Materials Characterization 58 (2007) 65 71

Effect of intermetallic precipitations on the properties of duplex stainless steel

Michael Pohl, Oliver Storz , Thomas Glogowski
Institute for Materials/Material Testing, Ruhr University Bochum, Germany Received 31 October 2005; received in revised form 30 March 2006; accepted 30 March 2006

Abstract The corrosion resistant group of ferritic austenitic duplex steels shows a rather complex precipitation and transformation behavior that affects the mechanical and corrosive properties. Most critical, concerning the change of properties, are the precipitations in the temperature field of 650950 C. 2006 Elsevier Inc. All rights reserved.
Keywords: Duplex; Stainless steel; Sigma phase; Chi phase

1. Introduction The ferritic austenitic duplex steels belong to the corrosion resistant steels. In contrast to the purely ferritic steels, they offer better corrosion resistance, as well as a higher strength compared to the pure austenitic grades. Hence, the duplex steels are widely used in the chemical industry or in offshore technologies, where a combination of high corrosion resistance and good tensile strength is required. Besides, the widely used standard duplex grades, the super duplex steels, with a Pitting Resistance Equivalent of N 35, have come into service (Table 1). The duplex steels are based on the ternary FeCrNi phase diagram
Presented at the Microscopy and Microanalysis Society/International Metallographic Society Technical Meeting, Honolulu, July 31August 4th, 2005. Corresponding authors. E-mail addresses: storz@wp.rub.de (O. Storz), glogowski@wp.rub.de (T. Glogowski).

(Fig. 1). The section at 70% iron shows the quasi-binary phase diagram (Fig. 2), which represents the duplex stainless steels. They solidify primarily as ferritic alloys and transform at lower temperatures by a solid state reaction partially to austenite. Hence, the austenite ferrite ratio is adjusted in a temperature upside 1000 C. Preferable a ration of 6050% austenite is achieved. Due to the high amount of alloying elements, the duplex stainless steels show a rather complex precipitation behavior. The effect on the mechanical and corrosive properties of several precipitations might be extensive. This is enhanced by a differential distribution of the alloying elements in the ferritic and austenitic phase.

Table 1 Standard duplex steel grades Steel no. Duplex Super-duplex 1.4462 1.4501 Name X2CrNiMo 22-5-3 X2CrNiMoCuWN 25-7-4 UNS S 31803 S 32760

1044-5803/$ - see front matter 2006 Elsevier Inc. All rights reserved. doi:10.1016/j.matchar.2006.03.015

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Fig. 1. Ternary FeCrNi phase diagram.

Because of the higher diffusion rate of the ferritic phase, all technically relevant precipitations can be found here. Most hazardous concerning a possible embrittlement is a precipitation of the hexagonal nitrides (Cr2N) in a tempe-

rature range of 700900 C, the precipitation (475 C embrittlement) and the intermetallic sigma and phase. The intermetallic precipitations are of greater interest, because besides their influence on the mechanical

Fig. 2. Pseudo-binary FeCrNi phase diagram at a 70% Fe section [1].

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properties, the corrosive properties are influenced severely, too. 2. Results and discussion 2.1. Precipitation of the phase The phase is non-magnetic and intermetallic. Its origin composition is based in the system of iron and chromium [2]. The phase has a tetragonal crystallographic structure [35], with an elemental cell of 32 atoms and 5 crystallographically different atom sites. These are occupied by different atoms, whereas the lattice occupation of atoms itself depends on the concentration. Concerning the ternary iron chromium nickel system, the sigma phase is a thermodynamically stable phase that forms itself on the chromium rich site of the pseudo-binary phase diagram FeCrNi (Fig. 1). Typically, the sigma phase precipitates between 600 and 1000 C. The mechanism of precipitation is a eutectoid transformation of ferrite into austenite and sigma phase. The denomination of the obtained austenite as tertiary austenite (3) enables an explicit separation from other austenitic phases with a different generation mechanism [6]. Generally, the denomination of the austenite is based on its forming mechanism (Table 2). As the time temperature transformation diagram shows (Fig. 3), the fastest precipitation rate for sigma phase can be found between 850 and 900 C [5,8]. According to the precipitation temperature, the morphology of the sigma phase precipitation changes (Fig. 4). At lower precipitation temperatures of 750 C, a coral-like structure of sigma phase can be found (Fig. 4c). The amount of single sigma nuclei at the beginning of the precipitation is rather high, depending on the shorter diffusion distances at lower precipitation temperatures. Hence, lower diffusion velocity causes higher local supersaturation and leads to a higher density of precipitations. A different precipitation behavior can be observed at higher temperatures of 950 C (Fig. 4a). The sigma phase is bigger and more compact at these temperatures and the linking between single sigma crystals is marginal, resulting from a lower nucleation formation force but a high diffusion rate at elevated temperatures.
Table 2 Types of austenite formation in duplex steels Formation mechanism Segregation of austenite stabilizing elements towards the eutectic rim (L + 1) Secondary Solid state transformation out of the ferrite (2) Tertiary Eutectoid transformation with consumption of ferrite (3 + ) Primary

Fig. 3. Isothermal TTT diagram of the standard duplex steel 1.4501 and the standard grade 1.4462 [7].

The transition in linking and particle size is found after a precipitation at 850 C (Fig. 4b). This change in morphology is numerically acquired by a form factor f. This factor describes the roundness of precipitations by means of the formula: f 4p area of the precipitation perimeter2 of the precipitation

The factor varies from 1, a completely round particle, to 0, corresponding to an idealized, line-shaped particle with a perimeter considerably greater than the surface area of this particle. Fig. 5 shows the measurements of the form factor for the standard duplex grade X2CrNiMo 22-5-3 with a sigma phase fractions of 15 vol.% each. 2.2. Precipitation of the phase In contrast to the sigma phase, the precipitation of the phase in duplex stainless steels is thermodynamically not stable. Concerning the examined alloys, the precipitation of the phase at 750 and 850 C was always prior to the sigma phase. With the beginning of the sigma precipitation, the phase vanishes in favor of the sigma phase, as can be seen in Fig. 6. Here, the phase residues were found partial soluted in sigma phase, located at the former grain boundaries. 2.3. Influence on the mechanical properties The formation of intermetallic phases between 750 and 950 C leads to a disastrous loss of toughness. Hence, the precipitation of intermetallic phases causes a detrimental loss of notch bar impact values. This is due

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Fig. 4. Morphology of the sigma phase with respect to the isothermal annealing temperature; (a) 950 C, (b) 850 C, (c) 750 C.

to the bad deformability of the phases because of their low fraction or metallic binding. Regarding the change in morphology between the different precipitation temperatures, notch bar impact tests were carried out with samples, heat treated at 750, 850 and 950 C. The experimental results of those tests show the above-mentioned detrimental loss of toughness at all temperatures (Fig. 7). One percentage of precipitated intermetallic phases leads to a loss of the notch bar impact value down to one third of the solution annealed state. Despite the strong decrement of toughness, distinctions were measured between the several precipitation temperatures.

The lower the precipitation temperature had been, the more brittle was the behavior. This incidence primarily depends on the morphology of the sigma phase. Even little deformations of the material cause transcrystalline, finely structured brittle fractures of sigma phase particles, due to the TCP structure of the phase. In the more net-like morphology precipitated at lower temperatures, cracks are enabled to run through sigma phase particles over long distances. The narrow fields of surrounding ferrite are forced to cleave, as the small austenitic phases show ductile failure.

Fig. 5. Results of the form factor measurement for the standard duplex grade X2CrNiMo 22-5-3.

Fig. 6. Precipitation of phase and growing of the phase in a cast duplex steel grade.

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Fig. 7. Influence of precipitation and morphology on the notch bar impact value.

Whereas in the bigger and more bulk sigma phase at higher precipitation temperatures has a bigger surrounding matrix of ferrite and austenite. This enhances the surrounding ferrite to a more ductile failure mode. Hence, the examination of the fractured samples showed less cleavage in the ferrite of samples annealed at 950 C than samples annealed at 750 C. The influence of the morphology of intermetallic phases on the tensile strength has a different character. The tensile and yield strength generally grows with the amount of precipitated intermetallic phases (Fig. 8). But as the samples annealed at 950 C barely show an increase of the tensile strength, the effect ambiguously is presented in the samples annealed at 750 and 850 C. The reason for this behavior can be traced back to the formation of a sigma phase network at lower temper-

atures. Hence, it was proved, that the yield strength grows with linking of sigma phase network. Additionally, the 850 C samples showed low stress fractures. In mechanical testing, low stress fractures occur beyond the general yield fracture level, because of internal brittle microcracking. Those fractures will appear, too, in the 750 C samples, as well, but equivalent amounts of sigma phase would take too long to precipitate. Since these tests would be technical irrelevant, they were not carried out. To observe the behavior of the sigma phase in situ, tensile tests were carried out in the SEM. The sigma phase showed first cracks at tensile stresses of 600 MPa, impartial of the phase morphology (Fig. 9). Cracking of phase particles was not observed during the whole testing.

Fig. 8. Influence of precipitation and morphology on tensile strength.

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Fig. 10. Selective corrosion of the tertiary austenite in a cast duplex grade.

Fig. 9. In situ tensile test of a sample annealed at 950 C; (a) initial state, (b) cracks at 741 MPa.

2.4. Influence on the corrosive properties The precipitation of the intermetallic sigma phase is accompanied by the formation of a new austenitic phase (3). As the sigma phase forms, chromium and molybdenum are enriched in these particles and simultaneously nickel diffuses into the ferrite. The enrichment of stabilizing elements in the ferrite and the loss of stabilizing elements lead to an unstable ferrite, transforming into an austenitic phase (3). This austenite is depleted in chromium and molybdenum. EDX measurements were carried out in the SEM showing depletion in chromium from 28% to 19% and a nearly total loss of molybdenum (Table 3). Calculations of Kobayashi and Wolynec have shown that as the chromium content of the tertiary austenite falls below

11%, the phase becomes prone to corrosion. This supposes that the width of the chromium-depleted zone is too small for detection by EDX. Examinations of technical failures have proved that this depletion is sufficient to make the austenitic phase prone to corrosion (Fig. 10). This is of particular concern if this steel grade is applied in highly corrosive media, such as desulphurization plants. The lower molybdenum and chromium content is not the only factor for being prone to corrosion. The neighborhood of the more noble phases will enhance the anodic dissolution of 3 extensively. The danger for components made of duplex stainless steel is that the ferritic phase forms a network-like matrix, especially in big dimensioned components. This allows deep corrosion attacking through the whole wall thickness of the component. With higher amounts of 3, the ferrite network changes into a continuous network of low alloyed 3. 3. Conclusion The intermetallic precipitations in duplex stainless steels affect the mechanical properties as well as the corrosive properties in a rather extensive way. Precipitation of brittle phases leads to a rapid reduction of the toughness and the forming of low alloyed tertiary austenite makes them prone to corrosion. References
[1] Hoffmeister H, Mundt R. Arch Eisenhttenwes 1981;52:15964. [2] Hall EO, Algie SH. The -phase. Met Rev 1966;11:6188. [3] Redjaimia A, Metauer G, Gantois M. Decomposition of ferrite in a Fe22Cr5Ni3Mo0.03C duplex stainless steel. A morphological

Table 3 EDX analysis of the phases in cast duplex steel GX3CrNiMoCuN 246-2-3 Phase 2 3 Chromium (wt.%) 25.6 19.6 28.3 32.7 Molybdenum (wt.%) 1.7 0.3 2.1 4.1 Nickel (wt.%) 7.2 6.9 5.5 3.1 Iron (wt.%) 65.5 73.2 64.1 60.1

M. Pohl et al. / Materials Characterization 58 (2007) 6571 and structural studyProc. Conf. Duplex Stainless Steels '91, Beaune; 1991. p. 11826. [4] Karlsson L. In: Stainless Steel World, editor. Conf. transcript. Duplex stainless steelKCL Publishing; 1997. p. 43. [5] Roscoe CV, Gradwell KJ, Lorimer GW. In: Institute of Metals book, editor. Conf. transcript, Stainless Steels; 1984. p. 563.

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[6] Pohl M, Storz O. Sigma phase in duplex stainless steels. Zeit Met 2004;95:7. [7] M. Mola Diploma thesis. Ruhr Universitt Bochum 2000. [8] Strutt AJ, Lorimer GW. Conf. Proc., Int. Conf. on Duplex Stainless Steel '86, The Hague; 1986. p. 310.