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Presenter:
Parvan Chavdarov Academic Education and Degrees Post-graduate student Weldability of duplex stainless steels Technical University of Sofia 2001 Master degree on technology of metals, Technical University of Sofia, Bulgaria Present professional position: Expert in Industrial Services in TUV Rheinland Bulgaria
Originally presented at the Stainless Steel World 2007 Conference, Maastricht, the Netherlands
Keywords: duplex stainless steel, welding parameters, ferrite content, microstructure, intermetallic phases, metallographic analysis Abstract: The aim of this paper is to present the influence of the welding parameters upon the shape of the weld, the microstructure and respectively the precipitation of second phases in superduplex stainless steel S32750. Plates with 10mm thickness have been butt welded with electron beam without filler by altering the heat input. Metallographic sections have been prepared and the ferrite content in the weld metal has been measured. The availability of intermetallic phases is examined.
Originally presented at the Stainless Steel World 2007 Conference, Maastricht, the Netherlands
1. Introduction
Duplex stainless steels are a family of grades combining good corrosion resistance with high strength and ease of fabrication. Their physical properties are between those of the austenitic and ferritic stainless steels and tend to be closer to those of the ferritic and to carbon steel. These steels are very attractive for various applications because of their advantages: Very high corrosion resistance especially against pitting and crevice corrosion in aggressive media containing chlorides and fluorides; Higher mechanical properties (because of the ferrite phase) than the austenite stainless steels which are predominantly used in practice; Higher ductility (because of the austenitic phase) than the ferrite stainless steels which reflects on the weldability. Better compatibility to C-Mn structural steels, because the coefficients of heat expansion are comparatively close, which results in lower thermal stresses. All these advantages result in extremely wider usage of duplex alloys in many industry branches like petrochemical, chemical, pulp and paper, off-shore, energy, gas fuel, mining, shipbuilding, power generations, marine transportations, food manufactures, etc. A balanced austenite/ferrite ratio of 50/50% is crucial for their high performance. Compared with normal austenitic steels, duplex steels contain less nickel which increases its cost-effectiveness considerably. The desire structure is obtained by heat treatment at approximately 1050 to 1100C (solution annealing). The optimum ratio between both phases can be influenced by the welding processes.
Fig.1: Concentration profiles in the ternary Fe-Cr-Ni constitution diagram at 70% and 60%Fe. The effect of nitrogen additions is shown in the first figure.
The alloy lean grades are the least prone to Intermetallic phase precipitation and requires exposure of at least 10 to 20 hours to initiate formation at temperatures below 900C. For that reason, a solution annealing temperature below 1000C can be chosen for this material. More alloyed grades are more sensitive to precipitation due to the molybdenum content. This element not only increases the rate of Intermetallic precipitation, but also extents the stability range to higher temperatures. That is why higher solution annealing temperatures are needed above 1000C. The superduplex alloys show the greatest propensity for precipitations, due to their higher Cr, Mo and W contents. However, it should be emphasized that the precipitation kinetics in these high alloy grades are, at worst, equivalent to the superaustenitic or superferritic stainless steels [2]. And still, by taking precautions during heat treatment, including rapid removal from the furnace followed by water quenching, the superduplex alloys can be used satisfactory in industrial applications. However, especial care is required for heavy section components during all stages of production. Precipitates re-dissolve during a solution anneal, which for the superduplex grades must be performed at 1050C or above. A few minutes at 1050-1070C are sufficient for grade S32750. Similar high temperatures are necessary for welds as consumables tend to contain higher Ni, Si and Mn contents than base materials. The higher Nicontent encourages high austenite contents when annealed and results in enrichment of Cr and Mo in the remaining ferrite. This fact, combined with higher Si and Mn levels, increases the stability of Intermetallic phases. And yet, lower annealing temperatures (1040C compared to 1100C) can be used for weldments made with matching consumables [3].
In welds of duplex stainless steels some detrimental second phases can occur in the temperature range of 300-1100C. The tendency to precipitation depends mainly on the content of alloying elements and therefore, it differs for the different duplex grades. The precipitation of phases is much more typical during heat treatment or welding of superduplex steels because of the higher content of such elements [4]. The following paragraphs describe the various phases which have been observed in duplex alloys. Their character and morphology of these phases vary considerably, as do the time for them to form and their influence over the properties. On fig.2 is given the diagram for the precipitation of the various phases for grade S32750. It can be easily seen what is the incubation time for the formation of a certain phase. Details for each phase can be observed in table1
Particle Chemical formula Fe-Cr-Mo Fe36Cr12Mo10 R Fe2Mo Fe7Mo13N4 Cu-rich Type 1 2 Type 2 Type 3 Cr2N CrN M7C3 M23C6
Cr 30 25 65 25 35
Ni 4 3 2,5 6 3
Mo 7 14 13 35 34
Formation range, C 600-1000 700-900 300-525 550-650 550-600 550-650 Not defined 650 650-800 700-900 700-950 950-1050 650-950
FCC
Originally presented at the Stainless Steel World 2007 Conference, Maastricht, the Netherlands
The deleterious Cr, Mo rich -phase is a hard embrittling precipitate, which forms between 650 and 1000C, often associated with a reduction in both impact properties and corrosion resistance. At the peak temperature of around 900C, ferrite decomposition to sigma takes as little as two minutes in superduplex alloys. According to some authors, the formation of sigma phase should be concerned with the requirement for pre-existing M23C6 particles [5]. Certainly, this phase has been found to nucleate at temperatures above 750C in association with such particles with the following order of preference: / phase boundaries, austenitised / sub-grain boundaries and high energy / grain boundaries (table 1). These nuclei can grow into coarse plates, lamellar eutectoid + 2 (fig.3), or + lamellar aggregates. In the last case, the interlamellar ferritic region has a high dislocation density attributed to the volumetric expansion from to . Further, in the case of phase boundaries, for instance when transforms to or 2, the remaining becomes enriched in Cr and Mo, and denuded in Ni, enhancing -formation and, for the same reason, growth progresses into the destabilized ferrite.
The formation of sigma is encouraged by the presence of Cr, Mo, Si and Mn. Ni is also found to enhance -formation, but reduce the equilibrium volume fraction [6]. This occurs as Ni induces -formation and so concentrates the -promoting elements in the remaining ferrite. Chi () phase
Like -phase, -phase forms between 700 and 900C, although in much smaller quantities. However, enrichment of ferrite with intermetallic forming elements during a long exposure to relatively low temperatures, i.e. 700C, favors the precipitation of phase (.2). Like sigma, -phase often forms on the / boundary and grows into the ferrite. The cube-cube orientation relationship (table 1) ensures continuity between and the -matrix. This phase has similar influence on corrosion and toughness properties as sigma, but, as both phases often co-exist, it is difficult to study their effects individually. Alpha prime ()
The lowest temperature decomposition within duplex steel is that of alpha prime (), which occurs between 300 and 525C, and is the main cause of hardening and 475 embrittlement in ferritic stainless steels. It is suggested that -formation is a consequence of the miscibility gap in the Fe-Cr system, whereby ferrite undergoes spinodal decomposition into Fe-rich -ferrite (table 1) and a Cr-rich , or, just outside the spinodal but still within the gap, classical nucleation and growth of occurs. Alpha prime is often associated with the co-precipitation of Cr2N in the form of sub-grain networks of Cr2N needles interspersed within a film of .
Originally presented at the Stainless Steel World 2007 Conference, Maastricht, the Netherlands
R, , phases
R phase, also known as Laves, (Fe2Mo) precipitate in small quantities between 550 and 650C after several hours exposure (table 1) [1]. They form at both intra- and intergranular sites, are molybdenum-rich and reduce pitting corrosion resistance. However, as those that precipitate at intergranular sites contain slightly more Mo (40% compared to 35%Mo), their influence on pitting resistance is more considerable. The -nitride has been identified at intragranular sites in duplex weld metal after isothermal heat treatment at 600 C for several hours [7]. It is Cr Mo rich and so has been previously confused with -phase. Heat treatment for several hours in the temperature range 550 to 650C (table 1) can lead to the formation of the heavily faulted needle-like -phase on / boundaries [8]. Cu-rich epsilon () phase
In alloys containing copper and/or tungsten, other hardening mechanisms can occur. In the case of Cu, the super saturation of the ferrite due to the decrease in solubility at lower temperature leads to the precipitation of extremely fine Cu-rich -phase particles after 100 hours at 500C, which significantly extend the low temperature hardening range of the duplex grades. Although the reported temperature range for their formation varies, it would seem that they all form in the same temperature regime as 2.
Fig.4: Optical micrograph of 2 in superduplex welds, x1000. Etch: electrolytic sulphuric acid.
Originally presented at the Stainless Steel World 2007 Conference, Maastricht, the Netherlands
In the 700-900C range, a eutectoid of 2 + can form (fig.3), as 2 absorbs and rejects Cr and Mo, encouraging Cr, Mo-rich precipitates, such as sigma phase. Similarly, one form of 2 which forms at / boundaries is found to be depleted in Cr. Either of these diffusion controlled reactions can render the area susceptible to pitting corrosion.
applications and there is every reason to expect that procedures will be developed more fully. Electron beam welding is especially suited to produce joints of heavy section materials in one or two passes. Unfortunately, it tends to produce rapid cooling rates and therefore highly ferrite in the melt zone, particularly in thin sections [12]. Nevertheless, the toughness remains high which can be attributed to the very low oxygen content in the weld. Still the qualification of the procedure must be alert to the possibility of excessive ferrite in the HAZ and even in the weld when the high speed welding capabilities of these methods are considered. Special feature of this welding method is the formation of the welding pool and bead. Because of the high temperature and concentration of energy, peculiar gas-steam channel in the welded metal is created. The electron beam continues to penetrate through this channel to bigger depth and thus it is possible thicknesses up to 200 mm to be fully penetrated with minimum width of the weld. This is a prerequisite for the formation of the so called dagger form of the weld (fig.5)
Fig. 5: Formation of dagger form of the bead. In this case the ration between the penetration depth and the weld width is 3,6:1 (10:2,75), but it can much bigger (50:1).
3. Experimental results
3.1 Welding machine
Installation LEYBOLD-HERAEUS EWS-1560 has been used for the welding. The sketch of the experimental configuration is shown on fig.6
Fig.6 1 Devices for computer driven control; 2 Electron gun; 3 Source for acceleration; 4 Cathode feed; 5, 6, 7 Deflection/focus coils; 8 Leading; 9 Vacuum chamber.
Originally presented at the Stainless Steel World 2007 Conference, Maastricht, the Netherlands
This electron beam machine is a conventional one. It is composed of an electron beam gun, a power supply, control system, motion equipment and vacuum welding chamber. The fusion of the base metals eliminates the need for filler material. Besides, the vacuum requirement for operation of the electron beam equipment eliminates the need for shielding gases and fluxes. The electron beam gun has a tungsten filament which is heated, freeing electrons. The electrons are accelerated from the source with high voltage potential between a cathode and anode. The stream of electrons then pass through a hole in the anode. The beam is directed by magnetic forces of focusing and deflecting coils. This beam is directed out of the gun column and strikes the workpiece. The potential energy of the electrons is transferred to heat upon impact of the workpiece and cuts a perfect hole at the weld joint. Molten metal fills in behind the beam, creating a deep finished weld. The electron beam stream and workpiece are manipulated by means of precise, computer driven controls, within a vacuum welding chamber of 0,5m3, and thus eliminating oxidation and contamination.
Weld No 1 2 3 4 5 6
Voltage, kV 53 53 53 53 53 53
Welding Current, mA 45 45 45 52 65 75
3.3 Influence of the welding parameters over the shape of the welds
For each weld macroscopic analysis has been done in order to be studied he influence of the welding parameters over the shape of the welds (penetration depth,
Originally presented at the Stainless Steel World 2007 Conference, Maastricht, the Netherlands
reinforcement height and the weld width). The etching is done by a mixture of 10 ml HNO3, 20 ml HCl and 30 ml H2O for 3-4 minutes depending on the temperature of the solution. n fig.7 is shown how the width of the weld (B) changes with the increase/decrease of the welding speed (Vw) and the current (I) accordingly with constant voltage (U=const) in both cases.
B(mm)
3.0 2.8 2.6
V(mm/s)
I(mA)
Fig.8: Influence of I on the weld width In the same way, the effect of changing the welding speed (Vw) and current (I) over the reinforcement height (Hr) and the penetration depth (Hpen) is studied and depicted on the following four fig.9-fig.12. The voltage again is constant U=53 kV.
U=const, I=const
Hr(mm)
1.2 1,3 1,8
Vw(mm/s) 25 15 10
Originally presented at the Stainless Steel World 2007 Conference, Maastricht, the Netherlands
H(mm)
1.8
1.7
1.6
1.5
1.4
1.3
1.2 8 10 12 14 16 18 20 22 24 26
V(mm/s)
H(mm)
U=const, Vw=const
1.70
Hr(mm)
1,45 1,65 1,70
I(mA) 52 65 75
1.65
1.60
1.55
1.50
1.45 50 55 60 65 70 75
I(mA)
H(mm)
10
U=const, I=const
Hpen(mm)
5,1 6,3 10,0
Vw(mm/s)
8
25 15 10
5 8 10 12 14 16 18 20 22 24 26
V(mm/s)
U=const, Vw=const
Hpen(mm)
I(mA)
7,15 52 7,60 65 Originally presented at the Stainless Steel World 2007 Conference, Maastricht, the Netherlands 8,45 75
8.6
H(mm)
I(mA)
The experiments have proved something which is known for a long time, namely that with the increase of the welding speed (it varies from 10 to 25 mm/s) under constant other circumstances, the values of all parameters pertaining to the shape of the weld diminish. The biggest influence has been exerted on the width of the weld from 2,75mm to 1,1mm. Certainly this is not a surprise, because the higher the speed is, the less the heat input is. At the same time the penetration depth also becomes much smaller from full penetration to 5,1mm, i.e. two times decrease. The smallest modification refers to the reinforcement height 40%. The effect of growing the welding current on the shape of the weld is just the opposite from what was said for the welding speed. With the increase of the current (from 52 to 75mA), all above mentioned parameters grow bigger, as the ratio is almost the same for all of them.
the measurement of the ferrite content has been increased to 100%. Thus the scope is raised, but the sensibility of the apparatus becomes smaller. The results from the measurements of the ferrite phase in the welds are ordered in table 3. Ferrite content in the welds, % Measurement results Mean value 1 63, 65, 57, 60 63,75 2 65, 60, 66, 62 63,25 3 50, 55 52,50 4 58, 60, 58, 53 57,25 5 57, 55, 60, 58 57,50 6 58, 50 54,00 Table 3: Ferrite content in the welds The ferrite content at the fusion boundaries is given in table 4. Weld No
Ferrite content at the fusion boundaries, % Fusion boundary for Weld No Measurement results Mean value 1 43, 48, 47, 45, 46, 48, 43, 45, 44 45,44 2 45, 44, 46, 48, 43, 45, 44, 43, 38 44,00 3 50, 48, 50, 53, 49, 48, 45 49,00 4 47, 47, 43, 45, 43, 45, 48, 48, 44 45,55 5 44, 44, 38, 45, 46, 53, 45, 45 45,00 6 44, 47, 46 45,67 Table 4: Ferrite content at the fusion boundaries The relevant values of this phase in the base metal are presented in the following table 5. Ferrite content in the base metal, % Measurement results Mean value 38, 37, 40, 45, 42, 44, 38, 41 40,63 Table 5: Ferrite content in the base metal The difference in the ferrite content pertaining to the welds, the fusion lines and the base metal is obvious. It is most in the welds, because the cooling rate is highest in these zones and the transformation from ferrite to austenite is impeded at low temperatures. As a result, more quantities of high-temperature ferrite can be observed in the structure. On the other hand the initial balance between both phases is disrupted also in the heat affected zones (which for the electron beam welding are very thin zones, like a line), but not to this extent like in the welds. That is why the mean value of the ferrite content in the HAZ is smaller than in the weld, but still is bigger in comparison with the base metal.
Originally presented at the Stainless Steel World 2007 Conference, Maastricht, the Netherlands
Fig.13: Microstructure in the weld under different magnifications: a-c) x200; d) x500; e) x1000
Originally presented at the Stainless Steel World 2007 Conference, Maastricht, the Netherlands
Fig.14: Microstructure at the boundary between the weld and the base metal under different magnifications: a) x200; b) x500
Weld 2
Fig.15: Microstructure in the weld under different magnifications: a-c) x200; b) x1000; c) x1500
Fig.16: Microstructure at the boundary between the weld and the base metal under different magnifications: a) x500; b-c) x1000
Weld 3
Originally presented at the Stainless Steel World 2007 Conference, Maastricht, the Netherlands
Fig.18: Microstructure in the weld under different magnifications: a) x750; b) x1000; c) x2000
Fig.19: Microstructure at the boundary between the weld and the base metal under different magnifications: a) x200; b) x1000; c) x2000
Weld 4
Fig.21: Microstructure in the weld under different magnifications: a) x200; b) x1000; c) x2000
Originally presented at the Stainless Steel World 2007 Conference, Maastricht, the Netherlands
Fig.22: Microstructure at the boundary between the weld and the base metal under different magnifications: a) x750; b) x1000; c) x2000
Weld 5
Fig.24: Microstructure in the weld under different magnifications: a) x200; b) x1000; c) x2000
Originally presented at the Stainless Steel World 2007 Conference, Maastricht, the Netherlands
Fig.25: Microstructure at the boundary between the weld and the base metal under different magnifications: a) x500; b) x750; c) x1000
Weld 6
Fig.26: Microstructure in the weld under different magnifications: a) x500; b-c) x1000
Fig.27: Microstructure at the boundary between the weld and the base metal under different magnifications: a) x200; b) x1000; c) x2000
3.4.2 Results
For all probes (welded with different regimes of electron beam welding) a typical structure with five distinguished zones can be observed (fig.28):
Zone1 Zone2 Zone3 Zone4 Zone5
1 - Zone 1 coarse grains in the middle part of the weld; - Zone 2 strongly prolonged through the front of the grains; - Zone 3 dispersive structure at the boundary with the base metal; - Zone 4 fusion boundary; - Zone 5 base metal.
Originally presented at the Stainless Steel World 2007 Conference, Maastricht, the Netherlands
The base metal has ferrite-austenite structure with ratio between both phases close to 50%-50% and with a texture of the grains (fig.29). Non-metallic inclusions are not outlined in the section field.
Fig.29: Microstructure of base metal: a) x200 (weld 3); b) 1000 (weld 4) The weld structure is non-equal and consists of grains with different sizes, which is a result of the different speed of heat-conduction in the material. In all welds the formation of skeleton-like structure can be seen (fig.30). Under big metallographic magnifications (1000, 2000) the structures which set up this skeleton are clearly discernable. On the periphery of the grains (1) white zones can be observed (2) and at the boundaries needle-shaped precipitations (3).
1 2 3
1 2 3
) weld 5; b) weld 4; c), d) weld 1 Main phase component in the welds is -ferrite. Inside the -ferrite grains precipitations of 2 are registered and at the boundaries austenite, which has particularly a Widmannstaeten structure. Intermetallic phases like -type are not registered upon using metallographic analysis.
The formed heat affected zone (zone 4) is very thin (10-35m) and is visible as a boundary between the weld and the base metal. The microstructure in this zone is identical as the one in the base metal. Intermetallic phases are not registered. In most of the welds some typical for electron beam welding imperfections in the root are visible porosity, non-uniform surface, etc.
Originally presented at the Stainless Steel World 2007 Conference, Maastricht, the Netherlands
4. Conclusions
With the increase of the welding speed all parameters which pertain to the shape of the weld, namely penetration depth, weld width and reinforcement height, become smaller because of the low heat input. This speed should be chosen very carefully, because there is a risk of lack of penetration if it is too high. The influence of the welding current over the shape of the weld is the following the higher the current is, the bigger are the geometrical dimensions of the weld. The ferrite content in the weld is bigger that the relevant one in the heataffected zone and the base metal, because the structure is not equilibrium in the weld. In comparison with the heat treatment, the welding processes are faster, the cooling rate is higher and the time for diffusion is shorter. As a result of this, high-temperature condition is fixed at lower temperatures. The ferrite content in the weld is more when the heat input is less, for example when the welding speed is higher or the current is lower than some initial values. The heat-affected zone in the materials, which are welded with electron beam is very thin, of the order of some m. This is an advantage for this welding method, because very small part of the base metal is affected by the welding process. The measurement of the ferrite in the base metal has shown that the volume of this phase is the range which is given in the literature between 40% and 60% in annealed and quenched condition. The initial position of the plates is annealed to 1050C and quenched in order to be re-dissolved all second phases in the structure. In comparison with the ferritic stainless steels, duplex alloys are famous with the slower diffusion rate, i.e. the incubation time for the phase precipitation is longer. This means that the nose of the curve is translated to the right. The review of the metallographic photos has not shown the precipitation of intermetallic phases. The explanation of this fact can be found in the timetemperature transformation diagram. According to this diagram the incubation time is enough long to secure that no phases will precipitate. Therefore electron beam welding is proper for welding of duplex stainless steel S32750 for the lack of second phases in the microstructure which could affect embrittlement and reduction in the corrosion resistance. The more alloyed is one duplex grade, the more susceptible it is to the precipitation of second phases. That is to say the standard duplex stainless grades are more susceptible to the precipitation than the lean ones. The chance these phases to form in the high alloyed grades are much bigger than in the standard steels. The superduplex alloys show the greatest propensity for precipitations, due to their higher Cr, Mo and W contents.
Originally presented at the Stainless Steel World 2007 Conference, Maastricht, the Netherlands
5. References
[1] Charles J: Proc conf Duplex Stainless Steels 91, Beaune, 1991, Vol.1, 3-48.
[2] Mancia F, Barteri M, Sasseth L, Tamba A, Lannaioli A: York 87, vide ref.11, 160-167. [3] Gunn R: Duplex Stainless Steels, Woodhead Publishing, 2003.
[4] Leif Karlson: Intermetallic Phase Precipitation in Duplex Stainless Steels and Weld Metals. Metallurgy, Influence on Properties, Welding and Testing Aspects. Doc. IX-1920-98. [5] [6] [7] [8] [9] [10] Goldsmith HJ: Interstitial Alloys, Plenum Press, 1967, 167. Maehara Y, Ohmori Y, Murayama J, Fujino N: Metal Science 17, 1983, 541. Nilsson J-O, Liu P: Mater Sci Technol 7, 1991, 853. Redjaimia A, Metauer G, Gantois M: Beaune 91, vide ref.2, Vol.1, 119-126. Soulignac P, Dupoiron F: Stainless Steel Europe 2, 1990, 18-21. Nilsson J-O: Materials Science and Technology 8, 1992, 685-700.
[11] Herzman S, Roberts W, Lindenmo M: The Hague 86, vide ref. 7, paper 30, 257-267. [12] Bonnefois B, Charles J, Dupoiron F, Soulignac P: Proc conf Duplex Stainless Steels 91, Beaune, France, Oct. 1991, Vol.1, 347-362;
Originally presented at the Stainless Steel World 2007 Conference, Maastricht, the Netherlands