Materials Science and Engineering A 444 (2007) 6468

Microstructural evolution in AISI 304 stainless steel during directional solidication and subsequent solid-state transformation
J.C. Ma a , Y.S. Yang a, , W.H. Tong a , Y. Fang b , Y. Yu b , Z.Q. Hu a
a

Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China b Baosteel Research Institute, Shanghai 201900, China Received 14 February 2006; accepted 10 August 2006

Abstract The microstructural evolution during solidication and subsequent solid-state transformation of AISI 304 stainless steel is studied by directional solidication and quenching methods in this paper. The phase transformation sequence in the steel directionally solidied is that the precipitation of primary ferritic dendrites, ferriteaustenite eutectic reaction, and the direct formation of austenite occur in sequence during the directional solidication of the austenitic stainless steel. At the eutectic reaction stage, plenty of columnar and cellular eutectic colonies composed of the coupled growth of lamellar ferrite and austenite take place. During the course of subsequent solid-state transformation, austenite grows into ferrite gradually, resulting in the disappearing of eutectic colonies and thinning of primary ferritic dendrites, and dendrite cores of primary ferrite are retained as the nal skeletal ferrite in the nal microstructure. 2006 Elsevier B.V. All rights reserved.
Keywords: Austenitic stainless steel; Directional solidication; Eutectic colony

1. Introduction The solidied microstructure of austenitic stainless steel typically contains a variety of complex austeniteferrite structure. This complex structure is a result of both the solidication behavior and subsequent solid-state transformation which are controlled by composition and cooling rate [13]. Although there are extensive discussions in the literatures on the solidication mechanism of austenitic stainless steel, no clear model has been accepted yet [35]. According to the FeCrNi ternary phase diagram, a threephase reaction region exists for compositions of chromium and nickel over 15 wt.% Cr and 10 wt.% Ni [37]. In this three-phase reaction region ferriteaustenite eutectic is expected at the primary ferrite ( ) boundaries when the liquidus composition reaches a monovariant eutectic trough, according to the solidication path [9,10]. However, the reaction in the three-phase trough is more unambiguous because the solid-state transformation from ferrite ( ) to austenite ( ) during subsequent cooling process makes the nal microstructure cannot be discriminated easily [214]. Furthermore, there are few reports referring to

this ferrite-austenite eutectic and its coupled growth [10]. So far, the solidication mechanism of austenitic stainless steel is not clear, especially the three-phase reaction mechanism in the (L + + ) region. Directional solidication is considered as an effective method to study microstructural evolution during solidication. A lot of investigations have revealed a wide range of solidication microstructures, and have led to improved microstructural theories [15]. Directional growth enables independent control of both the interface velocity and the temperature gradient over a given range, and thus allows direct comparison of their effects on the transformation product [1416]. However, there are few researches on microstructural evolution of stainless steel during directional solidication. In this paper, directionally solidied AISI 304 austenitic stainless steel is studied to investigate its solidication sequence and microstructural evolution. To keep the solidifying microstructure to room temperature for observation, a quenching method is used during the directional solidication of the steel. 2. Experimental Commercial AISI 304 stainless steel rods were used in the experiments, whose compositions (wt.%) were Cr 17.93, Ni

Corresponding author. Tel.: +86 24 23971728; fax: +86 24 23844528. E-mail address: ysyang@imr.ac.cn (Y.S. Yang).

0921-5093/$ see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.msea.2006.08.039

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8.76, Mn 0.77, Si 0.56, C 0.048, P 0.031, S 0.013, and Fe balance. The rods were machined into samples with 8 mm diameter to t the alumina tube for directional solidication. Directional solidication experiments were performed in an Ar atmosphere. The temperature gradient was 20.0 K/mm, and the withdraw velocity was 166.7 m/s. After the heated zone of the sample being melted for 20 min, the sample was withdrawn downward at the constant velocity for steady growth. In order to observe the microstructure at various stages of solidication, the sample with the alumina tube was dropped quickly into a brine quenching bath when the desired volume fraction of the melted alloy solidied. The solidied microstructure on the longitudinal section of the samples was observed with optical microscopy (OM) and SEM. The samples for OM and SEM observation were prepared by mechanical polishing and electrolytic etching with a solution of 10% oxalic acid. The concentrations of Cr and Ni in the solidied samples were measured by EPMA. 3. Results 3.1. Solidied microstructure The microstructure of the steel directionally solidied with temperature gradient of 20.0 K/mm and withdraw velocities of 166.7 m/s is shown in Fig. 1. The dark delta ferrite phase exists as skeleton in the austenite matrix after directional solidication of the AISI 304 stainless steel. 3.2. Quenched microstructures Quenched microstructures of the specimen directionally solidied at different time with the temperature gradient of 20.0 K/mm and withdraw velocity of 166.7 m/s are shown in Fig. 2. According to the quenched microstructures shown in Fig. 2, the process of directional solidication of the tested stainless steel can be classied into four stages. At the rst stage, primary ferritic dendrites precipitate directly from the melt (Fig. 2a); then, plenty of columnar and cellular eutectic colonies form among primary ferritic dendrites at the three-phase reaction

stage (Fig. 2b); as the directional solidication goes on, some eutectic colonies disappear gradually because transformation at the solid-state transformation stage (Fig. 2c); and nally almost all the colonies disappear and only skeletal ferrite is retained in the nal microstructure (Fig. 2d). Fig. 3 shows the enlarged columnar and cellular eutectic colonies. It can be seen that the connected ferrite together with the neighboring austenite constitutes the columnar and cellular colonies from Fig. 3a and b. The three-dimensional SEM images of delta ferrite in the columnar and cellular colonies are shown in Fig. 3c and d. In these columnar and cellular colonies the close-knit ferrite lamellae with curved planes are inter-tangled and arranged with a certain orientation. 4. Discussion 4.1. Solidication mode For austenitic stainless steels, the solidication mode is related to Ni equivalent (Nieq ) and Cr equivalent (Creq ) which are used to simplify a multi-composition system into the FeCrNi ternary system [1,17]. Depending on the ratio of Ni equivalent and Cr equivalent (Creq /Nieq ), the solidication modes of austenitic stainless steels can be divided into the following four modes [9,15]: A mode: L L + Creq /Nieq < 1.25; AF mode: L L + L + + + 1.25 < Creq /Nieq < 1.48; FA mode: L L + L + + + 1.48 < Creq /Nieq < 1.95; F mode: L L + Creq /Nieq > 1.95. Here, Nieq and Creq can be estimated by the following equations [2]: Nieq = %Ni + 30 %C + 30 %N + 0.5 %Mn Creq = %Cr + %Mo + 1.5 %Si + 0.5 %Nb (1) (2)

With Eqs. (1) and (2), Creq is calculated as 18.77 wt.%, Nieq as 10.59 wt.%, and Creq /Nieq as 1.77 for the tested AISI 304 stainless steel. So, the solidication mode of the steel falls into FA mode, i.e. the precipitation of primary ferrite, plus three-phase reaction (ferrite, austenite and liquid) at the terminal solidication stage, and continuing below the solidus line [4,6]. 4.2. Solidication sequence Based on the FA solidication mode, the solidication process of the AISI 304 stainless steel from liquidus to solidus can be divided into two stages: the primary ferrite precipitation stage and the three-phase reaction stage. At the primary ferrite precipitation stage, ferrite dendrites form directly from the melt, as shown in Fig. 2a. As the solidication goes on, it reaches the three-phase reaction stage when eutectic colonies appear among the primary ferrite dendrites (Fig. 2b). It is interesting that the more detail at terminal stage

Fig. 1. Skeletal morphology of delta ferrite in directionally solidied AISI 304 stainless steel.

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Fig. 2. SEM images of quenched microstructures of directionally solidied AISI 304 stainless steel at different stages. (a) Primary ferrite precipitation stage; (b) three-phase reaction stage; (c) solid-state transformation stage; (d) nal stage.

Fig. 3. SEM images of deep etched eutectic colonies. (a) Columnar colonies; (b) cellular colonies; (c) magnied image of (a); and (d) magnied image of (b).

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Fig. 4. Concentration proles of Cr and Ni at the three-phase reaction stage. (a) Backscattered image; (b) Cr concentration prole; and (c) Ni concentration prole.

Fig. 5. Concentration proles of Cr and Ni at the nal stage. (a) Backscattered image; (b) Cr concentration prole; (c) Ni concentration prole.

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of three-phase reaction can be obtained from the concentration proles of Cr and Ni shown under the three-phase reaction. As shown in Fig. 4, both Cr and Ni are enriched in the last solidied liquid region between primary ferrite and eutectic colonies, which solidies into austenite at the end of solidication. Based on above analysis, the solidication sequence of this directionally solidied steel is that primary ferritic dendrites precipitating from the melt at rst, then cellular and columnar eutectic colonies occurring in the inter-dendrite regions with the growth of primary ferrite, and then austenite precipitating directly from the nal melt enriched of both Cr and Ni between primary ferrite and eutectic colonies. 4.3. Solid-state transformation Solid-state transformation plays an important role in microstructural evolution of austenitic stainless steel. Based on the microstructural evolution during directional solidication, the transformation from ferrite to austenite is a gradual process for the stainless steel, which is controlled by element diffusion in the steel. During the solid-state transformation from ferrite to austenite, the growth of austenite is accompanied by the rejection of Cr and the acceptance of Ni, resulting in an enrichment of Cr and depletion of Ni in the residual ferrite [13]. Because the diffusion is limited by the cooling process, the transformation from ferrite to austenite is uncomplete. Therefore the thinner ferrite lamellae transform to austenite during the cooling process after solidication, while the thicker primary dendrites cannot be dissolved completely and the dendrite cores with rich Cr and poor Ni are retained as skeletal ferrite in the nal microstructure as shown in Fig. 5. 5. Conclusions Directional solidication experiments were carried out in commercial AISI 304 stainless steel to explore the microstructural evolution for the solidication and subsequent solid-state transformation. The conclusions derived from the experiments

are as follows: (1) The solidication sequence of directionally solidied AISI 304 austenitic stainless steel is that the precipitation of primary ferritic dendrites is followed by eutectic reaction occurring among the dendrite arms, and the rest of the solidication is completed with the direct precipitation and growth of austenite. (2) Cellular and columnar eutectic colonies composed of lamellar ferrite and austenite occur among the primary ferritic dendrites at the beginning of three-phase reaction stage. (3) Eutectic colonies disappear and skeletal ferrite obtained from the incomplete transformation of the primary ferritic dendrites is retained during the subsequent solid-state transformation. Acknowledgement This work was supported by the National Natural Science Foundation of China (No. 50434040). References
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