Austenitic stainless steel containing a large amount of uniformly distributed nano-sized precipitates and its manufacturing method

Abstract

Austenitic stainless steel contains 16-26 wt% chromium (Cr), 8-22 wt% nickel (Ni), 0.02-0.1 wt% carbon (C), 0.2-1 wt% niobium (Nb), and 2-3.5 wt% manganese (Mn), has an austenitic matrix structure, and fine niobium carbides are precipitated within the austenitic matrix structure, and the fine niobium carbides are uniformly dispersed within the austenitic matrix structure. The austenitic stainless steel may further contain 0.5-1.5 wt% molybdenum (Mo).

Description

[Technical Field]

[0001] An austenitic stainless steel containing a high amount of uniformly distributed nano-sized precipitates and a method for producing the same are provided. [Background technology]

[0002] Austenitic stainless steels are generally used widely in modern industries such as structures and buildings due to their excellent corrosion resistance, mechanical properties, and workability. Recently, structural materials used in the energy industry are exposed to extremely high operating temperatures to achieve high thermal efficiency. However, the use of austenitic stainless steel is limited due to the difficulty in maintaining its integrity at high temperatures. In particular, if austenitic stainless steel is used in nuclear reactor internal structures exposed to high-energy neutrons, the integrity of the reactor internal structures would be compromised due to the expansion of pores in the material caused by long-term reactor operation. Therefore, in order to improve the high temperature properties and irradiation resistance of general austenitic stainless steels, research is being conducted into dispersing fine precipitates within the austenitic matrix.

[0003] For example, there are cooling and stabilization heat treatment processes performed after solution treatment using high-temperature heat treatment, diffusion reaction processes using nitriding and carburizing techniques, and mechanical alloying processes. However, when applying conventional processes to austenitic stainless steels to form fine precipitates, it can take an excessively long time and require expensive processing methods, resulting in high manufacturing costs. In particular, currently used processes have limitations in forming precipitates of a few nanometers in size that are uniformly distributed and have a high density within the matrix.

[0004] Meanwhile, according to Korean Patent No. 1,943,591 invented by the inventors of the present application, niobium-containing austenitic stainless steel contains 16-26 wt% chromium (Cr), 8-22 wt% nickel (Ni), 0.02-0.1 wt% carbon (C), 0.2-1 wt% niobium (Nb), 0.015-0.025 wt% titanium (Ti), 0.004-0.01 wt% nitrogen (N), and 0.5-2 wt% manganese (Mn), and has an austenitic matrix structure in which fine niobium carbides (NbC) of 11 nm or less are present on average 1×10 22 # / m 3 It contains at a density of

[0005] However, according to Korean Patent No. 1,943,591, although it is possible to form nano-sized precipitates that are fine yet have high density within the austenite matrix, in order to further improve high-temperature strength, irradiation resistance, creep resistance, etc., it is necessary to distribute nano-sized precipitates that are even finer in size and have even higher density within the austenite matrix.

[0006] Prior documents include Korean Patent 1,943,591, Korean Patent Publication No. 2017-0074265, Korean Patent 1,401,625, and Japanese Patent 3,764,586. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Korean registered patent 1,943,591 [Patent Document 2] Korean Patent Publication No. 2017-0074265 [Patent Document 3] Korean registered patent 1,401,625 [Patent Document 4] Registered Japanese patents: 3,764,586 Summary of the Invention [Problem to be solved by the invention]

[0008] The austenitic stainless steel and the manufacturing method thereof according to the embodiment are intended to contain nano-sized precipitates that are uniformly distributed with a high number density within the austenitic matrix. The austenitic stainless steel and the manufacturing method thereof according to the embodiment are for uniformly distributing a large amount of fine nano-sized niobium carbide (NbC) or fine niobium-molybdenum carbide ((Nb,Mo)C) in the matrix of the austenitic stainless steel. The austenitic stainless steel and the manufacturing method thereof according to the embodiment are intended to improve the mechanical properties such as high-temperature strength of the austenitic stainless steel. The austenitic stainless steel and the manufacturing method thereof according to the embodiment are intended to improve the neutron irradiation resistance of the austenitic stainless steel. Austenitic stainless steels and methods for making same according to embodiments are intended to improve the creep resistance of austenitic stainless steels. Austenitic stainless steels and methods for producing them according to embodiments are intended to reduce the cost of producing austenitic stainless steels. The austenitic stainless steel and the method for producing the same according to the embodiment are intended to improve the productivity of austenitic stainless steel. In addition to the above object, the embodiments of the present invention can be used to achieve other objects not specifically mentioned. [Means for solving the problem]

[0009] An austenitic stainless steel according to one embodiment comprises 16-26 wt% chromium (Cr), 8-22 wt% nickel (Ni), 0.02-0.1 wt% carbon (C), 0.2-1 wt% niobium (Nb), and 2-3.5 wt% manganese (Mn), and has an austenitic matrix structure in which fine niobium carbide (NbC) is precipitated and uniformly dispersed within the austenitic matrix structure.

[0010] The austenitic stainless steel may further include 0.5-1.5 wt. % molybdenum (Mo). Fine niobium-molybdenum carbides are precipitated in the austenitic matrix structure, and the fine niobium-molybdenum carbides are uniformly dispersed in the austenitic matrix structure. The austenitic stainless steel may further contain more than 0% and not more than 0.3% by weight of silicon (Si). The fine niobium carbides may have an average size of 11 nm or less. In the austenitic matrix, the number density of fine niobium carbides is 1×10 14 -5×10 15 # / m 2 may be. In the austenite matrix, the density of fine niobium carbides is 1×10 22 -1×10 23 # / m 3 may be. The fine niobium-molybdenum carbide may have an average size of 6 nm or less. In the austenitic matrix, the number density of fine niobium-molybdenum carbides is 5×10 14 -5×10 15 # / m 2 may be. In the austenitic matrix, the density of fine niobium-molybdenum carbides is 1×10 22 -5×10 23 # / m 3 may be. The austenitic stainless steel may further contain more than 0% and not more than 0.01% by weight of phosphorus (P) and more than 0% and not more than 0.01% by weight of sulfur (S).

[0011] According to one embodiment, a method for producing an austenitic stainless steel includes the steps of melting a mixed steel containing 16-26 wt% chromium (Cr), 8-22 wt% nickel (Ni), 0.02-0.1 wt% carbon (C), 0.2-1 wt% niobium (Nb), and 2-3.5 wt% manganese (Mn) and casting the melted mixed steel to form a cast steel having an austenitic matrix structure; evaluating the high-temperature deformation behavior of the cast steel to derive a recrystallization stop temperature; homogenizing the cast steel; performing one or more passes of hot rolling at a temperature higher than the recrystallization stop temperature, followed by multi-pass hot rolling at a temperature lower than the recrystallization stop temperature; and heat treating the hot-rolled cast steel and then air-cooling it to precipitate fine niobium carbides within the austenitic matrix structure, the fine niobium carbides being uniformly dispersed within the austenitic matrix structure.

[0012] The mixed steel may further include 0.5-1.5 wt. % molybdenum (Mo). The hot-rolled cast steel material is heat-treated and then air-cooled to precipitate fine niobium-molybdenum carbides in the austenitic matrix structure, and the fine niobium-molybdenum carbides can be uniformly dispersed in the austenitic matrix structure. The mixed steel material may further contain more than 0% by weight and 0.3% by weight or less of silicon (Si).

[0013] In the multi-pass hot rolling stage, 5-15 passes of hot rolling can be performed. After 3-10 passes of hot rolling at a temperature above the recrystallization stop temperature, 2-5 passes of hot rolling at a temperature below the recrystallization stop temperature can be performed. As the hot rolling passes are performed sequentially, the temperature for each pass may be decreased by 10-50°C. In the stage of homogenizing the cast steel material, the heat treatment may be carried out at a temperature range of 1200-1300°C for 30 minutes to 2 hours. When the hot-rolled cast steel is heat-treated, it may be heat-treated at a temperature range of 700-800°C for 1-4 hours. [Effects of the Invention]

[0014] The austenitic stainless steel and the manufacturing method thereof according to the embodiments can contain nano-sized precipitates that are uniformly distributed with a high number density within the austenitic matrix, and can have a large amount of fine nano-sized niobium carbide or niobium-molybdenum carbide uniformly distributed within the matrix of the austenitic stainless steel, thereby improving the mechanical properties such as high-temperature strength of the austenitic stainless steel, improving neutron irradiation resistance, improving creep resistance, reducing the manufacturing cost of the austenitic stainless steel, and improving productivity. [Brief explanation of the drawings]

[0015] [Figure 1] 1 is a flowchart illustrating a method for manufacturing an austenitic stainless steel according to an embodiment. [Figure 2] FIG. 1 is a diagram illustrating a summary of the manufacturing process and conditions for an austenitic stainless steel according to an embodiment. [Figure 3a-3b] 1 is a graph showing the results of a high-pressure compression test in the stage of deriving the recrystallization stop temperature in Example 1. [Figures 4a-4c] 1 is a transmission electron microscope microstructure photograph of an austenitic stainless steel containing fine niobium carbides according to Example 5. [Figures 5a-5c] 1 is a transmission electron microscope microstructure photograph of an austenitic stainless steel containing fine niobium-molybdenum carbides according to Example 15. [Figure 6] 1 is a transmission electron microscope microstructure photograph of an austenitic stainless steel containing fine niobium carbides according to Comparative Example 8. [Figure 7a-7b] 1 is a graph showing the results of measuring the average size and density of precipitates according to heat treatment conditions of austenitic stainless steels containing fine niobium carbide or niobium-molybdenum carbide according to Examples 1 to 18 and Comparative Examples 1 to 9. DETAILED DESCRIPTION OF THE INVENTION

[0016]

[0023] The present invention will now be described in detail with reference to the accompanying drawings so that those skilled in the art can easily implement the present invention. The present invention may be embodied in various different forms and is not limited to the embodiments described herein. In the drawings, parts unnecessary for the explanation are omitted in order to clearly explain the present invention, and the same reference numerals are used throughout the specification for the same or similar components. Furthermore, in the case of well-known technology, detailed descriptions thereof are omitted.

[0017] Throughout the specification, when a part is said to "comprise" a certain element, this means that it may further include other elements, but not to the exclusion of other elements, unless specifically stated to the contrary.

[0018] Austenitic stainless steels according to embodiments include about 16-26 wt. % chromium (Cr), about 8-22 wt. % nickel (Ni), about 0.02-0.1 wt. % carbon (C), about 0.2-1 wt. % niobium (Nb), and about 2-3.5 wt. % manganese (Mn). The austenitic stainless steel may have an austenitic matrix structure. Austenitic stainless steels can contain nano-sized precipitates that are uniformly distributed with high number density within the matrix.

[0019] Austenitic stainless steels contain 16-26% by weight of chromium (Cr). Chromium is a ferrite stabilizing element and is an essential element used in stainless steel materials used in high temperature and high pressure environments where excellent oxidation resistance, corrosion resistance, and creep strength are required at the same time.

[0020] If the chromium content in austenitic stainless steel is less than about 16% by weight, the oxidation resistance and corrosion resistance of the stainless steel may be reduced, and if the chromium content exceeds about 26% by weight, a delta ferrite structure is formed, forming a duplex structure with the austenitic structure, which may reduce the strength and toughness of the stainless steel. It also reduces the stability of the austenitic phase at high temperatures, resulting in a decrease in creep strength.

[0021] Austenitic stainless steels contain approximately 8-22% nickel (Ni) by weight. Nickel can improve the corrosion resistance of austenitic stainless steel in non-oxidizing atmospheres and increase stacking fault energy, providing resistance to stress corrosion cracking. Nickel is an essential element for ensuring a stable austenitic structure, ensuring structural stability during long-term use, and achieving desired creep strength. To ensure a single crystal structure, the nickel content can be determined through thermodynamic calculations based on the chromium, iron, and nickel contents; for example, nickel can be controlled within the range of approximately 8-22 wt%.

[0022] Austenitic stainless steels contain approximately 0.02-0.1% carbon (C) by weight. Carbon is an element that stabilizes the austenite phase, and it can improve the strength of stainless steel by being supersaturated in the stainless steel and combining with elements such as chromium, niobium, and titanium during heat treatment or cooling to form precipitates. Therefore, from the perspective of ensuring high-temperature strength, it is preferable to include an amount of carbon appropriate to the amount of carbide-forming elements, as this strengthens the stainless steel through the precipitation of carbides within the grains. Carbon can also improve the room-temperature strength, high-temperature strength, weldability, formability, and other properties of stainless steel. If the carbon content of austenitic stainless steel is less than about 0.02 wt%, the mechanical strength properties of the stainless steel at room temperature may decrease, and if the carbon content exceeds about 0.1 wt%, the weldability and formability of the stainless steel may deteriorate and the toughness of the stainless steel may decrease.

[0023] Austenitic stainless steels contain approximately 2-3.5% by weight manganese (Mn). Manganese contributes to deoxidation during manufacturing, stabilizes the austenitic matrix structure, and has solid solution strengthening properties. It also indirectly contributes to increasing strength by increasing the solubility of N. In particular, it controls the diffusion rate of niobium within the austenitic matrix, preventing the coarsening of precipitates.

[0024] If the manganese content in austenitic stainless steel is less than about 2% by weight, it does not have a significant effect on refining precipitates, which can reduce the strength of the stainless steel. However, if the manganese content exceeds about 3.5% by weight, it promotes the precipitation of intermetallic compound phases such as sigma phases, which can lead to a decrease in toughness and softness due to a deterioration in structural stability in high-temperature environments. Furthermore, during welding, manganese turns into fumes and adheres to the weld, which can reduce the weldability of the stainless steel.

[0025] Austenitic stainless steels contain approximately 0.2-1 wt% niobium (Nb). Niobium element can combine with the above-mentioned carbon to form nano-sized fine niobium carbides, which can be uniformly dispersed in the austenitic matrix structure. Such fine niobium carbides uniformly dispersed in the austenitic matrix structure can significantly improve the mechanical properties such as strength of stainless steel, improve neutron irradiation resistance, and improve creep resistance.

[0026] If niobium is contained in austenitic stainless steel at less than about 0.2 wt%, the amount of precipitated niobium carbide or niobium-molybdenum carbide is small, and the degree to which the mechanical properties and irradiation resistance of the stainless steel are improved may be minimal. However, if niobium is contained in excess of about 1 wt%, coarse particle size niobium carbide or niobium-molybdenum carbide may be formed, which may reduce the strength and toughness of the stainless steel.

[0027] The austenitic stainless steel may further include about 0.5-1.5 wt. % molybdenum (Mo).

[0028] Molybdenum is an element that dissolves in the matrix and contributes to improving high-temperature strength, especially creep strength at high temperatures. In particular, molybdenum forms niobium-molybdenum carbide when added in combination with niobium, which reduces the unit cell length difference with the matrix compared to niobium carbide. The relatively slow diffusion rate of molybdenum between the austenite matrix and precipitates prevents the coarsening of precipitates, thereby increasing density and ensuring the phase stability of the precipitate phase in high-temperature environments.

[0029] In austenitic stainless steel, if the molybdenum content is less than about 0.5 wt%, it cannot affect the refinement of precipitates and may not ensure phase stability, while if the molybdenum content exceeds about 1.5 wt%, the austenitic structure may become unstable, reducing creep strength. In addition, a large amount of molybdenum content increases costs.

[0030] Niobium can combine with the carbon and molybdenum to form nano-sized or niobium-molybdenum carbides, which can be uniformly dispersed within the austenitic matrix. Such fine niobium-molybdenum carbides uniformly dispersed within the austenitic matrix can significantly improve the mechanical properties of stainless steel, such as strength, neutron irradiation resistance, and creep resistance.

[0031] The average size of the fine niobium carbide or niobium-molybdenum carbide can be about 11 nm or about 6 nm or less, and the number density of the fine niobium carbide or niobium-molybdenum carbide in the austenitic matrix structure can be about 1×10 14 -5×10 15 # / m 2 or 5×10 14 -5×10 15 # / m2 and the density of fine niobium carbide or niobium-molybdenum carbide is about 1×10 22 -1×10 23 # / m 3 or 1×10 22 -5×10 23 # / m 3 Within this range, the mechanical properties, neutron irradiation resistance, creep resistance, etc. of the stainless steel can be further improved.

[0032] The austenitic stainless steel may contain greater than 0% and up to about 0.3% by weight silicon (Si).

[0033] Silicon can perform a deoxidizing function and increase the amount of carbide precipitation. However, since silicon can cause precipitates to aggregate and become coarse, the silicon content of stainless steel may be about 0.3 wt% or less to refine the precipitates.

[0034] The austenitic stainless steel may contain greater than 0% to about 0.01% by weight phosphorus (P) and greater than 0% to about 0.01% by weight sulfur (S).

[0035] Phosphorus and sulfur are impurities that are unavoidably present in stainless steel, and if the content is high, they tend to segregate at grain boundaries, which can cause grain boundary embrittlement and reduce properties such as toughness. Therefore, the phosphorus and sulfur contents can be limited to approximately 0.01 wt% and approximately 0.01 wt% or less, respectively.

[0036] Hereinafter, a method for producing an austenitic stainless steel according to an embodiment will be described with reference to the drawings. The constituent elements and contents of stainless steel have been described above, so they will not be repeated here.

[0037] FIG. 1 is a flowchart showing a method for producing an austenitic stainless steel according to an embodiment, and FIG. 2 is a diagram showing an outline of the manufacturing process and conditions for producing an austenitic stainless steel according to an embodiment.

[0038] Referring to FIGS. 1 and 2, a method for producing austenitic stainless steel includes a thermodynamic simulation step of a model alloy, a melting and casting step, a step of deriving a recrystallization stop temperature, a homogenization heat treatment step, a multi-pass hot rolling step, and a step of precipitating fine niobium carbide or fine niobium-molybdenum carbide.

[0039] First, a thermodynamic simulation step of the model alloy is performed, followed by the melting and casting steps.

[0040] In the melting and casting step, a mixed steel containing 16-26 wt% chromium (Cr), 8-22 wt% nickel (Ni), 0.02-0.1 wt% carbon (C), 0.2-1 wt% niobium (Nb), and 2-3.5 wt% manganese (Mn) is melted, and the melted mixed steel is cast to form a cast steel having an austenitic matrix structure.

[0041] Here, the mixed steel may further include about 0.5-1.5 wt% molybdenum (Mo), more than 0 wt% and not more than 0.3 wt% silicon (Si), more than 0 wt% and not more than 0.01 wt% phosphorus (P), more than 0 wt% and not more than 0.01 wt% sulfur (S), residual iron (Fe), and unavoidable impurities.

[0042] The melting process may be a known process, for example, a vacuum induction melting process, but is not particularly limited thereto. The casting process may be a known process, for example, casting into an ingot, but is not limited thereto.

[0043] During the melting and casting stages, an austenitic matrix structure can be formed. Next, the high-temperature deformation behavior of the cast steel formed during the melting and casting stages was evaluated to determine the non-recrystallization temperature (TNR ) is derived.

[0044] The high-temperature deformation behavior of cast steel is evaluated through a hot torsion test or a dynamic physical property test. For example, a Gleeble dynamic physical property tester can be used to evaluate the high-temperature deformation behavior of cast steel, and the recrystallization stop temperature can be derived through a Gleeble compression test. The Gleeble compression test method is described in well-known papers (e.g., C.N. Homsher, "Determination of the Non-Recrystallization Temperature (T NR ) in Multiple Microalloyed Steels,” Colorado School of Mines, 2012).

[0045] This is followed by a homogenizing heat treatment step.

[0046] Homogenization heat treatment dissolves dendrites and unintended carbides in the cast steel material into the matrix, forming a single austenite phase in the heat treatment temperature range, which allows the subsequent multi-pass hot rolling process to be carried out effectively. This allows fine precipitates to be finely and homogeneously distributed in the matrix during the fine niobium carbide or niobium-molybdenum carbide precipitation process.

[0047] At this stage, the cast steel can be homogenized at a temperature range of about 1200-1300°C for about 30 minutes to 2 hours.

[0048] If the heat treatment is performed at a temperature below about 1200°C, the re-dissolution of dendrites and carbonitrides may not occur sufficiently, which may be detrimental to the homogenization of alloying elements. If the heat treatment is performed at a temperature above about 1300°C, not only will the production cost increase, but the austenite matrix may be locally melted, which may impair the microstructural homogeneity of the austenite matrix.

[0049] If the heat treatment is carried out for less than about 30 minutes, the redissolution of dendrites and unintended carbides may not occur sufficiently, and the solute atoms may be insufficiently diffused. If the heat treatment time exceeds about 2 hours, the grains may become coarse, which may increase production costs.

[0050] Within the aforementioned temperature and time ranges of the homogenization heat treatment, if the heat treatment temperature is increased, the heat treatment time may be correspondingly shortened, and if the heat treatment temperature is decreased, the heat treatment time may be correspondingly lengthened.

[0051] The homogenized heat treated cast steel can then be cooled in air or water and subjected to a multi-pass hot rolling step at the designed hot rolling start temperature.

[0052] The multi-pass hot rolling step is a step of performing one or more passes of hot rolling at a temperature higher than the recrystallization stop temperature based on the recrystallization stop temperature derived above, and then performing one or more passes of hot rolling at a temperature lower than the recrystallization stop temperature. Here, the multi-pass hot rolling may mean that hot rolling is divided into a plurality of sections and performed in stages, and each section may be defined as a pass.

[0053] For example, 5-15 passes of hot rolling may be performed overall, specifically, 3-10 passes of hot rolling may be performed at a temperature higher than the recrystallization stop temperature, followed by 2-5 passes of hot rolling at a temperature lower than the recrystallization stop temperature.

[0054] The hot rolling step in the conventional process for producing niobium-containing austenitic stainless steel is carried out at a temperature above the recrystallization stop temperature.

[0055] On the other hand, in the method for producing austenitic stainless steel according to the embodiment, hot rolling is performed at a temperature higher than the recrystallization stop temperature, and hot rolling is also performed at a temperature lower than the recrystallization stop temperature.

[0056] The temperature for each pass may differ by about 10-50°C. For example, when hot rolling is performed in multiple passes, the temperature for each pass may be lower by 10-50°C as the hot rolling passes are performed sequentially. Specifically, when five-pass hot rolling is performed, the first pass hot rolling is performed at a relatively highest hot rolling start temperature that is higher than the recrystallization stop temperature, the second pass hot rolling is performed at a temperature that is about 10-50°C lower than the first pass hot rolling temperature, the third pass hot rolling is performed at a temperature that is about 10-50°C lower than the second pass hot rolling temperature, the fourth pass hot rolling is performed at a temperature that is about 10-50°C lower than the third pass hot rolling temperature but lower than the recrystallization stop temperature, and the fifth pass hot rolling is performed at a hot rolling finish temperature that is about 10-50°C lower than the fourth pass hot rolling temperature.

[0057] FIG. 2 shows a multi-pass hot rolling stage in which six passes of hot rolling are performed at a temperature above the recrystallization stop temperature and two passes of hot rolling are performed at a temperature below the recrystallization stop temperature.

[0058] Such stepwise multi-pass hot rolling allows the potential in the matrix to be appropriately distributed, and accordingly, the fine niobium carbide or niobium-molybdenum carbide can be more finely and uniformly dispersed.

[0059] The reduction rate of the cast steel material by performing the multi-pass hot rolling step can be designed as required, thereby adjusting the thickness.

[0060] This is followed by a step of precipitating fine niobium carbide (NbC) or niobium-molybdenum ((Nb,Mo)C) within the austenitic matrix.

[0061] In this step, the steel material that has been through the multi-pass hot rolling step is subjected to stabilizing heat treatment at about 700-800°C for about 1-4 hours, followed by air cooling. During this process, nano-sized fine niobium carbide or niobium-molybdenum carbide is precipitated and uniformly distributed within the matrix.

[0062] If the stabilization heat treatment temperature is less than about 700°C, the amount of niobium carbide or niobium-molybdenum carbide precipitated may be too small. Also, if the stabilization heat treatment temperature exceeds about 800°C, a cellular structure is formed due to the movement of potential within the matrix, and at this time, the niobium carbide or niobium-molybdenum carbide is not distributed homogeneously within the matrix but precipitates along the boundaries of the cellular structure, which weakens the toughness of the stainless steel and can cause cracks.

[0063] In the case of a conventional method for manufacturing stainless steel containing niobium carbide, coarsening of precipitates and non-uniform distribution can occur because stabilization heat treatment is performed at a relatively high temperature range of approximately 900°C. However, according to the method for manufacturing stainless steel according to an embodiment, stabilization heat treatment is performed at approximately 700-800°C, which is the appropriate temperature for forming niobium carbide, so that nano-sized fine niobium carbide can be precipitated and distributed homogeneously within the austenitic matrix structure.

[0064] If the stabilization heat treatment time is less than about 1 hour, the amount of niobium carbide precipitated may be too small, and if it exceeds about 4 hours, the niobium carbide may become coarse and the M formed in the niobium-deficient region may increase. 23 C6 carbides can reduce the corrosion resistance of stainless steel, where M can include elements such as chromium and iron.

[0065] After the stabilization heat treatment, the steel is cooled by water cooling or air cooling rather than quenching so that fine niobium carbide or niobium-molybdenum carbide nuclei can be formed in the matrix by utilizing the difference in solubility of elements in the matrix depending on the temperature, thereby producing an austenitic stainless steel containing nano-sized precipitates that are uniformly distributed with a high number density in the matrix. The present invention will be described in more detail below with reference to examples. However, the following examples are merely examples of the present invention and the present invention is not limited to the following examples. [Example]

[0066] Examples 1 and 10 1) Casting A mixed steel material having the composition shown in Table 1 below is melted and cast using a vacuum induction melting furnace to form a cast ingot. Table 1 below shows the chemical composition values ​​measured by ICP-AES analysis, with each value being in weight percent. [Table 1] 2) Recrystallization stop temperature (T NR )setting To evaluate the high temperature deformation behavior, a Gleeble dynamic mechanical properties tester (Gleeble 3800) is used for high temperature compression testing. The specimen shape is a cylinder with a diameter of 10 mm and a height of 12 mm, which is the standard used in high-temperature compression tests. The Gleeble compression test is performed from 963°C to 1050°C at 12.5°C intervals for 5 seconds. -1 The high-temperature deformation constitutive equation was derived from the true stress-true strain curves obtained in each experiment. To prevent oxidation, the specimens were heated to 1200°C at a heating rate of 10°C / sec in a high-purity argon atmosphere, maintained at this temperature for 10 minutes, and then air-cooled. Two compression tests were performed at the test temperature, with a 20% deformation applied each time. The high-pressure compression test results are shown in Figures 3a and 3b. The recrystallization stop temperature determined through testing is 1013°C. 3) Homogenization heat treatment The cast ingot obtained from step 1) is subjected to a homogenization heat treatment at 1300°C for 1 hour. 4) Multi-pass hot rolling Based on the recrystallization stop temperature of 1013°C obtained in step 2), a total of eight multi-pass rolling steps were performed, resulting in a total reduction of 70%. The hot rolling start temperature was 1235°C, and six passes were performed at temperature intervals of about 40°C up to the recrystallization stop temperature. Similarly, two passes were performed at temperature intervals of about 40°C below the recrystallization stop temperature. [Table 2] 5) Fine niobium carbide or fine niobium-molybdenum carbide precipitation The steel material that has undergone step 4) is subjected to heat treatment at 700°C for 1 hour to form fine niobium carbide (Example 1) or niobium-molybdenum carbide (Example 10), and then air-cooled to produce an austenitic stainless steel containing fine niobium carbide or niobium-molybdenum carbide.

[0067] Examples 2 to 9 Austenitic stainless steels containing fine niobium carbides were manufactured by the same manufacturing process as in Example 1, except that the heat treatment in step 5) was performed at 700°C for 2 hours (Example 2), 700°C for 4 hours (Example 3), 750°C for 1 hour (Example 4), 750°C for 2 hours (Example 5), 750°C for 4 hours (Example 6), 800°C for 1 hour (Example 7), 800°C for 2 hours (Example 8), and 800°C for 4 hours (Example 9).

[0068] Examples 11 to 18 Austenitic stainless steels containing fine niobium-molybdenum carbides were manufactured by the same manufacturing process as in Example 2, except that the heat treatment in step 5) of Example 2 was performed at 700°C for 2 hours (Example 11), 700°C for 4 hours (Example 12), 750°C for 1 hour (Example 13), 750°C for 2 hours (Example 14), 750°C for 4 hours (Example 15), 800°C for 1 hour (Example 16), 800°C for 2 hours (Example 17), and 800°C for 4 hours (Example 18).

[0069] Comparative Examples 1 to 9 Unlike Examples 1 and 10, hot rolling is performed based on the recrystallization stop temperature set after homogenization heat treatment at 1200°C for 1 hour. The hot rolling start temperature is 1120°C, and four passes are performed at temperature intervals of about 27°C up to the recrystallization stop temperature, and two passes are performed at temperature intervals of about 27°C below the recrystallization stop temperature. The hot-rolled steel is then heat-treated according to a temperature and time range to form fine niobium carbides, and air-cooled to prepare an austenitic stainless steel containing fine niobium carbides. The austenitic steels containing fine niobium carbides, Comparative Examples 1 to 9, are stainless steels having similar chemical compositions to those of Examples 1 and 10, except for the manganese and molybdenum contents. The quantitatively analyzed chemical composition values ​​are shown in Table 3 below. Among the heat treatment conditions for preparing the austenitic stainless steel containing fine niobium carbides, the temperature ranges from 700°C to 800°C, which is the same as in the example, and the time ranges from 1 hour to 4 hours.

[0070] Austenitic stainless steels containing fine niobium carbide were manufactured through the same manufacturing process, except that the fine niobium precipitation heat treatment was performed at 700°C for 1 hour (Comparative Example 1), 700°C for 2 hours (Comparative Example 2), 700°C for 4 hours (Comparative Example 3), 750°C for 1 hour (Comparative Example 4), 750°C for 2 hours (Comparative Example 5), 750°C for 4 hours (Comparative Example 6), 800°C for 1 hour (Comparative Example 7), 800°C for 2 hours (Comparative Example 8), and 800°C for 4 hours (Comparative Example 9). A detailed description of the austenitic stainless steel containing niobium carbide of Comparative Example 1 is given in Korean Patent No. 1,943,591 invented by the inventors of the present application. [Table 3]

[0071] Experimental Example Transmission electron microscope microstructure photographs of the austenitic stainless steel containing fine niobium carbides according to Example 5 are shown in Figures 4a to 4c, transmission electron microscope microstructure photographs of the austenitic stainless steel containing fine niobium-molybdenum carbides according to Example 15 are shown in Figures 5a to 5c, and transmission electron microscope microstructure photographs of the austenitic stainless steel containing fine niobium carbides according to Comparative Example 8 are shown in Figure 6. In addition, the average size and density of precipitates according to the heat treatment conditions of the austenitic stainless steels containing fine niobium carbides or fine niobium-molybdenum according to Examples 5, 15, and Comparative Example 8, as well as Examples 1 to 18 and Comparative Examples 1 to 9, were measured, and the results are shown in Figures 7a and 7b.

[0072] 4a to 5c and 7a and 7b, it can be seen that the stainless steels of Examples 5 and 15 are distributed relatively homogeneously or uniformly within the matrix. At this time, the number density, density, and average diameter of fine niobium carbides are 1.67×10, respectively. 15 # / m 2 , 6.87×10 22 # / m 3 , 7.7 nm, and the number density, density, and average diameter of the fine niobium-molybdenum carbides are 2.45 × 10 15 # / m 2 , 1.21×10 23 # / m 3 , 5.9 nm.

[0073] On the other hand, in the case of the stainless steels according to Comparative Examples 1 to 9, the niobium carbide is distributed relatively homogeneously or uniformly within the matrix structure, but the density of the niobium carbide or niobium-molybdenum carbide is relatively low. The number density, density, and average size of the stainless steel according to Comparative Example 8 are 5.12 × 10, respectively. 14 # / m 2 , 1.13×10 22 # / m 3 , 9.4 nm.

[0074] Referring again to FIGS. 7a and 7b, the average diameter of the nano-sized niobium carbide precipitates according to the embodiment ranges from 5.2 nm to 10.8 nm, which is similar to or relatively smaller than that of the comparative example depending on the heat treatment conditions. The density is 0.07×10 22 # / m 3 to 13.48 x 10 22 # / m 3 It can be seen that the average density of the nano-sized niobium carbide precipitates in Examples 1 to 9 was increased by up to about 14 times compared to the comparative example.

[0075] In the case of Comparative Examples 1 to 9, although they had similar chemical compositions and were subjected to the same thermo-mechanical processes as the Examples, they contained relatively less manganese than the Examples or did not contain molybdenum, so the size of the carbides during the carbide formation process in the matrix structure was relatively coarser than in the Examples, and as a result, the density of the carbides was relatively lower than in the Examples.

[0076] On the other hand, the austenitic stainless steel according to the embodiments contains a relatively higher amount of manganese or molybdenum than the comparative examples, which promotes the homogeneous precipitation and distribution of nano-sized fine niobium carbides or niobium-molybdenum carbides within the austenitic matrix structure, forming carbides with a relatively higher density than the comparative examples and exhibiting relatively high temperature stability. As a result, the mechanical behavior of the stainless steel is superior to that of the comparative examples, and while having a high strength to specific gravity, the neutron irradiation resistance is significantly improved compared to the comparative examples, and the creep resistance is also improved compared to the comparative examples.

[0077] The manufacturing method for austenitic stainless steel can be applied to carbides of vanadium, titanium, tantalum, and hafnium, as well as niobium carbide, or nitrides thereof, as long as the precipitates are formed at the melting temperature of the base material.

[0078] Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concept of the present invention defined in the following claims also fall within the scope of the present invention.

Claims

1. The alloy has an austenitic matrix structure and is composed of 16-26 wt% chromium (Cr), 8-22 wt% nickel (Ni), 0.02-0.1 wt% carbon (C), 0.2-1 wt% niobium (Nb), 2-3.5 wt% manganese (Mn), and the balance being iron (Fe) and unavoidable impurities; Nano-sized niobium carbide (NbC) is precipitated in the austenitic matrix structure, and the nano-sized niobium carbides are dispersed in the austenitic matrix structure, The number density of the nano-sized niobium carbides in the austenitic matrix structure is 1×10 14 -5×10 15 / m 2 ; Austenitic stainless steel.

2. 16-26 wt% chromium (Cr), 8-22 wt% nickel (Ni), 0.02-0.1 wt% carbon (C), 0.2-1 wt% niobium (Nb), 2-3.5 wt% manganese (Mn), 0.5-1.5 wt% molybdenum (Mo), and the balance being iron (Fe) and unavoidable impurities; It has an austenitic matrix structure, Nano-sized niobium carbide (NbC) is precipitated in the austenitic matrix structure, and the nano-sized niobium carbides are dispersed in the austenitic matrix structure, In the austenitic matrix structure, the number density of the nano-sized niobium carbides is 1×10 14 -5×10 15 / m 2; Austenitic stainless steel.

3. 3. The austenitic stainless steel according to claim 2, wherein nano-sized niobium-molybdenum carbides are precipitated in the austenitic matrix structure, and the nano-sized niobium-molybdenum carbides are dispersed in the austenitic matrix structure.

4. 16-26 wt% chromium (Cr), 8-22 wt% nickel (Ni), 0.02-0.1 wt% carbon (C), 0.2-1 wt% niobium (Nb), 2-3.5 wt% manganese (Mn), 0.5-1.5 wt% molybdenum (Mo), more than 0 wt% and 0.3 wt% or less silicon (Si), and the balance being iron (Fe) and unavoidable impurities; It has an austenitic matrix structure, Nano-sized niobium carbide (NbC) is precipitated in the austenitic matrix structure, and the nano-sized niobium carbides are dispersed in the austenitic matrix structure, The number density of the nano-sized niobium carbides in the austenitic matrix structure is 1×10 14 -5×10 15 / m 2 , nano-sized niobium-molybdenum carbides are precipitated in the austenitic matrix structure, the nano-sized niobium-molybdenum carbides are dispersed in the austenitic matrix structure; Austenitic stainless steel.

5. 4. The austenitic stainless steel according to claim 3, wherein the average size of the nano-sized niobium-molybdenum carbides is 6 nm or less.

6. In the austenitic matrix structure, the number density of the nano-sized niobium-molybdenum carbides is 5×10 １４ -5 x 10 １５ / m ２ 4. The austenitic stainless steel according to claim 3, wherein

7. In the austenitic matrix structure, the number density of the nano-sized niobium-molybdenum carbide is 1×10 ２２ -5 x 10 ２３ / m ３ 4. The austenitic stainless steel according to claim 3, wherein

8. 2. The austenitic stainless steel of claim 1, wherein the nanosized niobium carbides have an average size of 11 nm or less.

9. In the austenitic matrix structure, the number density of the nano-sized niobium carbides is 1×10 ２２ -1 x 10 ２３ / m ３ 2. The austenitic stainless steel according to claim 1, wherein

10. 2. The austenitic stainless steel according to claim 1, wherein the unavoidable impurities include more than 0 wt. % and not more than 0.01 wt. % phosphorus (P) and more than 0 wt. % and not more than 0.01 wt. % sulfur (S).

11. a melting and casting step of melting a mixed steel material consisting of 16-26 wt% chromium (Cr), 8-22 wt% nickel (Ni), 0.02-0.1 wt% carbon (C), 0.2-1 wt% niobium (Nb), 2-3.5 wt% manganese (Mn), and the balance being iron (Fe) and unavoidable impurities, and casting the melted mixed steel material to form a cast steel material having an austenitic matrix structure; Evaluating the high-temperature deformation behavior of the cast steel material to derive a recrystallization stop temperature; subjecting the cast steel material to a homogenization heat treatment; A multi-pass hot rolling step in which one or more passes of hot rolling are performed in the recrystallized region, and then one or more passes of hot rolling are performed in the non-recrystallized region; and The hot-rolled cast steel is heat-treated at a temperature of 700°C to 800°C for 1 to 4 hours, followed by air cooling, thereby precipitating nano-sized niobium carbides in the austenitic matrix structure. Including, the nano-sized niobium carbides are dispersed in the austenitic matrix structure, The number density of the nano-sized niobium carbides in the austenitic matrix structure is 1×10 14 -5×10 15 / m 2 ; A method for producing austenitic stainless steel.

12. a melting and casting step of melting a mixed steel material consisting of 16-26 wt% chromium (Cr), 8-22 wt% nickel (Ni), 0.02-0.1 wt% carbon (C), 0.2-1 wt% niobium (Nb), 2-3.5 wt% manganese (Mn), 0.5-1.5 wt% molybdenum (Mo), and the balance being iron (Fe) and unavoidable impurities, and casting the melted mixed steel material to form a cast steel material having an austenitic matrix structure; Evaluating the high-temperature deformation behavior of the cast steel material to derive a recrystallization stop temperature; subjecting the cast steel material to a homogenization heat treatment; a multi-pass hot rolling step in which one or more passes of hot rolling are performed in the recrystallized region, and then one or more passes of hot rolling are performed in the non-recrystallized region; and The hot-rolled cast steel is heat-treated at a temperature of 700°C to 800°C for 1 to 4 hours, followed by air cooling, thereby precipitating nano-sized niobium carbides in the austenitic matrix structure. Including, the nano-sized niobium carbides are dispersed in the austenitic matrix structure, In the austenitic matrix structure, the number density of the nano-sized niobium carbides is 1×10 14 -5×10 15 / m 2; A method for producing austenitic stainless steel.

13. 13. The method for producing austenitic stainless steel according to claim 12, wherein the hot-rolled cast steel is heat-treated at a temperature of 700°C to 800°C for 1 to 4 hours, followed by air-cooling, whereby nanosized niobium-molybdenum carbides are precipitated in the austenitic matrix structure, and the nanosized niobium-molybdenum carbides are dispersed in the austenitic matrix structure.

14. a melting and casting step of melting a mixed steel material consisting of 16-26 wt% chromium (Cr), 8-22 wt% nickel (Ni), 0.02-0.1 wt% carbon (C), 0.2-1 wt% niobium (Nb), 2-3.5 wt% manganese (Mn), 0.5-1.5 wt% molybdenum (Mo), more than 0 wt% and 0.3 wt% or less silicon (Si), and the balance being iron (Fe) and unavoidable impurities, and casting the melted mixed steel material to form a cast steel material having an austenitic matrix structure; Evaluating the high-temperature deformation behavior of the cast steel material to derive a recrystallization stop temperature; subjecting the cast steel material to a homogenization heat treatment; A multi-pass hot rolling step in which one or more passes of hot rolling are performed in the recrystallized region, and then one or more passes of hot rolling are performed in the non-recrystallized region; and The hot-rolled cast steel is heat-treated at a temperature of 700°C to 800°C for 1 to 4 hours, followed by air cooling, thereby precipitating nano-sized niobium carbides in the austenitic matrix structure. Including, the nano-sized niobium carbides are dispersed in the austenitic matrix structure, The number density of the nano-sized niobium carbides in the austenitic matrix structure is 1×10 14 -5×10 15 / m 2 , The hot-rolled cast steel material is heat-treated at a temperature of 700°C to 800°C for 1 to 4 hours, and then air-cooled, whereby nano-sized niobium-molybdenum carbides are precipitated in the austenitic matrix structure, the nano-sized niobium-molybdenum carbides are dispersed in the austenitic matrix structure; A method for producing austenitic stainless steel.

15. The method for producing austenitic stainless steel according to claim 11, wherein 5 to 15 passes of hot rolling are performed in the multi-pass hot rolling step.

16. 12. The method for producing an austenitic stainless steel according to claim 11, wherein 3 to 10 passes of hot rolling are performed in the recrystallized region, and then 2 to 5 passes of hot rolling are performed in the non-recrystallized region.

17. The method for producing an austenitic stainless steel according to claim 16, wherein the temperature at which each pass is performed is reduced by 10-50°C during successive hot rolling passes.

18. 12. The method for producing austenitic stainless steel according to claim 11, wherein the step of homogenizing the cast steel material is performed at a temperature range of 1200-1300°C for 30 minutes to 2 hours.

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