Vacuum 174 (2020) 109220
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Short communication
Thermodynamics basis of saturation of martensite content during reversion annealing of cold rolled metastable austenitic steel Mohammad Javad Sohrabi, Hamed Mirzadeh *, Changiz Dehghanian School of Metallurgy and Materials Engineering, College of Engineering, University of Tehran, P.O. Box 11155-4563, Tehran, Iran
A R T I C L E I N F O
A B S T R A C T
Keywords: Stainless steels Phase transformation Reversion annealing Deformation-induced martensite Thermodynamical analysis
The dependency of martensite content on reversion temperature in a metastable austenitic stainless steel was studied based on the experimental and thermodynamics analyses. It was revealed that the formation and reversion of the strain-induced martensite can be rationalized based on the presence of ferrite phase at equi librium condition, which explains the metastability of the material. Accordingly, the saturation of the amount of martensite after annealing at moderate temperatures and the dependency of austenite finish temperature on chemical composition were unraveled.
The formation of strain-induced martensite (SIM) and its reversion in metastable austenitic stainless steels has received a considerable atten tion, which can be related to its utilization in magnetization [1,2], transformation-induced plasticity (TRIP) effect [3–5], and extreme grain refinement [6,7]. The formation of martensite during cold working has been related to the availability of a sufficient mechanical driving force to compensate the lack of chemical driving force. However, saturation below 100 vol% in the amount of attainable SIM has been reported, which is related to the austenite stability, deformation temperature, and other factors [8,9]. It is interesting to note that some authors have also reported the appearance of saturation in the amount of martensite during reversion annealing at temperatures below ~1000 K irrespective of the holding durations [10–12]. However, there is no clear explanation for this behavior and the slow kinetics of reversion was mentioned as the main reason. It has been suggested without any proof that the amount of martensite is expected to reach zero at very long holding times [12]. Some authors argued that the observed asymptotic behavior in the evolution of martensite content during annealing is related to the (I) carbide precipitation, carbon depletion, and an increase in the martensite start temperature (Ms) in AISI 301LN alloy [13] or (II) in hibition of reversion by TiC precipitation in titanium-stabilized AISI 321 alloy [14]. However, it might be possible to relate these results to the equilibrium conditions. It is noteworthy that the situation might become more complicated, where the volume fraction of martensite in the deformed austenitic stainless steels might increase during subsequent annealing treatments
[15–17]. Zhou et al. [15] reported an increase in the amount of martensite with increasing annealing temperature up to 400 � C with the subsequent decrease at higher temperatures. This resulted in the in crease of yield stress from 1400 MPa to 1720 MPa. There are other reports on the appearance of austenite start (As) and austenite finish (Af) temperatures during heating, where it was reported that by increasing the annealing temperature, the amount of martensite decreases and reaches zero at Af temperature [1,18,19]. The obtained values of As and Af temperatures were related to the amount of cold rolling (initial martensite content), annealing time, and chemical composition [1,20]. Among these parameters, the only reasonable one is the chemical composition of the materials. Therefore, these important subjects need much more attention from the experimental and ther modynamics standpoints. The present work aims to deal with these subjects. AISI 304L stainless steel with the chemical composition (wt%) of Fe0.01C-18.6Cr-8.3Ni-1.4Mn-0.4Si-0.1Mo-0.1 V was received in the annealed condition. The sheet was rolled at 0 � C up to the reductions in thickness of 20–90%. The 90% cold rolled sheet was isothermally annealed at temperatures between 400 and 725 � C up to 43200 s. A PHILIPS PW-3710 X-ray diffractometer (XRD) with Cu-Kα radiation was used for phase analysis, where the amount of martensite was calculated using Equation (1) [5,21]: fα0 ¼ Ið211Þα0 =fIð211Þα0 þ 0:65ðIð311Þγ þ Ið220Þγ Þg
(1)
After electrolytic polishing (H3PO4–H2SO4 solution at 40 V for 40 s) and electroetching (60% HNO3 solution at 2 V for 20 s), A FEI NOVA
* Corresponding author. E-mail address:
[email protected] (H. Mirzadeh). https://doi.org/10.1016/j.vacuum.2020.109220 Received 7 January 2020; Received in revised form 13 January 2020; Accepted 21 January 2020 Available online 24 January 2020 0042-207X/© 2020 Elsevier Ltd. All rights reserved.
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Fig. 1. XRD Analysis of the (a,b) Formation of martensite during cold rolling and (c,d,e,f) Reversion of martensite in the 90% cold rolled sample.
NANOSEM 450 FE-SEM was used for microstructural analysis. The grain size was measured based on the standard intercept method. The evolu tion of phases was also studied based on the thermodynamics funda mentals, where the JMatPro (Java-based Materials Properties) software was used to find the equilibrium amount of phases. Fig. 1a shows the XRD patterns of the cold rolled samples. It can be seen that by increasing the reduction in thickness, the peaks of BCC α0 –martensite appear and their intensities increase but the intensity of austenite peaks decline. Fig. 1b depicts the calculated amount of martensite by Equation (1), where it increases with the reduction in thickness and become saturated at ~93.6 vol% martensite. Fig. 1c shows the calculated martensite content for the 90% cold rolled sample after annealing for 3600 s at different temperatures. It can be seen that by increasing the temperature, the amount of martensite decreases and reaches zero at 725 � C. This Af temperature was obtained for 3600 s, and hence, at equilibrium conditions, a lower Af temperature is expected. Therefore, for the subsequent isothermal annealing exper iments, lower reversion temperatures such as 715 and 700 � C were considered, where the representative XRD results are shown in Fig. 1d
and e and the calculated amounts of martensite have been summarized in Fig. 1f. The latter figure clearly shows the presence of saturation in the martensite content at each temperature, where the volume fraction of martensite at the saturation point and the required time decrease with increasing temperature. While at 715 � C, a complete reversion was achieved at 5400 s, around 8 vol% martensite was achieved after 7200 s at 700 � C and remained even after long holding time of 43200 s. To provide another evidence for the obtained results, the microstructure of samples were studied as shown in Fig. 2. With the aid of XRD patterns in Figs. 1 and 2b reveals that 90% cold rolling results in the formation of pancaked martensite grains in place of equiaxed austenite grains in Fig. 2a. Annealing at 715 � C for 900 s resulted in the formation of ultrafine reversed austenite grains (0.3 μm on average) at the expense of some martensite grains (Fig. 2c). After 5400 s, the pancaked martensite grains cannot be seen and an equiaxed austenitic structure with average grain size of 0.9 μm was obtained (Fig. 2d). This reveals an extreme grain refinement when compared to the as-received microstructure with average grain size of 16.3 μm. Continued annealing up to 43200 s resulted in the coarsening of the 2
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Fig. 2. Representative microstructures of AISI 304L stainless steel after 90% cold rolling and reversion annealing at various conditions. RD and TD represent the rolling and transverse directions, respectively.
microstructure as shown in Fig. 2e (average grain size of 1.5 μm). At 700 � C, after holding time of 900 s, ultrafine reversed austenite and remained martensite grains were seen (Fig. 2f), where after 7200 s, ~8 vol% martensite remained (Figs. 2g and 1). However, continued annealing up to 43200 s resulted in the coarsening of the reversed grains (Fig. 2h) but the amount of martensite did not change (Fig. 1). There fore, it seems that the equilibrium martensite content is ~8 vol% at 700 � C, which needs to be evaluated based on the thermodynamics principles. Fig. 3a shows the calculated equilibrium phases versus temperature for the studied AISI 304L alloy. It can be seen that the equilibrium amounts of austenite and BCC phases at room temperature are ~10 wt% and ~90%, respectively. This is an indication of the metastability of the austenite phase, which can be realized based on the schematic diagram of chemical free energies of austenite and martensite phases as a
function of temperature [22] in Fig. 3b. It can be seen that a mechanical driving force (U) at temperatures above Ms is required for martensitic transformation, which was provided by cold rolling in the present work (~90% martensite phase at saturation point during cold rolling). In fact, the occurrence of the strain-induced martensitic transformation can be attributed to the plastic deformation effects by the formation of ener getically favorable nucleation sites. The deformation of the alloy tended to provide the equilibrium condition of the material, which was observed in other cases [23], and hence, the BCC phase in Fig. 3a at around room temperature is the martensite phase. Therefore, the equi librium amount of the BCC phase can be used to judge the dependency of the remaining martensite content on the reversion temperature. For this purpose, the thermodynamics analysis of the base AISI 304L alloy (Fe–18Cr–8Ni) was taken into account to make the discussion valid without implications from C, Ti, and similar elements [13,14], which is 3
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Fig. 3. Summary of thermodynamics analysis.
shown in Fig. 3c. The As and Af temperatures were obtained to be as ~400 � C and 716 � C, where the former was experimentally observed in previous works [19,20] and the latter was verified by the results shown in Fig. 1f (zero martensite content at 715 � C). The experimental satu rated martensite contents (Fig. 1f) and the results of the JMatPro anal ysis were compared in Fig. 3d, where a good agreement was reached. This implies that the martensite phase is the BCC ferrite phase in ther modynamics analysis. This is an important finding, which explains the dependency of saturation of martensite content on temperature and can be used for designing the reversion annealing for engineering purposes. These analyses can also be applied to previous works. In the case of AISI 301LN steel [13], reversion at 700 � C resulted in the complete reversion or tendency for complete reversion. This can be rationalized by the JMatPro results shown in Fig. 3e, where it was found that the Af
temperature is below 700 � C. In the case of Ti-stabilized AISI 321 steel [14], ~20 vol% martensite remained after annealing at 650 � C for long holding times, which can be rationalized by the JMatPro results shown in Fig. 3f (see the dashed lines). Complete reversion was reported by these authors at 800 � C [14], which is higher than the predicted Af temperature. Since these analyses can predict the Af temperature, the effect of Cr and Ni content on the Af temperature was modeled by JMatPro as shown in Fig. 3g for future applications. In summary, the reversion annealing of AISI 304L austenitic stainless steel was studied based on the experimental and thermodynamics ana lyses. Saturation in the amount of martensite was observed after cold rolling and after annealing at moderate temperatures, where at austenite finish temperature, complete reversion was achieved. The presence of ferrite phase at equilibrium condition was linked to the formation and 4
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reversion of the strain-induced martensite, which can be considered as the basis for the metastability of austenite phase in AISI 304L austenitic stainless steel. Accordingly, the saturation of the amount of martensite after annealing at moderate temperatures and the dependency of austenite finish temperature on chemical composition were unraveled.
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