1. Introduction
The heat treatment (HT) of austenitic stainless steels is a current problem not only in research but also in industrial practice. Due to their properties, these steels are widely used in nuclear engineering and the food and petrochemical industries. In addition to good mechanical and technological properties (weldability, formability), austenitic stainless steels are characterized by excellent corrosion resistance in normal environments and conditions. The weakness of the common grades is, however, their susceptibility to intergranular corrosion when exposed to higher temperatures and more aggressive environments [
1]. If the steel is sensitized in the temperature range of 425–870 °C [
2] (or 500–950 °C [
3]), chromium carbides can precipitate along the grain boundaries and cause local depletion of the steel by chromium [
2]. This problem can be solved either by reducing the carbon content of the steel or, for even better effect, by stabilizing the steel with an element with high carbon affinity (Ti or Nb) [
1]. During HT (so-called stabilization), the excess carbon is excluded in the form of stable carbides or carbonitrides of the stabilizing element, and thus, further precipitation of the chromium carbides is prevented. The material stabilized in this way may also show some increase in the values of its mechanical properties depending on the processing parameters. This is particularly useful for parts operating at higher temperatures due to the high thermal stability of the precipitates.
Many research papers discuss the heat treatment of stabilized austenitic stainless steels. Publications have very often dealt with the HT of parts after welding [
4,
5,
6,
7], corrosion resistance (especially intercrystalline corrosion) [
8,
9,
10,
11], fatigue properties [
12,
13,
14], or the mechanical properties of commercial steel AISI321 [
15,
16,
17]. However, what is not very common in the literature is the issue of the HT of stabilized grades in order to increase their mechanical characteristics, especially the cold and hot yield strength (YS) and ultimate tensile strength (UTS) [
18]. There is a particular lack of papers concerning non-commercial steel 08Ch18N10T according to GOST standards, developed especially for the needs of nuclear engineering, and which is subject to higher demands for its mechanical properties and micropurity. Some publications have also studied the deformation behavior of AISI321 steel [
19,
20,
21,
22], rolling or forging conditions and their effect on the strain hardening of 08Ch18N10T steel, or the course of solution and stabilization annealing [
23]. It is known that these forming operations have a certain effect on the production process of the steel. Although the importance of deformation hardening is not essential for the final hot yield strength (YS
350°C; the achieved strengths decrease again very rapidly due to the high-temperature solution annealing), the influence of the deformation strengthening on the kinetics of the precipitation processes, and thus, the secondary hardening was proved.
The processes currently used for the production of 08Ch18N10T steel have been proven in practice but are time-consuming and costly. In particular, efforts are being made to shorten and streamline the stabilization mode (720 °C for 10 h). It can be assumed that the original parameters of the stabilization were probably designed to achieve the required mechanical properties even with lower-quality formed semi-finished products. If this assumption is correct, then the possibility of re-evaluating the processing parameters in the individual stages of production, and thus, streamlining the production process becomes possible.
The material after processing must have high corrosion resistance together with good hot mechanical properties, which makes the issue of the HT of such material complex, requiring a thorough knowledge of the processing methods and the processes taking place during the treatments. Therefore, it is important to check the influence of the parameters of the individual production operations and determine the significance of their effects (i.e., metallurgy, forming, heat treatment) on the desired increase in the YS. This article, therefore, focuses on the temperature and dwell time during stabilization annealing. As the stabilization temperature increases, the kinetics of the precipitation processes increase, so we can assume that a slight increase in the stabilization temperature makes it possible to achieve the desired precipitation hardening in a significantly shorter time. Since a higher stabilization temperature generally also favors corrosion resistance, this combination appears to be particularly advantageous. However, the morphology of the precipitates and other aspects are also important. In order to shorten the production process while reaching the prescribed YS 350°C, it is necessary to obtain a comprehensive description and understanding of the processes taking place in the various stages of stabilization annealing, while also taking into account the previous processing history.
2. Experimental Methods
The austenitic stainless steel 08Ch18N10T stabilized with titanium (
Table 1) was chosen as the experimental material. Due to its use in nuclear engineering, this steel has a prescribed micropurity control, which is governed by the GOST 1778–70 standard. The content, morphology, and distribution of titanium carbonitrides are also monitored. However, the limits, which are optimal in terms of the micropurity and corrosion resistance, may go against the requirements for the strength characteristics—with a higher carbon content, the rate of precipitation hardening increases [
24]. Therefore, the carbon and titanium contents and their ratio are also closely monitored in this steel. The maximum carbon content is 0.08%, while there must be at least five times more titanium, to a maximum of 0.7%. Furthermore, the minimum required cold and hot mechanical properties (
Table 2), especially the YS
350°C (min. 177 MPa), are prescribed. Commercial equivalents of this steel are, for example, AISI 321 according to ASTM/ASME standards, and X6CrNiTi18-10 (1.4541) according to EN standards.
The processed semi-finished product was in the form of forged bars with a nominal diameter of 90 mm. The bars were a delivered solution annealed at 1020 °C for 110 min, subsequently cooled in water and stabilized at 720 °C for 600 min, cooled in air. With regard to the efficient use of the volume of material, the semi-finished product was cut using a water jet into smaller segments of about 45 × 20 × 110 mm (
Figure 1). Two tensile specimens were produced from each segment after HT. However, this method deviates from the rules of the methodology for micropurity evaluation and mechanical testing (according to the relevant standards, samples are always taken in the longitudinal direction, in the case of the bars with a diameter of >50 mm at a minimum distance of a quarter of the diameter from the rod surface). Therefore, the following labeling of individual tensile bodies was introduced: OO (segment and sample from the edge of the rod), OS (edge sample, middle segment), SS (middle sample and segment).
Thus, it was possible to monitor the influence of the sampling point in the cross-section of the rod on the development of the microstructure and mechanical properties. The selection of the segments for each HT mode was always the same—1 piece from each marking. It was proven (both on the samples after HT and in the initial state) that the proposed method of sampling did not significantly affect the results. The average values are presented in the graphs.
In order to determine the influence of the stabilization parameters on the mechanical properties and microstructure of 08Ch18N10T steel, segments with the approximate dimensions of 45 × 20 × 110 mm, cut from the supplied semi-finished product ø 90 mm, were heat-treated. A sequence was designed for the heat treatment of the experimental material, including solution annealing at 1020 °C for 30 min, and water quenching and subsequent stabilization with variable parameters (temperatures from 720 to 900 °C; dwell times from 30 min to 15 h—
Table 3). The heat treatment was performed in an atmospheric furnace. In order to determine only the effect of the solution annealing itself, a separate solution annealing at 1020 °C with a holding time of 30 min (without stabilization) was also tested. During processing, the temperature of the semi-finished products was measured using K-type thermocouples (Omega engineering Inc., Norwalk, CT, USA) placed in the drilled holes. A stabilization temperature of 720 °C was chosen in order to repeat the mode by which the supplied starting material was processed on the samples under laboratory conditions. Thus, it was possible to reliably compare this heat treatment mode with other modes.
Samples for mechanical tests and metallographic analyses were then produced from the processed segments by turning. Microstructural analyses were performed using light (LM) and scanning electron microscopy (SEM). The key property observed for this steel is the hot YS 350°C (min. 177 Mpa). Achieving this value is problematic, especially in combination with good corrosion resistance and the associated requirements of micropurity. Therefore, standardized tensile tests were performed at 350 °C, and at the same time, tests at room temperature (RT) were performed for comparison. Based on the results, 2 stabilization modes were selected for a detailed analysis of the precipitates and a study of the strengthening mechanism using diffraction analysis on thin films in a transmission electron microscope (TEM). These were samples with stabilization annealing at 800 °C for 1 and 10 h. Higher stabilization temperatures and different dwelling times were chosen to monitor the effect of higher stabilization temperatures on the kinetics and behavior of the precipitates.
Metallographic samples for light and scanning electron microscopy were prepared by mechanical grinding and polishing, followed by chemical etching using 221 reagent (hydrofluoric acid/glycerin/nitric acid). Microstructure images and analyses were obtained using an Olympus light microscope (Olympus, Darmstadt, Germany) and a Zeiss EVO MA 25 scanning electron microscope (Zeiss, Oberkochen, Germany).
TEM analyses were performed using a JEOL JEM-2200FX microscope (JEOL, Tokio, Japan). Thin foils were ground using metallographic fine-grained papers down to a thickness of 0.1 mm. This was followed by electrolytic jet-polishing using 6% HClO4 solution in methanol at a voltage of 23 V and a temperature of −60 °C. TEM used an accelerating voltage of 200 kV.
The mechanical properties were determined by a standardized tensile test (CWICK ROELL 250, Haan, Germany) at 350 °C and at RT. The tensile test at RT was performed according to ISO 6892-1 (corresponds to GOST 1497-84) with strain rates of 0.00025 s
−1 (up to the YS) and 0.0067 s
−1 (after reaching the YS). A tensile test at 350 °C was performed according to ISO 6892-2 (corresponds to GOST 9651-84) with strain rates of 0.00007 s
−1 (up to the YS) and 0.0014 s
−1 (after reaching the YS). The dimensions of the test bars were d = 10 mm, l
0 = 50 mm in both cases. The ultimate tensile strength (UTS), yield strength (YS), and elongation (A
5.65) were always measured. The test specimens for the tensile test were always taken from the edge (2 pcs) and the center (1 pcs) of the rod ø 90 mm. Thus, it was possible to check the influence of the sampling point and to find only negligible differences in the values measured for the samples from the center and the edge of the rod (according to the diagram in
Figure 1).
Author Contributions
Conceptualization, T.J., Š.J. and H.J.; methodology, T.J., L.K. and D.J.; validation, H.J. and L.K.; formal analysis, L.K. and D.J.; investigation, T.J. and R.L.; resources: T.J., R.L. and H.J.; data curation, T.J.; writing—original draft preparation—T.J.; writing—review and editing Š.J. and H.J.; supervision, Š.J. and H.J.; project administration, T.J.; funding acquisition, Š.J. and H.J. All authors have read and agreed to the published version of the manuscript.
Funding
This research was funded by the student grant competition of the University of West Bohemia in Pilsen. The APC was funded by the SGS-2021-025 Application of electron beam melting for welding of advanced high-strength steels.
Data Availability Statement
The research data are not publicly available due to ongoing research.
Acknowledgments
The present contribution has been prepared with the support of the student grant competition of the University of West Bohemia in Pilsen and the SGS-2021-025 Application of electron beam melting for welding of advanced high-strength steels. The project was funded by specific resources of the state budget for research and development.
Conflicts of Interest
The authors declare no conflict of interest.
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Figure 1.
Cross-section of the bar ø 90 mm—marking of the sampling points.
Figure 2.
Development of YS after RT tensile test depending on the mode of heat treatment used. Samples after solution annealing (A), stabilization (A/S), and initial state (IS). The minimum required YS value at RT is marked in red.
Figure 3.
Development of YS 350°C depending on the mode of heat treatment used. Samples after solution annealing (A), stabilization (A/S), and initial state (IS). The minimum required YS 350°C is marked in red.
Figure 4.
Images of microstructure of 08Ch18N10T steel after solution annealing at 1020 °C/30 min in combination with stabilization: 800 °C/1 h (a,c), 800 °C/10 h (b,d). LM micrographs (a,b) and SEM micrographs (c,d).
Figure 5.
EDX spectra of matrix (a), titanium carbide (b), and chromium carbide (c) at the grain boundary in the sample stabilized at 800 °C for 1 h.
Figure 6.
Sample stabilized for 1 h at 800 °C: (a) bright-field image of TiC precipitates and dislocations, (b) diffraction pattern of austenitic grain in orientation near the pole [2−21]. TEM micrographs.
Figure 7.
Sample stabilized at 800 °C for 1 h. Dislocation substructure of austenitic grain in orientation near the pole [112] with strong reflection type 111. TEM micrograph.
Figure 8.
Sample stabilized at 800 °C for 10 h. Dislocation substructure of austenitic grain in orientation near the pole [001] with strong reflection type 200. TEM micrograph.
Figure 9.
Sample stabilized at 800 °C for 10 h. Chains of fine precipitates along dislocations: (a) bright field, (b) dark field using reflection 220TiC, (c) dark field using reflection 411χ, (d) diffraction pattern with designated reflections of dark fields, (e) scheme of the matrix (yellow) and coherent precipitate (white) zones [−112], (f) scheme of matrix (yellow) and χ-phase (pink) diffraction spots. TEM micrographs.
Table 1.
Chemical composition of the material used for the experiment (08CH18N10T).
C (%) | Cr (%) | Ni (%) | Ti (%) | Mn (%) | Si (%) | P (%) | S (%) |
0.05 | 17.75 | 10.05 | 0.43 | 1.8 | 0.52 | 0.024 | 0.014 |
Cu (%) | Mo (%) | V (%) | N (ppm) | W (%) | Co (%) | H (ppm) |
0.1 | 0.08 | 0.11 | 120 | 0.03 | 0.02 | 2.4 |
Table 2.
Prescribed mechanical properties: cold (according to GOST 1497-84), hot (according to GOST 9651-84); test specimen type IV-4, l
0 = 50 mm; shape of test specimens according to EN ISO 6892-1, annex D, test rod d 10 mm [
25,
26,
27].
Requested Cold Mechanical Properties | Requested Hot Mechanical Properties |
---|
Evaluated Property | Dimension (mm)/Value | Evaluated Property | Value |
---|
5–60 | 61–100 | 101–250 |
---|
YS (MPa) | min. 206 | min. 196 | YS 350°C (MPa) | min. 177 |
UTS (MPa) | 500–750 | UTS 350°C (MPa) | min. 353 |
A (%) | min. 40 | min. 38 | A 350°C (%) | min. 25 |
Z (%) | min. 50 | Z 350°C (%) | min. 45 |
Table 3.
Proposed modes of heat treatment—stabilization of the samples.
Solution Annealing | Stabilization Temperature | Holding Time |
---|
1020 °C | 30 min | 720 °C | 2.5/5/7.5/10/15 h |
800 °C | ½.5/5/10 h |
850 °C | 0.5/1/2.5/5 h |
900 °C | 0.5/2.5 h |
Table 4.
Tensile test results.
Stabilization Temperature | Hold | Tensile Test at RT | Tensile Test at 350 °C |
---|
UTS | YS | A | UTS 350°C | YS 350°C | A 350°C |
---|
(MPa) | (MPa) | (%) | (MPa) | (MPa) | (%) |
---|
Delivered condition | 568 | 336 | 48 | 412 | 277 | 26 |
Annealed 1020 °C/0.5 h | 557 | 294 | 50 | 398 | 233 | 27 |
720 °C | 2.5 h | 541 | 294 | 53 | 391 | 228 | 34 |
5 h | 543 | 300 | 54 | 395 | 241 | 32 |
7.5 h | 548 | 305 | 53 | 388 | 235 | 31 |
10 h | 551 | 306 | 52 | 392 | 241 | 31 |
15 h | 545 | 297 | 53 | 388 | 236 | 32 |
800 °C | 1 h | 548 | 297 | 54 | 390 | 238 | 30 |
2.5 h | 544 | 284 | 53 | 388 | 235 | 32 |
5 h | 541 | 286 | 53 | 381 | 227 | 29 |
10 h | 547 | 282 | 52 | 382 | 225 | 31 |
850 °C | 0.5 h | 550 | 293 | 53 | 389 | 233 | 30 |
1 h | 544 | 290 | 54 | 385 | 228 | 31 |
2.5 h | 545 | 287 | 53 | 385 | 230 | 30 |
5 h | 550 | 288 | 52 | 385 | 225 | 31 |
900 °C | 0.5 h | 542 | 282 | 54 | 384 | 220 | 32 |
2.5 h | 546 | 280 | 54 | 383 | 217 | 31 |
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