Industry news. Welding guidelines for duplex, super duplex and hyper duplex stainless steels. a cura di: M. Frodigh, P.-Å.

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Welding guidelines for duplex, super duplex and hyper duplex stainless steels a cura di: M. Frodigh, P.-Å. Björnstedt When welding duplex and super-duplex steels, the biggest challenge is to maintain an optimized balance between the austenite-ferrite microstructure in the final weld metal in addition to the desired mechanical properties. The purpose of this paper is to share our knowledge regarding various aspects related to practical fabrication of duplex, super-duplex and hyper duplex stainless steel welding. The paper provides practical advice on how to bring out the best of these complex materials as well as recommendations on how to retain the optimal balance of the microstructure during and after welding, and describes chemical the composition of the grades and the effect that it has on their structural stability at a macro level during welding. Joint design, shielding and backing gas selection, heat input and interpass temperatures are all covered. KEYWORDS: DUPLEX - WELDING - SANDVIK - CORROSION - SHIELDING GAS - FABRICATION Mette Frodigh, Per-Åke Björnstedt Sandvik Materials Technology, Sweden INTRODUCTION This presentation is based on the aspects on welding and fabrication of stainless steel and a group of material called duplex stainless steels. These materials consist of a microstructure with two phases, a combination of an austenitic and a ferritic microstructure. The family of duplex stainless steels has increased over the last years, as also this group of material the development has been driven towards higher mechanical and corrosion properties. The family of duplex stainless steels consists today of the following materials: Sandvik SAF 2304, Sandvik SAF 2205, Sandvik SAF 2507, Sandvik SAF 2906, Sandvik SAF 2707HD and Sandvik SAF 3207HD. (SAF = Sandvik Austenitic - Ferritic). The higher the amounts of alloying elements are the freedom to act in regards to fabrication is more narrowed. Special welding requirement is needed as the properties of the construction is highly independent of the weldment and why the welding recommendations from manufacturer are important to follow. The Chemical Composition of the duplex familiy is seen in Table 1. 36 La Metallurgia Italiana - n. 9 2017

Attualità industriale Tab. 1 - Chemical composition of the duplex family [%] Chemical composition of the duplex family [%] Grade C Si Mn Cr Ni Mo N PRE Sandvik SAF 2304 <0.03 0.5 1.2 23 4-0.12 26 Sandvik SAF 2205 <0.03 <0.10 1.2 22.5 5.5 3 0.15 35 Sandvik SAF 2507 <0.03 <0.08 <1.2 25 7 4 0.25 42 Sandvik SAF 2707 HD <0.025 0.25 1.0 27 6.5 4.8 0.39 42.7 Sandvik SAF 2906 <0.03 0.40 1.0 29 7 2.4 0.36 49 Sandvik SAF 3207 HD <0.03 <0.8 <1.5 32 7 3.5 0.5 51.5 STRUCTURE STABILITY The stability of the microstructure decreases with increasing the alloying content e.q Chromium, Molybdenum and Nitrogen. The high nitrogen content in the materials gives a rapid austenite formation during welding. The sensitive temperature range for austenitic stainless steel is normally, 900-1050 C, whereas the sensitive temperature range for Austenitic-Ferritic Stainless is 600-1000 C. Austenitic-Ferritic stainless steels are also prone to 475 C embrittlement. Figure 1 shows the precipitations that can be present in the base metal and weldment due to the effect of alloying elements and the cooling rate. These physical properties influences the welding procedure by having a weldment more sensitive than base metal due to chemical composition and the texture of the molten weld pool (wrought materials), which will require good control of the heat input and cooling rate. A too high cooling rate will give a weldment consisting of a too high amount of ferrite and precipitates, and a too slow cooling rate will give a weldment with too high amounts of precipitations, see Figure 1. Different material producers have their own metallurgy based on the experience regarding intermetallic precipitations. The metallurgy Sandvik use for the duplex materials is based on the right combinations of the main alloying elements Cr, Ni, Mo and N, due to the fact that the alloying element W increases the formation of intermetallic phases such as chi, χ, and sigma, σ, see Table 2. Tab. 2 - Precipitations of intermetallic phases Precipitations of intermetallic phases Intermetallic phase Precipitation Temperature Intermetallic phase Precipitation Temperature ὰ (alfa-prime) 300-525 C G (G-fas) 300-400 C Fig. 1 - Intermetallic precipitations as a function of temperature and time γ 2 (Gamma) 650-900 C σ (Sigma) 600-1000 C χ(chi) 700-900 C R (Laves) 550-650 C Cr 2 N, CrN 700-950 C π (Pi) 550-600 C τ (Tau) 550-650 C M 7 C 3, M 23 C 6 650-950 C La Metallurgia Italiana - n. 9 2017 37

The formation of intermetallic phases also influence in what temperature range to do stress reliving or post weld heat treatment of duplex materials. If heat treatment is necessary, the best is to do a full quench annealing cycle, which often is difficult to do in practice. MECHANICAL PROPERTIES Fig. 2 - Mechanical properties of duplex materials and some austenitic materials The mechanical properties of the duplex family are higher than comparable austenitic materials. The increases in alloying elements give higher mechanical properties and corrosion properties. The increase in mechanical properties is enhanced by the content of ferrite and nitrogen. Figure 2 shows the yield strength of most of the duplex family and some austenitic stainless steels and Figure 3 the corrosion properties of the duplex family. The corrosion properties required for these materials is mostly pitting and stress corrosion cracking. Regarding the resistance against pitting corrosion the materials can be compared using the Pitting Resistance Equivalent (PRE): PRE = Cr + 3.3(Mo + 0,5W) + 16N This means that following alloying elements Cr, Mo, W and N give increased pitting resistance, but also high amounts of Cr, Mo and W promotes intermetallic phases, which will reduced impact strength and corrosion resistance. 38 La Metallurgia Italiana - n. 9 2017

Attualità industriale CORROSION PROPERTIES Fig. 3 - Corrosion properties of duplex materials FABRICATION When the material is to be cold worked there is a need for increased force due to a higher yield strength. In general, the higher alloy content the higher is the yield strength. Duplex stainless steels give more spring back than austenitic steels at cold forming. A cold work up to approximately 10% can be done without stress relieving and as mentioned earlier the steels have good resistance to stress corrosion cracking. A local stress reliving of the cold worked area is very difficult and not recommended. If heat treatment is necessary, a full quench annealing cycle has to be performed. Before starting fabrication in the workshop of the material, there has to be certain preparations regarding the groove etc. To ensure a good control of the heat input the duplex stainless steel need a wider gap and a more open angle compared to the austenitic steels, due to the fluidity of the weld pool, see Figure 4 describing examples of groove design for duplex materials. Fig. 4 - Examples of groove design for duplex materials La Metallurgia Italiana - n. 9 2017 39

When welding the duplex materials it is important to keep the microstructure balanced in the weld metal, as it will influence both the mechanical and corrosion properties. The heat input is to be controlled as the energy allowed will decrease with increased alloying elements, see Table 3 for recommended heat input and interpass temperature. Tab. 3 - Heat input and interpass temperature Heat input and interpass temperature Grade UNS no. Heat input [kj/mm] (1) Interpass [ C] SAF 2304 S32304 0.5-2.5 250 SAF 2205 S32205 0.5-2.5 150 SAF 2507 S32570 0.2-1.5 150 SAF 2906 S32906 0.2-1.5 100 SAF 2707HD S32707 0.2-1.0 100 SAF 3207HD S33207 0.2-1.0 50-100 (1) Without the process factor, k As the nitrogen content in the duplex materials is an important element due to the formation of austenite and the positive effect on the corrosion resistance the welding gas and root gas is of great importance. The shielding gas can be seen as a welding parameter as it will affect the properties of the weld metal. For GMAW (MIG/MAG, 131/135) the best weld result is achieved using pulse arc technique with shielding gas Ar + 30%He + 1-2.5% CO 2. For GTAW (TIG, 141) welding the best result is achieved with shielding gas Ar + 2-3% N 2. Purging gas would be 100% N 2. Welding with pure argon as shielding and root gas nitrogen is lost and must be compensated for in order to maintain the corrosion resistance. Duplex stainless steels are welded with matching filler metals, see Table 4. Dissimilar joints of duplex and highly alloyed austenitic steels, nickel-based fillers must be used. Welding duplex stainless steels with nickel-based filler metal gives phenomenon like un-mixed zones (UMZ) and a fusion line which is depleted from nitrogen. Tab. 4 - Duplex stainless steel filler metal Duplex stainless steel filler metal GTAW/TIG/141 GMAW/MAG/135 SMAW/MMA/111 SAW/12 LDX 2101 23.7.L 23.7.L 23.7.L SAF 2304 23.7.L 23.7.L 22.9.3.LR/LB 23.7.L SAF 2205 22.8.3.L 22.8.3.LSi 22.9.3.LR/LB 22.8.3.L SAF 2507 25.10.4.L 25.10.4.L 25.10.4.LR/LB 25.10.4.L SAF 2707 HD TM 27.7.5.L 27.7.5.L 27.7.5.L 1) SAF 2906 29.8.2.L 29.8.2.L 29.8.2.L SAF 3207 HD TM 27.7.5.L 27.7.5.L 27.7.5.L 1) 1) 27.7.5.L SAW only trial in overlay welding 40 La Metallurgia Italiana - n. 9 2017

Attualità industriale To ensure good structure stability in the weldment the range of ferrite is described within standards or specifications, eq. API 938 C (specify a ferrite content of 30-65% in the base metal, 40-65% in the HAZ and 25-60% in the weld metal), NACE MR0175 (Ferrite content 30-70 vol.%) and DNV-OS-F101 (Ferrite content of 35-65% both in the HAZ and the weld metal). The ferrite in a weld metal can be determined by different methods, most used in laboratories are Point counting according to ASTM E562 and as a best field instrument Fischer Feritscope is a rather accurate measurements tool. in the temperature ranges 300-400 C or 500-600 C to reduce at least some of the stresses, without deteriorating the physical and corrosion properties of the weldment. Figure 5 show the critical pitting temperatures for Sandvik SAF 2205, Sandvik SAF 2507, and Sandvik SAF 2707HD in 6% FeCl 3 according to the ASTM G48A where Samples where exposed to 6% FeCl 3 solution for 24h and the temperture when pitting starts to develop is determined. As expected the corrosion resistance of the weld metal is lower than the base metal due to texture and the effect of segregations and loss of alloying elements. Fig. 6 - Temperature range of post weld heat treatment duplex materials For temperatures 300 and 350 C no observations of reduced Impact Strength were noted even after 30 hours, see diagram in Figure 7 [1]. At 400 C, weld metal had substantial reduction of impact strength after only 5 hours. The same pattern was seen for all three welding methods. In the temperature range 500-580 C, only weld metal from the SAW process was tested, see diagram in Figure 8 [1]. Reduced Impact Strength was observed for all temperatures and times. Fig. 5 - CPT for base material and weld metal POST WELD TREATMENT There are often requirements, by the codes to which they are produced, to perform a post weld stress relief. Compared to austenitic stainless steels, duplex stainless steels are limited regarding post weld heat treatment. The reason for this limitation is well known. High ferrite levels which are prone to form alpha prime at around 475 C, and intermetallic phases in the temperature range 700-975 C. When looking at Figure 6, it should be theoretically possible to perform a post weld heat treatment Fig. 7 - Heat treatment of SAW SAF 2507 weld metal in temperature range 300-400 C. La Metallurgia Italiana - n. 9 2017 41

Fig. 8 - Heat treatment of SAW SAF 2507 weld metal in temperature range 500-580 C The stability of a weldment is the ability to have a stable microstructure, chemical composition and combination. It is important to know the ferrite austenite ratio in a duplex weld as it will have an influence on both mechanical and corrosion properties. Normal range of the ferrite content is between 30-70% within specifications and standards. The ferrite in a weldment can be determined by the different methods using either destructive testing (Schaeffler, DeLong, WRC 92, ASTM E56) or non-destructive measurement by instruments, such as Magne Gauge and Fischer Feritscope. Feritscope is the best field instrument today and give rather accurate values. To ensure good weldments it is important to know the materials. A thumb rule is that higher alloying content in a stainless steel requires more knowledge in fabrication; this could be welding, cold working and heat treatment. As a summary of the fabrication following should be in all checklist; Joint design - open grooves up or use U-groove Control of heat input and interpass temperature Use nitrogen in shielding gas and purging gas REFERENCES [1] Effect of Mechanical Properties at Aging or stress reliving Weld of Grade UNS 32750 Claes-Ove Pettersson & Guocai Chai, Sandvik Materials Technology, Stainless Steel World Mastrict 2005. 42 La Metallurgia Italiana - n. 9 2017