or not. - The ferrite content after normal welding procedures of the high nitrogen variant is 65 % maximum. - Nitrogen is governing the reformation of austenite during welding. - Nitrogen is beneficial as regards the pitting resistance of the base metal probably because it increases the pitting index of the weakest phase which is austenite. - In the weld metal a positive effect of N can be observed on the bulk structure (ground surfaces) due to the higher austenite content. However, the surface structure can vary considerably and high ferrite con-

Pitting corrosion
The results in this investigation show that the ferriteaustenite ratio in the weld surface is an important factor in determining pitting corrosion resistance, which to some extent confirms the results in other investigations

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References
1 Tsuge, H, Tarutani Y and Kudo T, Corrosion/86 Paper No 156, NACE 1986 2 Miyuki H et al, Duplex Stainless Steels, ASM Metals/ Materials Technology Series, Paper 8201 -005,1983, p. 95 3 Sakai, J et al, J Materials for Energy Systems, Vol. 5 No 2, Sept 1983, p. 105 4 Ishizawa Y, Corrosion/86, Paper No 159, NACE 1986 5 Guha P, dark CA, Duplex Stainless Steels, ASM Metals/Materials Technology Series, Paper 8201018 1983, p. 355 6 van Nassau, L, Welding in the World, Vol. 20, No 1/2, 1982. p. 23 7 Mundt R and Hoffmeister H, Stahl u Eisen No 12, 1983, p. 611 8 Gooch, T G, Duplex Stainless Steels, ASM Metals/ Paper Materials Technology Series, Paper 8201029, 1983, p. 573 9 Pleva, J and Nordin, S, Duplex Stainless Steels, ASM Metals/Materials Technology Series, Paper 8201030, 1983, p. 603 10 Pleva, J and Johansson, B, Corrosion/84, Paper No 218, NACE 1984 11 Kolts, J et al, Corrosion/82, Paper No 190, NACE 1982 12 Pleva, J, Proceedings of "Stainless Steels '84", Gteborg. The Institute of Metals, London 1985, p. 343 13 Bower, E N, Fielder, J W and King, K J, 25 Journees des Aciers Speciaux, St. Etienne, May 1986 14 Sridhar, N, Flasche, L H and Kolts, J, Corrosion/84, Paper No 244, NACE 1984 15 Ikeda A et al, Corrosion/86, Paper No 333, NACE 1986 16 Suutala, N et al, Met Trans Vol. 10A, Aug. 1979, p.1183 17 Kotecki D. J., Welding Research Suppl. Nov. 1982, p. 352s. 18 Runnsj, G, Carbon and Nitrogen in Steel Thesis Uppsala University, 1981 19 Nagano H., Kowaka M., Tetsu-To-Hagane, 66 (8), July 1980, p. 1150

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Textures and Anisotropy in Duplex Stainless Steel SS 2377

by W. B. Hutchinson, Swedish Institute for Metals Research, Stockholm, Sweden, U. v. Schlippenbach, RWTH, Aachen, FRG, and J. Jonson, Research and Development, Avesta AB, Avesta, Sweden

Abstract
Crystallographic textures have been measured in a number of plate samples of duplex stainless steel SS 2377 and in one case the textures have been examined in detail using orientation distribution functions (ODFs). With decreasing plate thickness (i.e. increased hot rolling reduction) the textures become sharper and the duplex microstructure is progressively refined. As a result of these changes the strength rises and becomes increasingly anisotropic. Calculations of mechanical anisotropy carried out using the ODF measurements show fair agreement with measured tensile test values. There is no evidence to support a significant fibre reinforcement effect arising from the duplex microstructure.

Materials and experimental procedure

All samples have been taken from commercially manufactured plates of this alloy which has a typical composition 22% Cr, 5.5% Ni, 3% Mo, 1.5% Mn, 0.5% Si and 0.15% N. The plates were produced by hot rolling with subsequent annealing and quenching to equalise the proportions of and phase. Since the cast slabs were of constant thickness the accumulated strain during hot working increased with decreasing final plate thickness. Mechanical properties have been assessed by standard tensile testing of plates of various thicknesses. Microstructures have been examined by optical microscopy, and crystallographic textures have been measured using reflection pole figures. Previous work (1) showed that the textures could vary considerably with depth below the surface of the rolled plates. The present measurements were restricted to the central 50% of the plate where the structure and texture were almost homogeneous. The texture of the thinnest plate, D, was investigated in greater detail using orientation distribution functions (ODFs) calculated according to the method of Bunge (2). The ferrite and austenite phases were treated independently; reflections from overlapping diffraction lines such as (110), (111) were omitted. Tensile test properties were calculated from these ODF data on the basis of Taylor's model (3) using the method described by Hosford and Backofen (4) as elaborated by Bunge and Roberts (5). It was assumed in these calculations that the two phases were of equal volume and had the same critical resolved shear stresses for slip. In previous work (1) it was found that the microhardness of the two phases was quite similar. Results of the calculations were compared with measurements carried out on specimens from which 25% of the thickness had been removed from both sides by grinding in order to eliminate the heterogeneous texture, existing near to the plate surfaces.

Introduction
The crystallographic texture and mechanical properties of duplex steel SS 2377 were reported in a recent paper (1). It was shown that both the ferrite and austenite were remarkably sharply textured and that the strength of the rolled plate was unusually anisotropic as a result of the contributions from the two phases and their mutual interaction. There was no evidence of composite reinforcement effect controlling the behaviour of the two-phase material. The present work extends that reported earlier to examine the situation in plates subjected to a range of hot rolling reductions. The semi-quantitative analysis of mechanical anisotropy which was presented earlier has been further refined by the application of orientation distribution functions to the textures of the two phases.

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Results and discussion

Figure 1 shows a summary of tensile test data for plates of different thickness representing typical flat rolled products. It can be seen that the strength rises with reduction in thickness and that transverse samples are consistently stronger than longitudinal ones. This directionality of strength becomes more pronounced with increasing rolling reduction, being as great as 15% of the mean value for the thinnest plates. Such high degrees of anisotropy are seldom encountered in materials with cubic crystal structures. Optical micrographs in Figure 2 show the structures for four plates of different thickness (A = 30 mm, B = 15 mm, C = 8 mm and D = 4 mm). In all cases there is evidence of a laminated structure composed of alternating ferrite and austenite bands. However, the perfection of the modulated structure becomes greater with increasing rolling reduction and the thickness of the individual lamellae decreases. Closer examination shows that both phases are comprised of recrystallised grains. In almost all cases the ferrite and austenite lamellae are essentially one grain thick so the lamellae spacing may be considered to a good approximation as the grain size in these steels. There is evidently a progressive refinement in grain size with decreasing plate thickness which is presumably responsible for the increasing strength levels. To demonstrate this effect the yield strengths, taken as an average of the

Figure 1 Representative yield stresses for tensile specimens from rolling and transverse directions as function of plate thickness.

Figure 2 Optical micrographs showing typical structures of the four plates of different thickness. A = 30 mm, B = 15 mm, C = 8 mm and D = 4 mm.

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15 values in the 0 and 90 directions to minimise anisotropic effects, have been plotted in Figure 3 as a function of grain size. Preferred crystallographic orientations of the plates A to D are shown in Figure 4 in the form of (200) pole figures for the ferrite and austenite phases. The textures of the different samples contain broadly the same components in each case but their sharpness is markedly enhanced with increasing rolling reduction. The thicker plates also show considerable asymmetry due to residual effects from the coarse as-cast structure. In the thinner plates the texture is remarkably sharp in both phases compared to single phase stainless steels and also differs in character. A complete description of the texture in plate D has been prepared in the form of orientation distribution functions (ODFs) for both phases. Figures 5 (a) and (b) show the ODFs for the ferrite and austenite phases respectively. The ferrite texture consists principally of a sharp fibre spread from (100) [011] to (211) [011]. There are also minor spreads away from this latter component towards (311) [232] and (322) [241]. An interesting feature of the -phase in this case is the almost complete absence of (111) [uvw] components which usually dominate bcc rolling and annealing textures. The austenite texture is well defined

Figure 3 Petch plot relating yield stress (average of 0 and 90 tests) to average grain thickness for the four plates A-D.

Figure 4 (200) pole figures for ferrite (upper half) and austenite (lower half) in the four plates A-D.

Figure 5 Orientation distributions for plate D (a) ferrite, and (b) austenite.

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16 although not so sharp as that of the ferrite. It comprises a peak at the orientation (110) [223] with ridges of high intensity connecting this to additional peaks at approximately (230) [001] and further to (230) [324]. This is not a common preferred orientation in fcc metals but does bear some similarity to that found after cold rolling and recrystallisation of copper containing small additions of phosphorus (6). The textures observed in these duplex stainless steels are difficult to interpet in that they may evolve both during hot rolling and during subsequent annealing. Temperature influences not only the tendency for recrystallisation but also the relative proportions of the two phases. It is quite possible that the growth of one phase into the other with changing temperature is a form of recrystallisation which plays a role in determining the final texture. Further work is necessary to elucidate these phenomena. Using the ODF texture data shown above for steel D, the anisotropy of mechanical properties has been calculated for the ferrite and austenite respectively, and also for the aggregate two-phase material. The calculation (4,5) involves finding the most favourable conditions for plastic flow by varying the assumed strain ratio (r-value). The result gives the r-value and Taylor strength factor which are predicted on the basis that all grains undergo the same shape change. It is important to note that calculations for the duplex case are not average values of the two phases separately. Mutual interactions take place which can, for example, result in the aggregate having a greater strength than both of the constituent phases. Figure 6 shows the result of calculations of plastic strain ratio (r-value) and Taylor strength factor (M) for tensile testing along different directions in the plane of the sheet. The calculations were carried out assuming [111] <110> slip for the fcc phase and [110] <111> slip for the bcc phase. Some calculations were also made for the latter phase based on <111> pencil glide. For both phases the textures produce a maximum in the r-value near to 45 to the rolling direction with minima at 0 and 90. The anisotropy is considerably more pronounced for ferrite than for austenite. The calculation for both phases together produces an intermediate behaviour which lies somewhat closer to ferrite than austenite. The Taylor factor which defines the strength level is almost constant for austenite but varies greatly in case of ferrite. There is a minimum near 45 and maxima at 0 and 90. For the duplex material the Taylor factor is intermediate between the ferrite and austenite values except close to the rolling direction where it lies above both of these. Figure 7 compares the experimentally determined r-values and flow stresses (at plastic strain = 1 %) with the calculated values for the duplex material. The predicted directionality of properties has the correct form although there are some substantial deviations from the measured values. With regard to the r-values it is seen that the predicted anisotropy is greater than that found experimentally although the reverse is true in the case of the yield stresses. Note that the yield stress values have been fitted using the 0 test (rolling direction) since a calculation of the absolute strength level is not possible. It is often observed in bcc pure metals that slip is of a pencil glide type rather than being restricted to [110] planes as assumed in the above calculations. Accordingly, some calculations were performed where the ferrite phase was assumed to deform by <111> pencil
Figure 7 Comparison of calculated and experimentally determined anisotropy for duplex stainless steel D. Lower figure shows r-values and upper figure shows 1 % proof stresses.

Figure 6 Calculations of anisotropy of r-value (lower curves) and Taylor strength factor (upper curves) using texture ODF data. The calculations are shown for both phases separately and combined together in the duplex structure.

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17 glide while the austenite retained the expected [111] <110> systems. These calculations for 0, 45 and 90 test directions are shown by the stars in Figure 7. Somewhat worse fit was obtained regarding strength levels in this case than in the previous calculation suggesting that pencil glide is not an appropriate description for the slip mechanism in this type of highly alloyed ferrite. The discrepancy between experiment and theory may to some extent be explained by the assumption of equal resolved shear stresses for slip in the two phases, although microhardness values are observed to be virtually the same in each. There is no evidence in the present study of a fibre reinforcement effect contributing to the directionality in strength properties. Such an effect would require a substantial difference in strength between the two phases which is not observed, and should produce maximum and minimum strengths in the 0 and 90 directions respectively which is again contrary to observations. Finally, it should be noted that the calculations based on texture data and the accompanying measurements apply only to the central zone of the plate. In full-thickness tests the results are strongly influenced by the subsurface zones which have differing textures and contribute significantly to the difference in strength levels between 0 and 90 directions as shown in Figure 1.

References
1 W.B. Hutchinson, K. Ushioda and G. Runnsj, Mat. Sci. & Techn. 1985, 1, 728. 2 H.-J. Bunge, Mathematische Methoden der Texturanalyse, 1969, Akademieverlag, Berlin. 3 G.I. Taylor, J. Inst. Met, 1938, 62, 307. 4 W. F. Hosford and W. A. Backofen, in Fundamentals of Deformation Processing, Syracuse Univ. Press, 1964, p. 259. 5 H.-J. Bunge and W.T. Roberts, J. Appl. Cryst, 1961, 2, 116. 6 V. Schmidt, K. Lcke and J. Pospiech, 4th Int. Conf. on Textures, 1975, Cambridge, p. 147.

Conclusions
The strength of duplex stainless steel SS 2377 increases with refinement of the l phase dispersion which may be considered as a grain size strengthening effect. Both the austenite and ferrite may show unusually sharp textures which result in a marked directionality of strength. Fair agreement is obtained between measured anisotropy and that calculated on the basis of quantitative texture determinations. There is no evidence of a significant fibre reinforcement effect arising from the duplex structure.

Acknowledgements
The authors thank Professors R. Lagneborg and K. Lcke for provision of laboratory facilities. Useful contributions to the work were also made by K. Ushioda and G. Runnsj.

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Applications and Uses of Duplex Stainless Steels

by
Jan Olsson, Research and Development, Avesta AB, Avesta, Sweden, and Sten Nordin, Avesta Projects AB, Karlstad, Sweden

Abstract

Table 1: Typical chemical compositions of different stainless steels mentioned in this paper
Grade SS 2324* 3RE60-old 3RE60-modified 25-5-1 L 25-6-1 L 2205 SS 2343 304L 316L AISI 317 904L 254 SMO Cmax 0.10 0.030 0.025 0.025 0.030 0.030 0.05 0.030 0.030 0.05 0.020 0.020 Cr 25 18.5 18.5 25 25 22 17 18 17 18 20 20 Ni 5 4.7 5 5 6 5.5 11 10 11 14 25 18 Mo 1.5 2.8 2.8 1.5 1.5 3 2.7 2.3 3.5 4.5 6 N 0.08 0.09 0.17 0.15 0.20 Others

Duplex stainless steels offer a combination of strength and corrosion resistance which makes them attractive for a variety of applications. Today their major use is in sour gas and sour oil. In this paper their engineering properties are discussed with emphasis on applications in chemical and petrochemical industries, environmental control, pulp and paper, food production and transportation of chemicals.

Introduction
Ferritic-austenitic or duplex stainless steels have been available on the market for approximately 50 years. However, the very first duplex steels had an unfavourable ferrite-austenite balance which resulted in rather poor mechanical properties of the heat affected zone after welding. Besides, the heat affected zone could be prone to intergranular corrosion due to a high carbon level in combination with the above mentioned unfavourable ferrite-austenite balance, viz. close to 100 percent ferrite. Today duplex steels are often composed in a way which ensures a high safety against the disadvantages described above and they should therefore be ideal materials for general engineering purposes having the combination of high mechanical strength, good corrosion resistance, good weldability and good formability in mind. Despite this, the main field of application for modern duplex stainless steels have been piping for oil and gas exploration and to some extent heat exchanger tubing, which, from design and fabrication point of view, are rather simple applications. The purpose of this paper is to emphasize the possibilities to utilize modern duplex stainless steels as general purpose engineering materials. The grades discussed are Avesta 3RE60, 25-5-1 L, 25-6-1 LN and above all, 2205.

Cu Cu

* Traditional duplex stainless steel

The first commercial installations of Avesta 3RE60 were made late 1972 and the first failure due to intergranular corrosion in the heat affected zone was reported in 1973. Two syrup tanks in a Swedish sugar plant, steel grade SS 2343 (AISI 316), had suffered stress corrosion cracking in the bottom area and new lower parts, made of 3RE60, were installed early 1973. Late 1973 leakages were reported and at an inspection in January 1974 and by the subsequent laboratory investigation it was established that the leakage was caused by intergranular corrosion. The heat affected zone contained almost 100 percent ferrite and the carbon, which could not be dissolved in the ferrite, had precipitated as chromium carbides along the grain boundries. The syrup contained up to 1 percent of chlorides, it had a pH of approximately 5 and it was stored at max 80C. A few months later similar damages were reported for hot water tanks and calorifiers in Australia. Most probably the chloride containing water (up to 1000 ppm chlorides were reported) had initiated pitting and then the acid solution formed in the pits caused the propagation of intergranular corrosion. These cases clearly demonstrated that despite the more favourable austenite-ferrite ratio in 3RE60, this first attempt to create a more versatile duplex stainless steel for general engineering purposes was not entirely successful. More austenite in the heat affected zone was required! It should be noted, however, that the number of failures, (a few more were reported later) was very small compared to the total number of installations.

Historical background
One of the first modern duplex stainless steels for general engineering purposes was Avesta 3RE60, introduced on the market close to 15 years ago. Compared with the traditional duplex stainless steels it had a lower chromium level, which reduced the ferrite content. In order to maintain an acceptable corrosion resistance the reduced chromium level was compensated for by an elevated content of molybdenum, see also Table 1. These measures gave a ferrite-austenite ratio of approximately 60:40 compared to 70:30 for the old grades.

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Duplex of today
Improvement of 3RE60 The above described failures resulted in further development of 3RE60 aiming at a higher austenite content. The parameter used was the ratio between the chromium and nickel equivalents acc. to the Schaeffler-de Long diagram and Table 2 shows a summary of the test results leading to the modified 3RE60 with a high resistance to intergranular corrosion. It was found that a material with a chromium equivalent - nickel equivalent ratio in the range 3.0-3.2 could be susceptible to intergranular cracking while a ratio of 2.6 or less ensured sufficient resistance to this type of corrosion. 3RE60 has been produced according to this formula ("modified" composition acc. to Table 1) since 1974 without one single case of intergranular corrosion reported. More than 2000 tons of sheet and plate material have been supplied and the replacement of the syrup tanks described above, see "Historical background", was among the very first installations.

Mechanical properties The yield strength is approximately twice as high as for conventional austenitic grades and the tensile strength is also higher. The ductility is inferior when compared to the austenitic grades but still acceptable for several operations, see below under coldforming. The most severe deep-drawing operations, e.g. the pressing of sheets with complicated patterns for plate heat exchangers, cannot be conducted, however. The toughness is acceptable for sub-zero temperatures, also in welded condition for temperatures down to at least -40C. Fatigue The duplex stainless steels in general have far better resistance to fatigue than the austenitic grades both in inert environments and corrosive environments. In the latter case, the alloy composition and the corrosion resistance also play an important role, see Table 3. Hot forming The duplex grades are readily hot formed and at low deformation rates they show a superplastic performance at temperatures in the range 800 to 1000C. Cold forming All types of coldforming operations can be performed but the lower ductility does not permit so severe pressing operations as with the austenitic grades. Also the duplex grades workharden at coldforming but not to the same extent as the austenitic grades. Spinning, e.g. for the fabrication of dished ends, can be performed. Table 4 shows some results achieved at the test spinning of cones.

Engineering properties
The engineering properties of the duplex stainless steels are mainly determined by the ferritic-austenitic structure and by the ferrite-austenite balance in the heat affected zone after welding.

Table 2: Intergranular corrosion in neutral and acidified chloride containing waters. Welded 3RE60 U-bend samples.
Cl ppm 5000 1 3 7 1 3 7 1 3 7 1 3 10000 10000 15000 15000 1 3 1 3 1 3 3 90 70 90 70 50 PH C 3.2 X X X X X X X X X X X X Cr equiv./Ni equiv. 3.0 0 0 X 0 0 X X 0 0 0 X 0 0 X 0 0 2.6 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Table 3: Fatigue and corrosion fatigue strengths in water for some stainless steel grades.
Grade SS 2343 3RE60 2205 (20) (25) (50) Distilled water 225 MPa 320 MPa not tested Synthetic sea water 215 MPa 305 MPa 365 MPa

Figures within brackets give test material plate thickness. Rotating bending with 1500 cycles/min. fatigue limits are 7 given for 10 cycles.

5000

70

5000

90

10000

50

Table 4: Results from the spinning of welded cones made of austenitic and duplex stainless steels.
SS 2343 Wall, mm original spinning 1 spinning 2 Cone length, mm original spinning 1 spinning 2 Final hardness, Hv Base-matrix Base-weld Top-matrix Top-weld 3.0 2.5 1.5 190 215 313 327 306 311 345 2205 3.1 2.7 1.7 190 210 291 380 390 357 413

Chlorides added as sodiumchloride, acidified by additions of hydrochloric acid x = intergranular cracking O = no intergranular cracking - = not tested

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20 Welding Welding can easily be performed utilizing the same welding techniques as for austenitic grades. There are two hazards discussed in connection with the welding of older types of duplex stainless steels - too low heat input enables the heat affected zone to cool down too rapidly, thereby retaining an almost completely ferritic structure. This is in reality no hazard since the latest duplex steels, e.g. Avesta 2205, have sufficiently high austenite stability also at high temperatures. - too high heat input causes grain growth of the ferritic grains in the heat affected zone giving as a result reduced toughness of this area. Several modern duplex steels e.g. Avesta 2205, have sufficiently high austenite content of the heat affected zone to prevent such grain growth. As indicated above neither low nor high heat input implies any great risk of deteriorating the material properties of the heat affected zone after welding, but using a normal heat input means being on the safe side. Driers One special type of drier has been used forthe drying of spent grains from whisky distilleries and breweries, Fig 1. Rotating discs made of 3RE60 on a hollow shaft are internally heated with steam of 170C. The spent grains have a high moisture content, several thousands ppm of chlorides and a slightly acid pH. Ten such "Rotadisc" driers made of 3RE60 are in service in Great Britain and Ireland, the oldest since 1974. Similar driers have also been used for the drying of fish meal and blood meal.

Corrosion resistance
One consequence of the duplex structure is excellent resistance to stress corrosion cracking. Resistance to general corrosion, pitting and crevice corrosion is determined by the contents of alloying elements, mainly chromium, molybdenum, and nitrogen. When compared with the austenitic grades, Avesta 3RE60 has approximately the same corrosion resistance as molybdenum alloyed steel of type SS 2343 (AISI 316) while the higher alloyed grade 2205 is superior to conventional grades like AISI 316 and 317 and very close to Avesta 904L Figure 1 Rotadisc drier made of Avesta 3RE60 for a brewery. (Courtesy of Stord Bartz A/S) Suction rolls One of the biggest applications for 3RE60 has been suction rolls for paper machines, Fig 2. More than seventy such rolls have been supplied for paper machines, the biggest being three rolls with a length of 10 m and a weight of 30 tonnes per piece for a US paper mill.

Applications and uses

Avesta 3RE60 Having in general the same corrosion resistance as SS 2343 with the extra merits of having superior resistance to stress corrosion cracking and corrosion fatigue, 3RE60 has mainly been used to resist SCC and corrosion fatigue. Tanks As mentioned above one of the first installations of 3RE60 was for tanks where warm syrup was stored. After the first failure the 3RE60 tanks have been in service for more than 10 years without any problems reported. Hot water tanks and hot liquor tanks for breweries are other examples where 3RE60 has been used successfully for up to 7 years. The following data have been reported for the stored liquids chlorides up to 280 ppm pH 7.2-7.5 temperature max 100C 3RE60 has also been used for hot water tanks in other types of plants connected with food production, e.g. abattoirs.

Figure 2 Suction roll made of Avesta 3RE60 for a paper machine.

Others Avesta 3RE60 has also been used for a great number of other applications, some of them listed below. In general, however, it has been used to solve stress corrosion cracking problems and in a few cases fatigue or corrosion fatigue problems. - Calorifiers - Centrifuges - Distillation columns - Expansion bellows - Fans - Heat exchangers - Process vessels

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Avesta 25-5-1 L and 25-6-1 LN

Like 3RE60 the above mentioned grades are less common today but the following examples show how duplex stainless steels can be used to solve specific corrosion problems. Pressure Vessel Fabrication Four large pressure vessels for chemicals recovery in a styrene plant were fabricated. The process conditions indicated risks for stress corrosion cracking and due to the "non-productive" service the investment costs had to be kept at a minimum. The engineering firm had specified the material to be 44LN duplex stainless steel, i.e. equal to Avesta 25-6-1 LN (R DirscherI and S Barth, "Duplex Stainless Steel Fabrication", 1982ASM Metals Congress, Paper No 8201-026). Design pressure was 2.7 atm (25 psig), max, and maximum design temperature 260C. At that time no ASME Code existed so the fabricator had to apply for a Code Case to permit the material for welded construction in accordance with Section VIII, Division 1 of the ASME Boiler and Pressure Vessel Code. By the same token the weldability had to be evaluated and was found to be good and the results of the mechanical tests met the requirements of the ASME code as per above, Section IX. The approval was designated Code Case 1893. Two of the vessels were 4.5 m OD x 14.6 m with shell thickness 14 mm and head thickness 21 mm. The other two were 5.5 m ID x 11.3 m with thickness of 17 mm for shells and heads. Welding methods included SAW, SMAW and GTAW. After completed fabrication all butt welds were fully radiographed. Only 8 m (out of 652 m) were rejected due to slag inclusions, 178 mm due to porosity and another 178 mm due to lack of fusion. Not a single crack was found in a material that was belived to be susceptible to cracking. This example shows that duplex stainless steels are well suited for heavy vessels and that available fabrication techniques can be used successfully. Stripper Vessels in PVC Production In the production of polyvinylchloride, PVC, whether by the emulsion polymerization or the suspension polymerization method, unreacted Vinyl Chloride Monomer (VCM) needs to be reclaimed and the PVC-slurry purified from the monomer. In the VCM recovery stage VCM is recovered by simple flashing and stripping. However, in the stripping vessel, conditions that may cause stress corrosion cracking in austenitic stainless steels of the type 304L or 316L are at hand. In the mid seventies, duplex stainless steel was supplied for such vessels. For this particular process the operating temperature is about 85C, pH value 3-3.5 and the water phase has an average chloride content of 60 ppm, occasionally up to 150 ppm. The fabricated vessels appear on Figure 3. They were made from 5, 6,12 and 14 mm thick plates and welding methods were SMAW and SAW. The units went on stream in 1976 and have performed satisfactorily since then. Refuse Incineration A new concept for refuse incineration, utilizing the principle of wet air oxidation, has been developed in the US. Moist household refuse is being pressed down a vertical pipe several hundred meters into the ground. Pressurized air is added and the waste is being incinerated in an exothermic chemical reaction. Hence, the temperature

Figure 3 Vessels for vinyl chloride monomer stripping made of Avesta 25-5-1 L

increases down the tube and approaches 300C before the waste has been fully oxidized. The residual ashes are brought to surface in a jacket around the pipe and then deposited. The high temperature and the oxygen-rich atmosphere makes stress corrosion cracking a potential risk also at low chloride concentrations. Accordingly, a duplex stainless steel was selected for this service. The high strength simplified the design, which had to take care of the weight of the piping, and provide anti-collapse properties. The system has operated for several years now and the duplex stainless steel has given excellent service. Protein Recovery Hydrocarbons are used for extraction of valuable ingredients from various sources, e.g. waste from abattoirs. For the extraction of proteins trichloroethylene is used. From a corrosion point of view the use of this solvent requires special attention. In the presence of water it has a tendency to decompose leaving free chlorides and the decomposition also brings about a decrease of the pH value. Hence, if austenitic stainless steels are used stress corrosion cracking may occur. A Danish slaughter-house installed a system for the recovery of proteins with trichloroethylene some years ago. The extraction takes place in a cylindrical vessel with trichloroethylene flowing countercurrent to the feed of meat remainders. Heating is done by steam so the temperature is approximately 125C. The shell of the extraction vessel as well as internals were made of duplex stainless steel. It has behaved very well since put in service in 1980.

Avesta 2205
Contrary to the above described grades, 2205 has been used not only to solve SCC-problems but also pitting, crevice corrosion and general corrosion problems. FGD-Scrubbers Close to 300 tons of 2205 sheet, plate and piping was used for flue gas desulphurization scrubbers at a steel works in New Zealand. The gas enters a pre-cooler made of 904L, brick lined in the hot parts, where it is cooled from 1000C to 300C and then further to 150-200C before it enters the venturi cooler scrubber. 2205 is used from the outlet of the pre-cooler and onwards. In the venturi the gas is cooled to 85C and saturated with water, then it passes a fan

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22 The new 2205-drum was installed in the chlorine stage filter washer in the summer 1985 and has performed well during the first year of service. The following environmental data have been reported temperature residual chlorine pH 35C 12-15 ppm 2

Chloride level is not known but normal levels in C-stage washers are several thousands of ppm. Fig 6 shows the fabrication of this drum.

Figure 4 Precooler in a New Zealand FGD-unit made of Avesta 2205 and 904L. (Courtesy of Flkt Industri AB)

before it via a dewatering cyklone of 15 m height and 5 m diameter is emitted through a stack, all made of 2205. The recirculation liquor has a pH of 3-3.5, a chloride content of maximum 300 ppm and the temperature is maximum 85C. The scrubbers were installed in 1984. Fig.4 shows the pre-cooler made of 2205 and 904L. Chimney in an FGD-system Fig. 5 shows the fabrication of a 40 m high chimney intended for a Swedish pulp plant. The diameter is 4 m. Flue gas from the soda recovery boiler is desulphurized in a spray tower scrubber (made of Avesta 254 SMO) before emitted via the chimney. Despite the scrubbing, the emitted gas contains aggressive compounds like sulphur trioxide and hydrogen chloride which condensed and caused corrosion on the previously used chimney made of SS 2343. The new chimney was installed in late 1985. Figure 6 Pulp bleach plant filter washer drum made of Avesta 2205 under fabrication. (Courtesy of AB Hedemora Verkstder) Freon recovery units In the tobacco industry freon is used to fluff up tobacco leaves which have been packed for several years. Tobacco leaves are blasted with high pressure steam plus freon gas at 80C. The freon takes up odours, contaminants and steam. The spent freon is cleaned over activated carbon beds in a column containing trays of activated carbon. Previously AISI 304 was used for these units but presence of chlorides caused pitting. Three units made of 2205 were installed in early 1986. Others Avesta 2205 has also been used for several of the applications described for 3RE60. Reason being because it is in general a more common grade with better availability but also because it has been found that the corrosion resistance of 3RE60 in same cases has been inadequate. Some of these installations and also others are listed below
Figure 5 A chimney made of Avesta 2205 under fabrication.

Pulp bleach plant filter washer The environment in an acid stage pulp bleach plant filter washer is always aggressive due to low pH, chlorides and residual chlorine from the bleaching process. The conditions have been aggravated concurrently with the increased demands from environmental authorities, forcing the plants to close their systems and recirculate the liquids. In one Swedish plant where SS 2343 previously had been used for a filter drum it was decided to replace it with a drum made of 2205 when they had to close their washing water systems.

- Butadiene rubber holding tank - Calorifiers - Chemicals tankers, an entirely new field of application for duplex steels where the combination of corrosion resistance and high strength (fatigue strength included) are utilized. - Fans - Flow lines for natural gas - Heat exchangers, tubular and fabricated from sheets, for different types of industries, e.g. chemical and petrochemical industries, pulp and paper plants. - Hot water tanks and hot liquor tanks for breweries. - Press rolls for the pulp and paper industry (but not the big suction rolls, yet). - Process reactors for brown coal. - Rotadisc driers - Valves

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Discussion
The purpose with this paper has been to show that modern duplex stainless steels can, fora great number of applications, be used as conventional construction materials where one or more of the following features are utilized, - good corrosion resistance including other types of corrosion but stress corrosion cracking - good fatigue and corrosion fatigue properties - good mechanical strength - good fabrication properties. It is not necessary to consider this type of stainless steel only when the environment implies a SCC-risk for austenite grades. This is especially true for Avesta 2205, which has been used for applications where highly alloyed and more expensive austenitic grades very often are selected.

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acom No. 1-2-86

to Dr. Sten Nordin, Avesta Projects AB, P.O. Box 557, S-651 09 KARLSTAD, Sweden

acom No. 1-2-86