SIGMA PHASE PRECIPITATION IN DUPLEX PHASE STAINLESS STEELS

1)

Zbigniwe Stradomski1, Dariusz Dyja 2 Proffesor, Director Institute of Materials Engineering, 2) MSc, PhD students, 1,2) Czestochowa University of Technology, Institute of Materials Engineering dyjad@mim.pcz.czest.pl
The financial support by the Polish State Committee for Scientific Research No 3 T08 B 001 26 is gratefully acknowledged

Introduction. Precipitation processes occurring in duplex steels are determined by the possibility of formation of various intermetallic phases (, , , R) and carbides. The sigma phase has particular importance among them, as already its small amount causes a considerable reduction in plasticity and impairment in corrosion resistance. The Fe-Cr-Ni system indicates that all duplex steels are subject to the precipitation of the sigma phase, with ferrite stabilizing elements, chiefly chromium and molybdenum, increasing the rate of its precipitation. From a practical viewpoint, the occurrence of this phase as early as in the production process with associated brittleness constitute a problem of paramount importance, more especially as the duplex cast steel belongs to a family of steels, whose equilibrium structure is composed of ferrite, austenite and intermetallic phases. The desirable structure of those materials, composed of approximately equal parts of ferrite and austenite, without intermetallic phases, is a non-equilibrium structure that can be achieved solely by means of properly performed heat treatment. Materials and Methods. The GX2CrNiMoCu25-6-3-3 stainless steels used in this study were in as-cast condition. The chemical composition of the two test materials are listed in Tab.1
C 0.06 0.10 Cr 24.2 24.0 Ni Cu 7.5 2.6 7.6 2.6 S 0.01 0.01

Table 1
Si 0.9 0.9

0.06-0.1% results in a possibility of carbides precipitation in the cast steel examined. As the locations of nucleation of M23C6 carbides are primarily ferrite/austenite interfaces, hence these precipitates may constitute preferable spots for phase nucleation.

Mn 0.13 0.25

P 0.02 0.02

Mo 2.41 2.35

The optical microscope (OM) was used for microstructure observation of duplex steel with different C contents. The ImagePro Plus analyzer was used to estimate the stainless steel phase contents. The redistribution of the substitutional alloying elements Cr, Mo, Ni, Mn and Si between the ferrite, the austenite and the intermetallic phase was followed by means of scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). Theoretical thermodynamic analysis sigma phase participation with Thermo-Calc software package was done. Results. In cast steel of duplex type the main ferritestabilizing elements are chromium, molybdenum and silicon. To provide high corrosion resistance for these steels, a large amount of either chromium or molybdenum is necessary. In the presence of large quantities of these elements the possibility of occurring the brittle tetragonal sigma phase in this steel increases. The effect of chemical composition and cooling rate on the range of occurrence of various precipitates is illustrated in Fig. 1. The carbon present at a level of

Figure 1 An analysis carried out using the Thermo-Calc program has shown that the precipitation of the intermetallic sigma phase in investigated steel takes place during cooling a cast after its solidification in a temperature range from 8500C to approx. 5500C. The chemical composition of this phase includes, in addition to Fe, approx. 30-60% Cr and 4-10% Mo. The sigma phase appears much more quickly in ferrite than in austenite, not only due to the fact that the ferrite is closer to the sigma phase in chemical
27.829.2 4.545.60 2.653.95 0.791.23 1.352.25 20.922.3 7.929.79 1.372.26 0.831.19 3.063.91

Table 2

Cr Ni Mo Si Cu

' 20.322.4 8.179.64 2.154.06 0.711.18 2.744.4

32.166.9 1.583.31 6.3510.6 1.411.54 1.41

composition, but primarily because of a higher diffusion rate. The formation of phases enriched in chromium and molybdenum causes the ferrite to be depleted in these alloying constituents, as a consequence of which it may transform into austenite depleted in the above-mentioned elements (Fig. 2). As the diffusion in the austenite surrounding the depleted ferrite, as a result of which the equalization of chromium and molybdenum contents should occur, is slow, therefore the corrosion resistance of the metal bordering the sigma phase, and thus that of the whole alloy, decreases.

Table 3

% % %

1 48.9 48.8 2.30

2 48.4 45.2 3.40

Cooling rate 3 51.2 44.7 4.30

4 50.5 42.5 6.50

5 48.2 37.7 13.1

the amount of the undesirable sigma phase increases, and this increase is accompanied by a reduction in delta ferrite content of the microstructure. Fine, rounded phase precipitates are distributed not only at the ferrite/austenite interfaces, but also inside the austenite and ferrite grains, and it can also be noticed that sigma phase precipitates tend to surround the austenite grains, which substantially influences the service properties of the cast steel. Conclusions and discussion. During solidification and subsequent cooling process, duplex steel casts, especially those of large cross-sections, will tend to develop sigma phases. Therefore, in respect of casts, the necessity of carrying out heat treatment after removing the cast from the mould is obvious. Every cast must be heat treated at a high temperature that assure the dissolution of undesirable phases, and then cooled quickly so as to prevent the appearance of the sigma phase. In the light of the investigation carried out it should be noted, however, that no complete elimination of the sigma phase is possible in massive casts, and properly performed heat treatment operations will only allow its adverse effect to be minimized. The above-mentioned factors favouring sigma phase precipitation in cast steel of duplex type show that the higher cooling rate after the cast solidification process the lower tendency of sigma phase precipitation in the material. Therefore, in order to increase cooling rate, casts of this material should be removed from the mould immediately after being solidified. A lot of attention should also be given to the design of the cast, chills and the supply of metal to the mould cavity (thermal centres in the cast should be avoided, and in addition, the machining allowance should be as small as possible, not only for saving reasons, but also with a view to increasing cast wall thickness and thus lengthening the solidification time).
References [1] Dong L., Effect of phase formation on mechanical properties of stainless steel SUS309L isothermal aging, Steel Research, 2004, [2] Premachandra K., Effect of stabilising elements on formation of phase in experimental ferritic stainless steel containing 39% Cr, Materials Science and Technology, 1992, [3] Erneman J., Quantitative metallography of sigma phase precipitates in AISI 347 stainless steel, Materials Science and Technology, 2004

Figure 2 The sigma phase nucleates at the ferrite/austenite interface and grows towards the ferrite grains as a result of the following eutectoid reaction: + (1). A schematic diagram of sigma phase nucleation at the ferrite/austenite interface and its increase in the ferrite is shown in Fig. 2. The structure of the alloy examined, as shown in Fig. 4, confirm that the sigma phase forms by way of decomposition according to reaction (1). Sigma phase precipitation may also occur directly in the ferrite, with preferable nucleation locations being other precipitates, particularly carbides. In order to establish of how the rate of cooling after the solutioning process influences sigma phase precipitation in massive casts, samples taken from the cast were soaked in laboratory conditions at 10900C for 3 hours, and then cooled in: 1-water, 2-oil, 3compressed air, 4-air, and 5-with the furnace. The results show that phase precipitation can be avoided by using high cooling rates after the solution heat treatment (Tab. 3). With decreasing cooling rate

Figure 4