WELDABILITY AND JOI NTNABILITY OF DUPLEX STAI NLESS STEELS Prof. Dr.

Srgio Duarte Brandi Escola Politcnica da Universidade de So Paulo, Departamento de Engenharia Metalrgica e de Materiais sebrandi@usp.br Abstract. Welding and joining of stainless steels, in particular of duplex stainless steels (DSS), has been one of the research lines of the Welding and Joining Group at Metallurgical and Materials Engineering Department in University of So Paulo since 1992. This paper is a brief report on the work done in this subject up to 2012. Weldability studies of multipass welding at low temperature HA Z (LTHA Z) as well as at high temperature HA Z (HTHA Z) and FZ (fusion zone) were conducted on s amples of UNS S32101, S 32304, UNS S31803, UNS S 32550, UNS S32750 and UNS 32760 DSS. Microstructure, mechanic al and corrosion properties in simulated (dilatomet er and or Gleeble equipment) and real welds were characterized using different techniques and tests. Intermetallic phase precipitation (sigma phase and chromium nitride) and secondary austenite were characterized and a model for secondary austenite precipitation in multipass welding of HTHA Z was proposed. Simulated samples were compared to real welds to validate the multipass thermal model and presented a very good agreement between t hem. Consequently the phase transformations studied by simulated samples represent real weld microstructure. The behavior of multipass FZ using filler met als (AWS E2259-17 and E N 25 9 4L) was also addressed. Intermetallic precipitation diagrams were determined for both filler metals and t wo DSS to compare reheated weld met al regions for three different welding procedures. The crescent heat input technique presented the best res ults. Some dissimilar welding studies using lean duplex, such as UNS S32101 and UNS S32304, and austenitic stainless steels (AIS I 304L and AIS I 316L), were also carried out. Brazeability of UNS S32101, S32304, S31803, S32750 and UNS S32707 DSS was also considered. Experiments were carried out in a hydrogen continuous furnace using three different nickel bas ed filler metals (AWS BNi-1, BNi-2 and B Ni-7). S everal brazing conditions were tested using different brazeability tests such as the sessile droplet test, the edge test, and the capillary raise test. Best wetting and

spreading results were obtained for BNi -7 for the equipment used in the experiment, but brazing thermal cycling in such furnace impaired base metal corrosion resistance due to intermet allic phase precipitation, except UNS S32101 and S32304. Introduction Weldability (and brazeability) of materials should be analyzed as an interaction among materials (base material, filler metal, and weld metal), welding/joining process (thermal, mec hanical, and physico-chemical proc ess characteristics), microstructure (FZ, PFZ, HA Z) and in-s ervice behavior. Based in this approach, weldability studies in DSS were accomplished using real welds and simulated samples of fusion welding processes [1-6]. To carry out theses studies DSS HA Z should be divided in two parts, low temperature HA Z (LTHA Z) and high temperature HA Z (HTHA Z)[2, 3,7]. By low temperature one can understand a temperature range enough to avoid changes in the as -received microstructure o of DSS plat es, which is from 950 to 650 C depending upon DSS type. In other words, LTHA Z is a region of HA Z which has minor changes in microstructure due to a small amount of int ermetallic phases precipitation (chromium nitride and sigma phase), usually not clearly observed by optical microscopy, but enough to modify mechanic al and/or corrosion behavior[2]. On the ot her hand, HTHA Z is a region where asreceived microstructure is completely modified and sec ondary austenite precipitation competes with chromium nitride precipitation or dissolution, depending on the peak temperatures and cooling rates of subsequent welding passes during fabrication of an equipment. As a rule, these temperatures range from solidus o temperature to approximat ely 1000 C. Depending on the thermal cycle characteristics, intermet allic phases and/or sec ondary austenite can precipitat e and might change loc ally the DSS properties. Research re sults HAZ re search. In the beginning, DSS weldability studies started welding UNS S31803 with autogenous one-pass GTAW and EBW processes [1]. Heat inputs were calculated to give a rec ommended t1200-800 [8] for GTAW weld bead (approximat ely 9 s) and

a lower t1200-800 for EBW (0,3 s). The amount of austenite observed in FZ and in HTHA Z of these welds was (17 3) vol. % for GTAW and (3 1) vol. % in as-welded condition, whereas after 30 o min heat treatment at 1050 C volumetric fraction of austenite changed to (40 1) vol. % and (44

2) vol. % , respectively. Results of mechanical and corrosion properties of post welding heat treatment (PWHT) where similar to as-received plates. Figure 1 presents a result of generalized corrosion of EBW sample[9].

Fig. 1 Generalized corrosion in an EBW joint. (a) As-welded condition; (b) PWHT condition. Optical microscopy. 40X. [9] UNS S 31803, S 32550[2], S 32304, S32750, and S32760[3] DSS samples were simulated in a dilatometer and in a Gleeble machine using a thermal modeling for LTHA Z[2,10] assuming three passes at a place in the root joint, which o As PWHT is almost impractical for industrial undergoes to a peak temperature of 950 C in conditions, the concept of a continuos PWHT the first pass, and using heat inputs from 0.4 to during welding come to light, and multipass 1.0 kJ/mm. Intermetallic phase precipitation was welding issue was addressed in further research characterized by extracting precipitates by studies. The idea involved in this concept was to dissolving the DSS matrix and carrying out Xinvestigate the effect of multipass welding rays diffraction of extracted residues in a Debyethermal cycles in precipit ation of intermet allic Scherrer c hamber. Sigma phase and chromium phases (sigma phase and chromium nitride); nitride precipitations were found in. and recovering the volumetric fraction of S32550[2,11], S32750, and S 32760[3]. On the austenite (by nucleating intergranular and other hand, UNS S 31803 and S32304 intragranular secondary austenite in parallel with simulated samples did not presented any chromium nitride precipitation/dissolution) into intermet allic precipitation det ected by this mechanic al and corrosion resistance of DSS. technique. The amount of chromium nitride was These phas e transformations during welding calculated for UNS S32550 and, it was characterize LTHA Z and HTHA Z of a DSS, measured an amount of 0.35 vol. % for 1.0 respectively. kJ/mm[2,11]. Thus, ductility of simulated samples of UNS S 31803 and S32550 where LTHAZ research. compared using a bend test. Results are presented in figure 2.

Fig. 2 Bended surfac e of simulated samples with 1.0 k J/mm welding heat input. (a) UNS S31803; (b) UNS S32550. SEM.[2] Comparing figure 2(a) to figure 2(b) one can see opened grain boundaries and interfaces in simulated sample of UNS S32550 due to intermet allic precipit ation at these regions, which was confirmed by AS TM A262 practice A intergranular corrosion test. Also, pitting corrosion resistance where measured using artificial sea water and cyclic polarization tests at temperatures close to pitting potential critical temperatures. Results are pres ented in table 1.

Table 1 Pitting and protection pot entials for as-received and LTHA Z simulated samples of UNS S32304, S32750, and S32760. [3]. Material UNS S32304 (25 o C test temperature) UNS S32750 o (50 C test temperature) UNS S32760 o (50 C test temperature) Condition as-received simulated, 0.6 kJ/mm simulated, 0.8 kJ/mm simulated, 1.0 kJ/mm as-received simulated, 0.6 kJ/mm simulated, 0.8 kJ/mm simulated, 1.0 kJ/mm as-received simulated, 0.6 kJ/mm simulated, 0.8 kJ/mm simulated, 1.0 kJ/mm Pitting potential (mV, SCE) 487 73 531 37 459 32 481 24 1008 21 1073 25 1110 10 1083 11 1030 37 1090 17 1053 25 1060 17 Protection potential (mV, SCE) -117 41 -150 24 -151 41 -164 10 299 284 -90 18 -67 27 -93 14 409 138 307 13 250 29 256 46

Analyzing table 1 one can note a significant drop in corrosion resistance observed for all heat inputs and materials studied c ompared to as received condition, that is due to precipit ation in LTHA Z. In summary, all these results are regarding to LTHA Z, which is, as previously mentioned, a region where almost no change in as-received microstructure is observed. Therefore, most of

the res earc h published in literature in DSS welding is related to HTHA Z, which presents a huge change in microstructure in this region. HTHAZ re search. During a stay at The Ohio State University/Edison Welding Institute, a research on simulat ed HA Z multipass welding of UNS

S32550 and UNS S32750 was conducted using a simple thermal cycle model to investigate multipass welding effect on HA Z microstructure and mechanical and corrosion joint properties[12,13]. A fterwards HTHA Z of UNS S32205, S32304, S32550, S32750, and S32760 were studied using GTAW welding proc ess and in a Gleeble equipment. A multipass thermal cycle model for HTHA Z [14] was developed, using a distributed heat sources methodology proposed by Grong and isten [15], with a purpose of simulate HTHA Z samples. Fundamental aspects of intergranular and intragranular secondary austenite and chromium nitride precipitation were considered and a model of intragranular secondary austenite precipitation was proposed. In this model, a cooperative precipitation of sec ondary austenite and chromium nitride followed by nitride dissolution was proposed [4, 16]. A scheme of this model is presented in figure 3.Based on t his model [4,16], chromium nitrides first nucleate

and precipitate at ferrite/austenit e interface and growth into ferrit e due to a favorable orientation among ferrite/chromium nitride/austenit e. During precipitation, the regions adjac ent to precipitates are depleted in ferrite stabilizers alloying elements, promoting austenite precipitation. Moreover, austenite has a higher nitrogen solubility and a dissolution of nit rides complet ely involved by austenite takes place during multipass welding [16]. Mechanical and corrosion properties were related with secondary austenite precipitation. Charpy V absorbed energy in multipass HTHA Z tends to be lower than as-received material[4]. Pitting corrosion resistance was determined by artificial sea water cyclic polarization curves and results showed an increase in pitting potential with reheating after third pass and with increasing heat input. Results of pitting pot ential after third pass of UNS S32550, S32750 and S32760 were almost the same of as-received plates[4].

Fig. 3 Picture showing the dissolution of nit rides (white phase) in a secondary austenite region. Scheme of cooperative precipitation of secondary austenite and chromium nitride followed by nitride dissolution.[4,16]

FZ re search. A similar res earc h was conducted in fusion zone of duplex stainless steels using two filler metals, AWS E2209-17 and EN 25 9 4L. A TTP diagrams were obtained for these two filler metals and als o to two DSS (UNS S32750 and S32760). Comparing the results, filler metal EN 25 9 4L presented the most favorable kinetic to precipitat e sigma and chi phases [5]. This means that the filler metal is more susceptible to intermet allic precipitation than base met als

studied in this work, depending on welding procedure. Crescent heat input technique presented better results than other tested welding techniques. Fig. 4 shows the result for the weld metal submitted to three reheating thermal cycles. The effect of welding current frequency on the weld metal grain size was also studied for UNS S32101 and UNS S 32304, which is depicted in figure 5. In this figure is also shown, for UNS S32102, EBSD images to compare grain size in a non-pulsed current and 20 Hz current frequency.

AWS E 2610-17

Fig. 4 Picture showing the TTT sigma phase precipitation c urve for weld metal from E N 25 9 4L and thee reheating thermal cycles and the microstructure of the weld metal in this regio n.[5]

Analyzing figure 5 on can see a trend to increase the weld met al grain size of UNS S32101. On the ot her hand UNS S32304 presented also a slightly trend to increase the grain size with the increase of the welding current frequency. To investigate thes e results, the nitrogen content was det ermined for each weld metal, for both base metals. The results are pres ented in table 2.

The loss of nitrogen was calculated based upon the original amount of the bas e metal before welding. The nitrogen loss increased with welding current frequency for both duplex stainless steels. UNS o nitrogen.S32101 present ed a higher nitrogen loss than UNS S32304. This behavior might be due to the different chemical composition. UNS S32304 has a higher amount of chromium, which has a higher chemical affinity

Fig. 5 E ffect of GTA welding current frequency on the grain size of UNS S 32101 and UNS S 32304. In this figure is shown EBS D images of weld metal grain size for non-pulsed welding current and 20Hz welding current frequency. [18] Table 2 Nitrogen amount and nitrogen loss related to duplex stainless steel grades and different welding current frequency [18].

UNS S32101 Base metal no pulsed 1 Hz 5 Hz 10 Hz 20 Hz

Nitrogen (%) 0,213 0,153 0,125 0,110 0,091 0,110

Nitrogen loss 0,060 0,088 0,103 0,122 0,103

UNS S32304 Base metal no pulsed 1 Hz 5 Hz 10 Hz 20 Hz

Nitrogen(%) 0,120 0,080 0,065 0,064 0,060 0,047

Nitrogen loss 0,040 0,055 0,056 0,060 0,073

A multicomponent phase diagram for UNS S32101 was built up to confirm the effect of

nitrogen in weld metal presented in figure 6.

grain

growth,

as

As the frequency increases, the amount of nitrogen decreases and, as a consequence, the. temperature interval in the ferritic field incre ases. As the heat input is constant for all experiments,

the cooling rate is almost the same. It means, the higher the interval, more time in the ferritic field, producing a larger grain size.

Fig. 6 - Phase diagram of the LDSS UNS S32101, a) Complete phase diagram, b) Enlarged area of the ferritic field and the nitrogen loss according to welding current frequency, compared to base metal. [18]

Di ssimilar welding research In some applications duplex stainless steels are welded to other steels grades, such as carbon steels or austenitic stainless steels. In figure 7 is shown a microstructure of a similar welded joint of UNS S 32304 and a dissimilar welded joint of UNS S3234 and A ISI304. These materials were welded with coated electrode E2209-17. In figure 7 is also pres ented the result of AS TM A262 P ractice A corrosion test in the regions

indicated. The results indicates a sensitized region in t he HA Z of UNS S32304 and in HA Z of AISI 304.

AISI 304

E2209-17

UNS S32304

Fig. 7 A similar and a dissimilar welded joint of UNS S32304 to A ISI 304. In the picture is shown the result of AS TM A262 Practice A corrosion test. [19]

Brazeability research.

Brazeability is a property which involves aspects related to filler met al, base metal and its interaction with flux or atmosphere and thermal effects in base metal during brazing [6]. In other words, filler met al, base metal and brazing process characteristics should be chosen in such a way that no embrittlement of base metal occurred during brazing, liquid met al flow through all the joint gap and joint region protected by flux or suitable atmosphere. Based on this definition, brazing temperature should avoid Change in volumetric fraction indicates that other phases might precipit ate depending on temperature and time during brazing thermal cycle. For UNS S31803 the temperature range o to be avoided is from 950 to 700 C, due to sigma phas e precipit ation in base metal. The best brazing temperature for duplex stainless o steels is around the heat treatment at 1050 C. Temperat ures higher than this can produce a change in ferrite/ austenite balance and might produce nitride precipitation. For this reason, brazing thermal cycle should be c arefully designed to avoid embrittlement in the whole component. As duplex stainless steels have a good corrosion resistance, t he brazing filler metal should have also a good corrosion resistance. Nickel base filler metals present

good corrosion resistance and a suitable brazing temperature range. Nickel base filler metals are alloyed with boron and silicon (B Ni-2) and phosphorus (B Ni-7) to reduce brazing temperature [6]. These elements also affect liquid viscosity and, as a cons equence, gap joint filling extension. Each filler metal presents an ideal clearance to provide a defect free joint. All these aspects together characterize brazeability of a material. In other words, contact angle, spreading final area, ideal joint clearance determined by edge test, and phase transformation in base metal during brazing thermal cycle are important to characterize brazeability. Brazing of UNS S31803 DSS was done in a continuous furnace under a pure hydrogen atmosphere and using different brazing filler o metals, BNi-2 and BNi-7 at 1100 C. Brazing parameters were changed to produce different brazing and after-brazing cooling times. Results showed that B Ni-7 presented better wettability results than BNi-2 [6]. However the cooling time after brazing was low enough to deteriorate DSS base metal, producing approximately 10% of sigma phase. B ased on this result, continuous furnace brazing are not suitable for UNS S31803 DSS brazing, unless a cooling system might be used to reduce cooling time and avoid sigma phase precipitation[6].

Fig. 8 Relationship between joint strength and joint gap [6].

Edge test provides important information regarding to ideal brazing joint clearance. The minimum joint clearance that produces a joint completed filled and the maximum gap where eutectic phase in the center of joint is discontinuous define this ideal range. In the case of duplex stainless steels there is a fcc nickel rich phase adjac ent to bas e metal and a eutectic with hard and brittle phases in the middle of the joint. There is a strong correlation between the microstructure and the mechanical properties of a brazed joint. The mechanical strength of a brazed joint is achieved when the gap is into t he ideal gap range. Figure 2 presents an schematic plot of the strength of the joint as a function of the joint gap. Region 1 presents a drop in the mechanical properties due to a lack of joint filling, reducing the brazed area in t he joint. Region 2 shows the higher strength, due to the Ni rich continuous

phase in the gap and also due to a mechanical constraint produced by a triaxial stress state. Region 3 depicts a region with the eutectic phase in the joint middle, producing a mechanic al resistance close to the filler metal. Figure 9 presents a microstructure of a non ideal gap of a UNS S 31803 brazed joint with BNi -2 filler metal. In figure 3(a) one can see the rich nickel phase at brazed joint/base metal interface and some rich in silicon and/or boron phases, represented by the dark grey phases. Figure 3(b) shows a precipitation of intermet allic phases in base metal. These phases are sigma phase and boron rich phas es. During brazing, boron can diffuse to base metal faster than silicon and phosphorus.

(a)

(b)

Fig. 9 Brazed joint of UNS S31803 with B Ni-2. (a) shows the microstructure of the brazed joint. (b) depicts the intermetallic phases produced during brazing in base metal. B ack scattered electrons pictures.

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Figure 10 shows a microstructure of a brazed joint of a UNS S31803 joined with BNi -7 filler metal. In figure 4(a) one can see the rich nickel phase at brazed joint/base met al interface and some phosphorus rich phases. Figure 4(b) depicts a back scattered electrons picture of the joint. The light gray in the joint was identified by

microanalysis as (Ni,Cr,Fe)P and the dark gray as (Ni,Cr,Fe)3P. Sigma phase precipitation was also observed in these braz ed samples.

(a)

(b)

Fig. 10 Brazed joint of UNS S31803 with BNi -7. (a) shows the mic rostructure of the brazed joint. Etch: 10% oxalic acid. (b) depicts the intermetallic phases produced in the brazed gap. Back scattered electrons picture.

A EBSD technique was utilized to c haracterize ferrite and austenite in UNS S32750 joined with

BNi-2 brazing filler metal. Results are presented in figure 11.

11

Figure 11(a) shows the presence of a large amount of nickel rich phase in the eutectic phase, as previously presented.

(a)

(b)

Fig. 11 EBSD image of ferrite and austenite in the brazed joint of UNS S32750 with BNi -2. (a) shows austenite and ferrite as solid colors. (b) depicts the region characteriz ed by EBSD technique. Back scattered electrons picture.

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Final comments This paper is an overview of t he research done at University of So P aulo in weldability and jointability of DSS in the last 10 years. Details of tests and additional results and discussions can be found in the mentioned literature. Acknowledgments Author would like to acknowledge his students (Antonio, Claudia, Ricardo, Clvis, Vinicius, Francisco, Adriano, Marcos, Reginaldo, Alcio, Jos Antonio, Silveli),whic h make these ideas come through. Also I appreciate FAPESP and CAPES for funding these works.

[7] J.C Lippold; W. Lin; S.D. Brandi; W.A. Baeslack III; I. Varol - "A review of heat affected zone microstructure and properties of duplex stainless steels". IN: Proceedings, Conference on Duplex Stainless Steels, Glas gow, Scotland, 1994, paper 118. [8] J. Honeycomb; T.G.Gooch A rc welding ferritic-austenitic stainless steels (Welding Institute Res. report 286/1985) [9] S.D. Brandi; A.F. Padilha; S. Wolynec, -

Corrosion resistance of GTAW and EBW welded joints of DIN W. Nr. 1.4462 (UNS S31803): E ffect of post weld heat treatment. IN: Proceedings, Offshore Mechanics and A rtic Engineering, OMAE 96; Florence, Italy; 18-21 July, 1996; p. 309-322. [10] A.J Ramirez Londoo,.; S.D. Brandi, A proposed modific ation of Rosenthals Solution of heat transfer equation to simulate multipass welding of duplex stainless steels. IN: Proceedings, International Conference Trends in welding research, AWS e ASM, Georgia, EUA, 1-5 June 1998, pg 19-24. [11] S.D. Brandi,; A.J. Ramirez-Londoo, Precipitation of intermet allic phases in the HA Z of multipass welding of duplex and super -duplex stainless steels. IN: Proceedings, Duplex 97 International Conferenc e, Maastricht, Holand, 21-23 October 1997 , pg. 405-410. [12] S.D. Brandi, J.C.Lippold, W. Lin, - The corrosion resistance of simulated multipass welds of duplex and super-duplex stainless steels. IN: Proceedings, Duplex 97 International Conference, Maastricht, Holand, 21-23 October 1997, pg. 411418. [13] S.D. Brandi; J.C. Lippold Effect of Interpass temperature on the heat-affected zone performance of simulated multipass welds in duplex and superduplex stainless steels (EWI Summary Report SR 9707, November 1997, 4 pgs.) [14] A.J Ramirez Londoo; J.C. Lippold; S.D.

References [1] S.D. Brandi. Weldability study of duplex stainless steel DIN W.Nr. 1.4462 (UNS S31803) (PhD t hesis, University of So Paulo, SP, Brazil, 1992, 265 pgs). in Portuguese [2] A. J. Ramirez Londoo. Precipitation studies of chromium nitride and sigma phase b y thermal simulation of multipass heat affected zone of duplex stainless steels (MSc thesis, University of So Paulo, SP, Brazil, 1997, 151 pgs ). in Portuguese [3] C. P. Serna Giraldo. I ntermetallic phases precipitation at low t emperat ure heat affected zone of duplex stainless steels multipass welding (MSc thesis, University of So Paulo, SP, Brazil, 2001, 123 pgs). in Portuguese [4] A. J. Ramirez Londoo. Intermetallic phases and s econdary austenite precipitation at multipass heat affected zone of duplex stainless steels) (P hD thesis, University of So Paulo, SP, Brazil, 2001, 241 pgs). in Portuguese [5] R.A. Fedele. Heat input influence on multipass fusion zone performance of duplex stainless steels. (MSc thesis, University of So Paulo, SP, Brazil, 2001, 175 pgs). in Portuguese [6] C. Carvalho Jr. Braseability studies of duplex

stainless steel using nick el base filler metals. (MSc thesis, University of So Paulo, SP, Brazil, 1999, 135 pgs). in Portuguese

Brandi "Application of puntiforme heat sources discrete distribution to simulate multipass welding heat flow". Submitted to Science and Tec hnology of Welding and Joining, 2003. 13

[15] O. Grong Metallurgical modeling of welding (The Institute of Materials, London, 1994, pg 77 -80). [16] A.J Ramirez Londoo; J.C. Lippold; S.D. Brandi "The Relationship bet ween Chromium Nitride and Secondary Austenite Precipitation in Duplex Stainless Steels". Paper submitted to Met. Trans., 2003. [17] S.D Brandi; C. Carvalho Jr, Brazability of UNS S31803 duplex stainless steels by nickel base filler metals in a continuous furnace brazing". IN: Proceedings, International Brazing and Soldering Conference " IBSC 2000", American Welding Society, Albuquerque, New Mexico, 2000, p.162169. [18] Vargas G, E. R., Brandi, S.D. - B ehavior of grain size in the weld bead of lean duplex stainless steel UNS S 32101 and UNS S32304 using pulsed GTAW process. MSc thesis, USP, 2010. [19] Assis, C. A. - Comparao da junta similar de ao inoxidvel duplex UNS S 32304 com a junta dissimilar de ao inoxidvel duplex UNS S32304 com ao inoxidvel AIS I 304, soldadas com E220917.

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