WO2023093464A1 - High-entropy austenitic stainless steel, and preparation method therefor - Google Patents

High-entropy austenitic stainless steel, and preparation method therefor Download PDF

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WO2023093464A1
WO2023093464A1 PCT/CN2022/128626 CN2022128626W WO2023093464A1 WO 2023093464 A1 WO2023093464 A1 WO 2023093464A1 CN 2022128626 W CN2022128626 W CN 2022128626W WO 2023093464 A1 WO2023093464 A1 WO 2023093464A1
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stainless steel
entropy
austenitic stainless
ingot
preparation
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French (fr)
Chinese (zh)
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沈同德
温康康
孙宝茹
蔡学成
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燕山大学
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Priority to JP2023563148A priority Critical patent/JP2024504210A/en
Priority to EP22897547.0A priority patent/EP4257717A1/en
Priority to US18/271,916 priority patent/US20240093339A1/en
Publication of WO2023093464A1 publication Critical patent/WO2023093464A1/en

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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B21B3/02—Rolling special iron alloys, e.g. stainless steel
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/56—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
    • C21D1/60—Aqueous agents
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/76—Adjusting the composition of the atmosphere
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/021—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular fabrication or treatment of ingot or slab
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0273—Final recrystallisation annealing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite

Definitions

  • the invention belongs to the field of materials, in particular to the technical field of stainless steel materials, in particular to a high-entropy austenitic stainless steel and a preparation method thereof.
  • Stainless steel is widely used in many industrial fields such as aviation, aerospace, ocean and nuclear industry because of its good corrosion resistance and oxidation resistance.
  • austenitic stainless steel has good plasticity but low strength
  • ferritic stainless steel and martensitic stainless steel have slightly higher strength but general plasticity
  • precipitation hardening stainless steel has the highest strength among stainless steel species, but the lowest plasticity.
  • the austenitic stainless steel commonly used in the market is 201, 301, 304, 316 and other stainless steels with low strength and good plasticity and their derived materials.
  • the mass ratio of chemical elements is: C ⁇ 0.15%, Si ⁇ 2.0 %, Mn ⁇ 2.0% (in 201, 202: 5.0% ⁇ Mn ⁇ 10.5%, each component is different), P ⁇ 0.045%, S ⁇ 0.03%, N ⁇ 0.025%, 15.0% ⁇ Cr ⁇ 28.0%, 3.5% ⁇ Ni ⁇ 36.0 (Cr, Ni content is related to each system), others are trace doping elements such as Cu, Nb, W, Ta, B and Al, iron and other unavoidable impurities.
  • High-entropy alloys contain at least five main elements, each in an amount of 5-35 at%.
  • High-entropy alloys have excellent properties that are difficult for conventional alloys, such as high hardness, high strength, oxidation resistance, corrosion resistance, fatigue resistance, high temperature softening resistance, creep resistance, wear resistance, unique magnetic properties, and excellent low-temperature mechanical properties.
  • CTLiu et al. introduced a design scheme for strengthening FeCoNiTiAl high-entropy alloys by using L1 2 -Ni 3 (TiAl) precipitates. By introducing L1 2 -Ni 3 (TiAl) precipitates into the multi-principal alloy matrix, the material strength is greatly improved. , and there is almost no loss of tensile plasticity [Science, 2018, 362, 933-937].
  • the strength is improved by introducing high-density nano-precipitated phases, and during tensile deformation, dislocations will shear through the precipitated phases, so that stress concentration occurs on the grain boundaries, thereby maintaining its high plasticity. Therefore, the introduction of fine and high-density nano-precipitated phases in the matrix alloy plays a very important role in the strengthening and toughening of structural materials.
  • the high-entropy alloy contains the expensive strategic metal cobalt, which is difficult to apply in large quantities.
  • composition ratio of the high-entropy austenitic stainless steel in the present invention is mainly designed based on the following ideas:
  • Ni element can broaden the phase region formed by nano-precipitated phases and inhibit the formation of other harmful intermetallic compounds to avoid brittleness.
  • Ti element can refine the grain and uniform structure, and at the same time form nano-precipitated phases with Ni and Al to improve the strength of stainless steel, and Ti can replace expensive Cu, Co, Nb, Mo to reduce production costs and reduce production costs. Destroy the microstructure of the nano-precipitated phase.
  • the alloy preparation is inconvenient and causes a lot of waste; the existence of Cu may cause segregation of the material and bring inhomogeneity to the structure. Therefore, the alloy in the present invention needs to remove these two elements.
  • the change rule of the content of each element in the alloy is: the content of Ti and Al is determined by the content of the other three elements.
  • the content of Cr and Ni is higher than that of Ti and Al, it is necessary to reduce the content of Ti and Al in an appropriate amount; when When the content of Cr and Ni is lower than that of Ti and Al, it is necessary to increase the content of Ti and Al appropriately.
  • the content of Cr element increases, the content of Ni element needs to be increased at the same time. On the one hand, it can ensure that the matrix is an austenite structure, and on the other hand, it can ensure that there are enough Ni atoms to form nano-precipitated phases.
  • the object of the present invention is to provide a high-strength, high-plastic high-entropy austenitic stainless steel and a preparation method thereof.
  • the technical means used in the present invention are as follows:
  • a high-entropy austenitic stainless steel characterized in that, by atomic percentage, the elemental components of the stainless steel are as follows:
  • the elemental composition of the stainless steel is as follows:
  • the size of the nano-precipitated phase in the stainless steel is ⁇ 30 nm, and the number density of the nano-precipitated phase is ⁇ 5.0 ⁇ 10 21 m -3 .
  • a method for preparing high-entropy austenitic stainless steel the specific steps are: mixing various raw materials according to the requirements of atomic ratio, melting and pouring in a vacuum argon arc furnace to obtain ingots, solid solution treating the ingots, and (1) cooling After rolling and recrystallization or after (2) hot rolling, cold rolling and recrystallization, aging treatment is carried out to obtain high-entropy austenitic stainless steel.
  • the cold rolling process in (1) is as follows: the reduction in each pass is no more than 0.2 mm, and the total reduction is 60% to 70%.
  • the process of hot rolling and cold rolling in (2) is as follows: hot rolling at 800°C-1150°C, the reduction in each pass is not more than 0.5mm, and the guaranteed temperature during the hot rolling process is 800-1150°C In the range, if the temperature drops, it can be returned to the furnace and kept in the rolling temperature range for 5 to 15 minutes. After the total reduction reaches 50% to 60%, it will be replaced with a cold rolling process. The reduction of each pass of cold rolling should not exceed 0.2mm. The total down pressure is 60% to 70%.
  • the specific operation of the recrystallization is: heat the rolled ingot in (1) or (2) at 1140°C-1160°C for 1-3 minutes; (if the ingot volume is too large, increase recrystallization time);
  • the heating rate of the recrystallization is 10°C/min-20°C/min.
  • the argon arc furnace is filled with argon below 5.0 ⁇ 10 -3 Pa so that the pressure in the furnace reaches 5.0 ⁇ 10 3 Pa, and the oxygen content and nitrogen content in the furnace are within 180 minutes. Melting starts when it is lower than 0.002%;
  • the mass of pure Ti is 30-40g, which is neither used as raw material nor involved in smelting;
  • the vacuum argon arc furnace is smelted at least four times.
  • the specific operation of the solution treatment is: heating the cast ingot below 1.0 ⁇ 10 -3 Pa to 1140°C-1160°C, keeping it warm for 1h-2.5h, and then water quenching or cooling in air;
  • the heating rate of the solution treatment is 10°C/min ⁇ 20°C/min.
  • the specific operation of the aging treatment is: heat the recrystallized ingot at 500°C-600°C for 0.5h-1.5h, then water quench or air cool;
  • the heating rate of the aging treatment is 5°C/min ⁇ 15°C/min.
  • the present invention provides a high-entropy austenitic stainless steel, in terms of atomic percentage content, the atomic ratio of each element is Cr: 5-30%; Ni: 5-50%; Ti: 1-15%; Al: 1-15%; the rest is Fe and other impurity elements (C, N, O, etc.)
  • the stainless steel composition system is simple, reducing some precious metals and trace doping elements, reducing the addition of alloying elements to the greatest extent, and only using five alloying elements (three main elements: Fe, Cr, Ni, two small elements: Ti , Al), by adjusting the atomic ratio of each component, the maximum amount of nano-precipitated phases can be precipitated, so that the prepared high-entropy austenitic stainless steel has both high strength and high plasticity.
  • the strength and corrosion resistance of stainless steel can be improved by adding Cr; the addition of Ni can be used to widen the phase region formed by nano-precipitated phases and inhibit the generation of harmful intermetallic compounds; the addition of Al can endow the material with oxidation resistance and corrosion resistance, and has Contribute to the formation of nano-precipitated phases; adding Ti elements to refine grains and uniform structure, and form nano-precipitated phases with Ni and Al to improve the strength of stainless steel, while Ti replaces expensive Cu, Co, Nb, Mo to reduce production costs and Does not destroy the microstructure of the nano-precipitated phase.
  • the stainless steel uses Fe ⁇ Cr ⁇ Ni as the matrix.
  • Cr 5-19%; Ni: 5-29%; Ti: 6-15%; Al: 5-15%, and the balance is iron.
  • the amount of Cr and Ni is reduced, further reducing the production cost.
  • the present invention also provides a preparation process of a high-strength, high-plasticity high-entropy austenitic stainless steel, which simplifies the heat treatment process, reduces production costs, has a simple preparation process, and has broad application prospects.
  • the solid solution treatment method in the present invention can fully dissolve the alloy elements into the austenite matrix, making the alloy composition more uniform, adopting high-temperature and short-time recrystallization treatment, and obtaining uniform and relatively coarse equiaxed crystals to ensure that the alloy is good At the same time of plasticity, it can greatly improve production efficiency and save costs.
  • the rolling process of cold rolling after hot rolling is adopted, which helps to solve the problem of difficult rolling of large ingots.
  • Hot rolling can eliminate the cracks caused by rolling at the initial stage, and make a good job for subsequent cold rolling. Prepare and reduce risk.
  • Subsequent aging treatment will help the precipitation of nano-precipitation strengthening phase, thereby improving the strength and plasticity of stainless steel. Due to its good combination of strength and plasticity, the stainless steel prepared by the preparation method of the present invention has better mechanical properties than most commercial stainless steels, and is suitable for most stainless steel service fields.
  • Figure 1 is the X-ray diffraction pattern of high-entropy austenitic stainless steel Fe 47 Cr 16 Ni 26 Ti 6 Al 5 ;
  • Figure 2 is the transmission electron microscope image and element distribution map of high-entropy austenitic stainless steel Fe 47 Cr 16 Ni 26 Ti 6 Al 5 ;
  • Fig. 3 is the engineering stress-strain curve figure measured at room temperature of high entropy austenitic stainless steel
  • Fig. 4 is the comparative figure of yield strength R eL and elongation at break E of commercial stainless steel performance under the prior art and high entropy austenitic stainless steel mechanical performance of the present invention
  • Fig. 5 is the comparative figure of the tensile strength Rm and elongation at break E of commercial stainless steel performance under the prior art and high entropy austenitic stainless steel mechanical performance of the present invention
  • Fig. 6 is a comparison chart of the yield strength and the strength-plastic product (tensile strength ⁇ elongation at break) of the commercial stainless steel performance under the prior art and the mechanical performance of the high-entropy austenitic stainless steel of the present invention.
  • This embodiment provides a high-entropy austenitic stainless steel, its chemical composition is: Fe 47 Cr 16 Ni 26 Ti 6 Al 5 (atomic ratio) or Fe 48.56 Cr 15.39 Ni 28.24 Ti 5.32 Al 2.5 (weight ratio), smelting
  • impurity elements C, N, O, etc.
  • the diffraction pattern is shown in Figure 1.
  • the diffraction peaks in the figure can be marked as (111), (200), (220), (311), (222) of the face-centered structure Diffraction peaks, so the resulting structure is austenite, because the size of the nano-precipitated phase is too small, no visible diffraction peaks are displayed on the X-ray diffraction pattern.
  • This embodiment provides a high-entropy austenitic stainless steel whose chemical composition is: Fe 47 Cr 16 Ni 26 Ti 6 Al 5 (atomic ratio) or Fe 48.56 Cr 15.39 Ni 28.24 Ti 5.32 Al 2.5 (weight ratio), wherein smelting
  • the impurity elements (C, N, O, etc.) introduced into the process and heat treatment process with a very small content can be ignored and have negligible impact on the material properties.
  • the ingot after solid solution treatment is deformed by cold rolling after hot rolling.
  • the rolling process is as follows: the hot rolling temperature is 1150 °C, and the temperature during the hot rolling process is guaranteed to be within the range of 800 to 1150 °C. If the temperature is lowered, it can be Return to the furnace and keep warm for 5 to 15 minutes in the rolling temperature range.
  • the reduction in each pass shall not exceed 0.5mm. After the total reduction reaches 50%, it shall be replaced with a cold rolling process. The reduction in each pass shall not exceed 0.2mm.
  • the pressure is 66.7%.
  • the rolled ingot was heated up to 1140°C at a rate of 15°C/min, and held for 1.5min to complete recrystallization.
  • the recrystallized ingot was heated to 550°C at a rate of 15°C/min and kept for 1.5 hours, then cooled in air to complete the aging treatment.
  • the material was characterized by a transmission electron microscope.
  • the transmission electron microscope image and element distribution diagram are shown in Figure 2.
  • the composition is Ni-Ti-Al
  • the crystal structure is face-centered cubic.
  • the size is 14.4nm (diameter), and the number density is 1.68 ⁇ 10 22 m -3 .
  • This embodiment provides a high-entropy austenitic stainless steel whose chemical composition is: Fe 39 Cr 20 Ni 30 Ti 6 Al 5 (atomic ratio) or Fe 40.33 Cr 19.25 Ni 32.6 Ti 5.32 Al 2.5 (weight ratio), wherein The impurity elements (C, N, O, etc.) introduced into the process and heat treatment process with a very small content can be ignored and have negligible impact on the material properties.
  • An embodiment of the present invention provides a high-entropy austenitic stainless steel, the chemical composition of which is: Fe 31 Cr 24 Ni 34 Ti 6 Al 5 (atomic ratio) or Fe 32.08 Cr 23.12 Ni 36.98 Ti 5.32 Al 2.5 (weight ratio), wherein The impurity elements (C, N, O, etc.) introduced into the smelting process and heat treatment process with very small content can be neglected and have negligible impact on the material properties.
  • the embodiment of the present invention provides a high-entropy austenitic stainless steel, its chemical composition is: Fe 42 Cr 16 Ni 28 Ti 7 Al 7 (atomic ratio) or Fe 43.88 Cr 15.56 Ni 30.75 Ti 6.27 Al 3.53 (weight ratio), wherein
  • the impurity elements (C, N, O, etc.) introduced into the smelting process and heat treatment process with very small content can be neglected and have negligible impact on the material properties.
  • An embodiment of the present invention provides a high-entropy austenitic stainless steel, the chemical composition of which is: Fe 49 Cr 16 Ni 28 Ti 4 Al 3 (atomic ratio) or Fe 49.9 Cr 15.17 Ni 29.98 Ti 3.49 Al 1.48 (weight ratio), wherein The impurity elements (C, N, O, etc.) introduced into the smelting process and heat treatment process with very small content can be neglected and have negligible impact on the material properties.
  • Example 1-6 The materials prepared in Examples 1-6 were randomly sampled and analyzed, and the statistical analysis results of yield strength ReL , tensile strength Rm , elongation at break E, and yield strength ratio ( ReL / Rm ) are shown in Table 1. Among them, each sample in the table was tested three times, and random sampling was adopted.
  • Fig. 3 shows the engineering stress-strain curve of high-entropy austenitic stainless steel measured at room temperature, and the strain rate used is 1 ⁇ 10 -3 s -1 .
  • the yield strength, tensile strength and elongation at break of high-entropy austenitic stainless steel are shown in Table 1. The elongation was 37%.
  • Fig. 4 is the comparison of the yield strength R eL and the elongation at break E of commercial stainless steel properties under the prior art and the mechanical properties of the high-entropy austenitic stainless steel of the present invention, and this figure shows that the high-entropy austenitic stainless steel of the present invention
  • the yield strength is higher than that of most commercial stainless steels and maintains high plasticity.
  • the product of yield strength and elongation at break is 14.5-30.3GPa%, which is higher than 2.62-17.2GPa% of commercial stainless steels.
  • Fig. 5 is the contrast of tensile strength R m and elongation at break E of commercial stainless steel properties under the prior art and high-entropy austenitic stainless steel mechanical properties of the present invention, and this figure shows, high-entropy austenitic stainless steel of the present invention While maintaining high plasticity, it also has high tensile strength.
  • the product of tensile strength and elongation at break is 18.0-46.1GPa%, which is higher than 2.9-42.8GPa% of commercial stainless steel.
  • Fig. 6 is the comparison of the yield strength and the strong-plastic product (tensile strength ⁇ elongation at break) of the commercial stainless steel properties under the prior art and the high-entropy austenitic stainless steel mechanical properties of the present invention, and this figure shows that the present invention has high
  • the yield strength and strength-plastic product of the entropic austenitic stainless steel are higher than those of the stainless steel of the prior art, while maintaining high plasticity while having high strength, the comprehensive performance is better than that of the stainless steel of the prior art.

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Abstract

Disclosed in the present invention are a high-entropy austenitic stainless steel, and a preparation method therefor, which belong to the technical field of stainless steel materials in the material field. The stainless steel developed in the present invention comprises the following elementary components in atomic percentages: 5-30% of Cr, 5-50% of Ni, 1-15% of Ti, 1-15% of Al, and the balance of Fe and inevitable impurities, preferably, 5-19% of Cr, 5-29% of Ni, 6-15% of Ti, 5-15% of Al, and the balance of Fe. By means of regulating and controlling the atomic ratio of each element, the precipitation of a nanometer precipitated phase is maximized to the greatest possible extent, and the strength is also improved to the maximum extent while a high plasticity is maintained. The stainless steel provided in the present invention has a simple component system, a low manufacturing cost, high strength and high plasticity, can be widely applied to various industrial fields such as aviation, spaceflight, oceanography and nuclear power, and has wide market prospects.

Description

一种高熵奥氏体不锈钢及其制备方法A kind of high entropy austenitic stainless steel and preparation method thereof 技术领域technical field
本发明属于材料领域，具体涉及不锈钢材料技术领域，尤其涉及一种高熵奥氏体不锈钢及其制备方法。The invention belongs to the field of materials, in particular to the technical field of stainless steel materials, in particular to a high-entropy austenitic stainless steel and a preparation method thereof.
背景技术Background technique
不锈钢因其良好的耐腐蚀和抗氧化性被广泛应用于航空、航天、海洋、核工业许多工业领域，但是，目前所有的商用不锈钢都很难兼具优异的强度与高塑性。比如，奥氏体不锈钢其塑性好而强度太低，铁素体不锈钢和马氏体不锈钢其强度稍高而塑性又一般，沉淀硬化不锈钢在不锈钢种里具有最高的强度，但是塑性最低。目前，市场上普遍使用的奥氏体不锈钢是201、301、304、316等强度低而塑性好的不锈钢及其衍生出的材料，其化学元素质量配比为：C≤0.15％、Si≤2.0％、Mn≤2.0％(201,202中：5.0％≤Mn≤10.5％，各个成分不同)、P≤0.045％、S≤0.03％、N≤0.025％、15.0％≤Cr≤28.0％、3.5％≤Ni≤36.0(Cr、Ni含量与各个体系有关)，其他为Cu、Nb、W、Ta、B和Al等微量掺杂元素以及铁和其他不可避免的杂质。Stainless steel is widely used in many industrial fields such as aviation, aerospace, ocean and nuclear industry because of its good corrosion resistance and oxidation resistance. However, it is difficult for all commercial stainless steels to have both excellent strength and high plasticity. For example, austenitic stainless steel has good plasticity but low strength, ferritic stainless steel and martensitic stainless steel have slightly higher strength but general plasticity, and precipitation hardening stainless steel has the highest strength among stainless steel species, but the lowest plasticity. At present, the austenitic stainless steel commonly used in the market is 201, 301, 304, 316 and other stainless steels with low strength and good plasticity and their derived materials. The mass ratio of chemical elements is: C≤0.15%, Si≤2.0 %, Mn≤2.0% (in 201, 202: 5.0%≤Mn≤10.5%, each component is different), P≤0.045%, S≤0.03%, N≤0.025%, 15.0%≤Cr≤28.0%, 3.5%≤Ni ≤36.0 (Cr, Ni content is related to each system), others are trace doping elements such as Cu, Nb, W, Ta, B and Al, iron and other unavoidable impurities.
近年来，研究人员利用大塑性变形手段，代表技术为液氮冷轧、机械合金化、高压扭转和挤压等，通过马氏体反转为奥氏体的强化方法，使材料晶粒尺寸细化至纳米级，有效提高了材料的强度，晶粒细化对于强化强度作用明显，但使材料的塑韧性损失极大。在材料科学领域，近年来兴起了一种全新的金属材料，称之为高熵合金或者多主元合金。高熵合金包含至少五种主要元素，每种元素含量介于5-35at％。高熵合金具有常规合金难以企及的优异性能，比如高硬度、高强度、抗氧化、抗腐蚀、抗疲劳、抗高温软化、抗蠕变、抗磨损、独特的磁性和优异的低温力学性能等。C.T.Liu等人介绍了一种利用L1 2-Ni 3(TiAl)析出相强化FeCoNiTiAl高熵合金的设计方案，通过在多主元合金基体中引入L1 2-Ni 3(TiAl)析出相大幅提升材料强度，且拉伸塑性几乎没有损失[Science,2018,362，933～937]。该方法中通过引入高密度的纳米析出相来提升强度，而在拉伸变形过程中，位错会剪切过析出相，使得应力集中发生在晶界上，从而保持其高塑性。因此，基体合金中引入细小且高密度的纳米析出相在实现结构材料的强韧化中起了十分重要的作用。但是，该高熵合金含有昂贵的战略金属钴，难以大批量应用。因此开发一种新型的、不含元素钴的高熵奥氏体不锈钢来填补现有商用奥氏体钢中强度和塑性难以兼顾的技术瓶颈，达到远超现有奥氏体不锈钢的强度塑性匹配是极其必要的。 In recent years, researchers have used large plastic deformation methods, representative technologies are liquid nitrogen cold rolling, mechanical alloying, high-pressure torsion and extrusion, etc., through the strengthening method of martensite inversion to austenite, so that the material grain size is fine Refinement to the nanometer level effectively improves the strength of the material, and the grain refinement has a significant effect on strengthening the strength, but the plasticity and toughness of the material are greatly lost. In the field of material science, a new kind of metal material has emerged in recent years, called high-entropy alloys or multi-principal alloys. High-entropy alloys contain at least five main elements, each in an amount of 5-35 at%. High-entropy alloys have excellent properties that are difficult for conventional alloys, such as high hardness, high strength, oxidation resistance, corrosion resistance, fatigue resistance, high temperature softening resistance, creep resistance, wear resistance, unique magnetic properties, and excellent low-temperature mechanical properties. CTLiu et al. introduced a design scheme for strengthening FeCoNiTiAl high-entropy alloys by using L1 2 -Ni 3 (TiAl) precipitates. By introducing L1 2 -Ni 3 (TiAl) precipitates into the multi-principal alloy matrix, the material strength is greatly improved. , and there is almost no loss of tensile plasticity [Science, 2018, 362, 933-937]. In this method, the strength is improved by introducing high-density nano-precipitated phases, and during tensile deformation, dislocations will shear through the precipitated phases, so that stress concentration occurs on the grain boundaries, thereby maintaining its high plasticity. Therefore, the introduction of fine and high-density nano-precipitated phases in the matrix alloy plays a very important role in the strengthening and toughening of structural materials. However, the high-entropy alloy contains the expensive strategic metal cobalt, which is difficult to apply in large quantities. Therefore, a new type of high-entropy austenitic stainless steel that does not contain elemental cobalt is developed to fill the technical bottleneck of the existing commercial austenitic steel that is difficult to balance the strength and plasticity, and achieve a strength-plastic matching that far exceeds that of the existing austenitic stainless steel. is extremely necessary.
发明内容Contents of the invention
本发明中高熵奥氏体不锈钢的成分配比主要是基于以下思想进行设计：The composition ratio of the high-entropy austenitic stainless steel in the present invention is mainly designed based on the following ideas:
(1)Cr元素的添加可以在提高不锈钢强度的同时保证其耐腐蚀性，高Cr含量有助于适应在核材料服役环境(超临界水、铅铋溶液等)中的应用。(1) The addition of Cr element can improve the strength of stainless steel while ensuring its corrosion resistance. High Cr content helps to adapt to the application in the service environment of nuclear materials (supercritical water, lead-bismuth solution, etc.).
(2)Ni元素的添加可以加宽纳米析出相形成的相区，并抑制其他有害的金属间化合物的形成以避免带来脆性。(2) The addition of Ni element can broaden the phase region formed by nano-precipitated phases and inhibit the formation of other harmful intermetallic compounds to avoid brittleness.
(3)Al元素的适量添加可以赋予合金抗氧化性和抗腐蚀性，同时促进纳米析出相的析出，使纳米析出相与基体保持高共格度。(3) The addition of an appropriate amount of Al element can endow the alloy with oxidation resistance and corrosion resistance, and at the same time promote the precipitation of nano-precipitates, so that the nano-precipitates and the matrix maintain a high degree of coherence.
(4)Ti元素的适量加入可以细化晶粒和均匀组织，同时与Ni、Al形成纳米析出相提升不锈钢的强度，并且Ti替代昂贵的Cu、Co、Nb、Mo降低生产成本的同时也不破坏纳米析出相的微观结构。(4) Adding an appropriate amount of Ti element can refine the grain and uniform structure, and at the same time form nano-precipitated phases with Ni and Al to improve the strength of stainless steel, and Ti can replace expensive Cu, Co, Nb, Mo to reduce production costs and reduce production costs. Destroy the microstructure of the nano-precipitated phase.
(5)由于Mn在冶炼过程中存在挥发问题给合金制备带来不便，且造成较大的浪费；Cu的存在可能会使材料出现偏析，给组织带来不均匀性。因此，本发明中的合金需去除这两种元素。(5) Due to the volatilization of Mn during the smelting process, the alloy preparation is inconvenient and causes a lot of waste; the existence of Cu may cause segregation of the material and bring inhomogeneity to the structure. Therefore, the alloy in the present invention needs to remove these two elements.
(6)合金中各元素含量变化规则为：Ti、Al的含量由其他三种元素的含量决定，当Cr、Ni的含量高于Ti、Al的含量时需要适量减少Ti、Al的含量；当Cr、Ni的含量低于Ti、Al的含量时需要适量增加Ti、Al含量。当Cr元素含量升高时，需同时提高Ni元素的含量，一方面可以保证基体为奥氏体结构，另一方面可以保证有足够的Ni原子形成纳米析出相。(6) The change rule of the content of each element in the alloy is: the content of Ti and Al is determined by the content of the other three elements. When the content of Cr and Ni is higher than that of Ti and Al, it is necessary to reduce the content of Ti and Al in an appropriate amount; when When the content of Cr and Ni is lower than that of Ti and Al, it is necessary to increase the content of Ti and Al appropriately. When the content of Cr element increases, the content of Ni element needs to be increased at the same time. On the one hand, it can ensure that the matrix is an austenite structure, and on the other hand, it can ensure that there are enough Ni atoms to form nano-precipitated phases.
为了解决现有技术的不足，本发明的目的是提供一种高强度、高塑性高熵奥氏体不锈钢及其制备方法，本发明采用的技术手段如下：In order to solve the deficiencies in the prior art, the object of the present invention is to provide a high-strength, high-plastic high-entropy austenitic stainless steel and a preparation method thereof. The technical means used in the present invention are as follows:
一种高熵奥氏体不锈钢，其特征在于，按原子百分比含量计，所述不锈钢的元素组分如下：A high-entropy austenitic stainless steel, characterized in that, by atomic percentage, the elemental components of the stainless steel are as follows:
Cr：5～30％；Ni：5～50％；Ti：1～15％；Al：1～15％；余量为Fe。Cr: 5-30%; Ni: 5-50%; Ti: 1-15%; Al: 1-15%; the balance is Fe.
优选地，按原子百分比含量计，所述不锈钢的元素组分如下：Preferably, in terms of atomic percent content, the elemental composition of the stainless steel is as follows:
Cr：5～19％；Ni：5～29％；Ti：6～15％；Al：5～15％；余量为Fe。Cr: 5-19%; Ni: 5-29%; Ti: 6-15%; Al: 5-15%; the balance is Fe.
进一步地，所述不锈钢中纳米析出相的尺寸≤30nm，纳米析出相的数量密度≥5.0×10 21m -3。 Further, the size of the nano-precipitated phase in the stainless steel is ≤30 nm, and the number density of the nano-precipitated phase is ≥5.0×10 21 m -3 .
一种高熵奥氏体不锈钢的制备方法，具体步骤为：按原子比要求将各原料混合，经真空氩弧炉熔炼和浇注获得铸锭，将铸锭固溶处理后，经(1)冷轧、再结晶后或经(2)热轧、冷轧、再结晶后，进行时效处理，得到高熵奥氏体不锈钢。A method for preparing high-entropy austenitic stainless steel, the specific steps are: mixing various raw materials according to the requirements of atomic ratio, melting and pouring in a vacuum argon arc furnace to obtain ingots, solid solution treating the ingots, and (1) cooling After rolling and recrystallization or after (2) hot rolling, cold rolling and recrystallization, aging treatment is carried out to obtain high-entropy austenitic stainless steel.
进一步地，所述(1)中冷轧的工艺为：每道次压下量不超过0.2mm，总压下量为60％～70％。Further, the cold rolling process in (1) is as follows: the reduction in each pass is no more than 0.2 mm, and the total reduction is 60% to 70%.
进一步地，所述(2)中热轧、冷轧的工艺为：在800℃～1150℃下热轧，每道次压下量不超过0.5mm，热轧过程中保证温度为800～1150℃区间内，若温度降低，可回炉在轧制温度区间内保温5～15min，总压下量至50％～60％后换为冷轧工艺，冷轧每道次压下量不超过0.2mm，总下压量为60％～70％。Further, the process of hot rolling and cold rolling in (2) is as follows: hot rolling at 800°C-1150°C, the reduction in each pass is not more than 0.5mm, and the guaranteed temperature during the hot rolling process is 800-1150°C In the range, if the temperature drops, it can be returned to the furnace and kept in the rolling temperature range for 5 to 15 minutes. After the total reduction reaches 50% to 60%, it will be replaced with a cold rolling process. The reduction of each pass of cold rolling should not exceed 0.2mm. The total down pressure is 60% to 70%.
进一步地，所述再结晶的具体操作为：将(1)或(2)轧制完的铸锭，于1140℃～1160℃下保温1～3min；(如果铸锭体积过大，可适量增加再结晶时间)；Further, the specific operation of the recrystallization is: heat the rolled ingot in (1) or (2) at 1140°C-1160°C for 1-3 minutes; (if the ingot volume is too large, increase recrystallization time);
优选地，所述再结晶的升温速率为10℃/min～20℃/min。Preferably, the heating rate of the recrystallization is 10°C/min-20°C/min.
进一步地，所述真空氩弧炉熔炼工序中氩弧炉在5.0×10 -3Pa以下充入氩气使炉内气压达5.0×10 3Pa后，炉内氧含量和氮含量在180min内均低于0.002％时开始熔炼； Further, in the vacuum argon arc furnace smelting process, the argon arc furnace is filled with argon below 5.0×10 -3 Pa so that the pressure in the furnace reaches 5.0×10 3 Pa, and the oxygen content and nitrogen content in the furnace are within 180 minutes. Melting starts when it is lower than 0.002%;
进一步地，在开始熔炼前还包括用纯Ti去除氧气；Further, it also includes using pure Ti to remove oxygen before starting smelting;
进一步地，所述纯Ti质量为30～40g，不作为原材料也不参与熔炼；Further, the mass of pure Ti is 30-40g, which is neither used as raw material nor involved in smelting;
优选地，所述真空氩弧炉熔炼次数至少四次。Preferably, the vacuum argon arc furnace is smelted at least four times.
进一步地，所述固溶处理的具体操作为：将浇注后的铸锭在1.0×10 -3Pa以下加热至1140℃～1160℃，保温1h～2.5h，然后水淬或于空气中冷却； Further, the specific operation of the solution treatment is: heating the cast ingot below 1.0×10 -3 Pa to 1140°C-1160°C, keeping it warm for 1h-2.5h, and then water quenching or cooling in air;
优选地，所述固溶处理的升温速率为10℃/min～20℃/min。Preferably, the heating rate of the solution treatment is 10°C/min˜20°C/min.
进一步地，所述时效处理具体操作为：将再结晶完的铸锭于500℃～600℃下保温0.5h～1.5h后水淬或空冷；Further, the specific operation of the aging treatment is: heat the recrystallized ingot at 500°C-600°C for 0.5h-1.5h, then water quench or air cool;
优选地，所述时效处理的升温速率为5℃/min～15℃/min。Preferably, the heating rate of the aging treatment is 5°C/min˜15°C/min.
本发明得到的有益效果为：The beneficial effect that the present invention obtains is:
(1)本发明提供了一种高熵奥氏体不锈钢，以原子百分比含量计，各元素的原子配比为Cr：5-30％；Ni：5～50％；Ti：1～15％；Al：1～15％；其余为Fe以及其它冶炼过程或热处理过程中引入的不可避免且含量极少的杂质元素(C、N、O等)。该不锈钢成分体系简单，减少了部分贵金属以及微量掺杂元素，最大程度的减少了合金元素的添加，仅用五种合金元素(三种主要元素：Fe、Cr、Ni，两种少量元素：Ti、Al)，通过调节各组分的原子占比，实现纳米析出相最大量的析出，使制备的高熵奥氏体不锈钢兼具高强度和高塑性。(1) The present invention provides a high-entropy austenitic stainless steel, in terms of atomic percentage content, the atomic ratio of each element is Cr: 5-30%; Ni: 5-50%; Ti: 1-15%; Al: 1-15%; the rest is Fe and other impurity elements (C, N, O, etc.) The stainless steel composition system is simple, reducing some precious metals and trace doping elements, reducing the addition of alloying elements to the greatest extent, and only using five alloying elements (three main elements: Fe, Cr, Ni, two small elements: Ti , Al), by adjusting the atomic ratio of each component, the maximum amount of nano-precipitated phases can be precipitated, so that the prepared high-entropy austenitic stainless steel has both high strength and high plasticity.
通过加入Cr提高不锈钢的强度和耐腐蚀性；加入Ni可用于加宽纳米析出相形成的相区且抑制有害金属间化合物的产生；Al的添加以赋予材料抗氧化性和抗腐蚀性，且有助于纳米析出相的形成；加入Ti元素细化晶粒和均匀组织，同时与Ni、Al形成纳米析出相提升不锈钢的强度，同时Ti替代昂贵的Cu、Co、Nb、Mo以降低生产成本且不破坏纳米析出相的微观结构。该不锈钢以Fe～Cr～Ni为基体，通过控制Cr、Ni的含量，调整添加Ti、Al两种元 素的含量形成纳米析出相以强化基体。其中，当Cr元素含量升高时，需提高Ni元素的含量，一方面保证基体为奥氏体结构，一方面保证足够的Ni原子形成纳米析出相，同时适量降低Ti、Al含量，防止形成脆性的金属间化合物，反之亦然。The strength and corrosion resistance of stainless steel can be improved by adding Cr; the addition of Ni can be used to widen the phase region formed by nano-precipitated phases and inhibit the generation of harmful intermetallic compounds; the addition of Al can endow the material with oxidation resistance and corrosion resistance, and has Contribute to the formation of nano-precipitated phases; adding Ti elements to refine grains and uniform structure, and form nano-precipitated phases with Ni and Al to improve the strength of stainless steel, while Ti replaces expensive Cu, Co, Nb, Mo to reduce production costs and Does not destroy the microstructure of the nano-precipitated phase. The stainless steel uses Fe～Cr～Ni as the matrix. By controlling the content of Cr and Ni, adjusting and adding the content of Ti and Al to form nano-precipitated phases to strengthen the matrix. Among them, when the content of Cr element increases, the content of Ni element needs to be increased. On the one hand, ensure that the matrix is an austenite structure; intermetallic compounds, and vice versa.
在一个优选的方案中，Cr：5～19％；Ni：5～29％；Ti：6～15％；Al：5～15％，余量为铁。在保证合金强度和塑性的前提下，降低了Cr和Ni的用量，进一步降低了生产成本。In a preferred scheme, Cr: 5-19%; Ni: 5-29%; Ti: 6-15%; Al: 5-15%, and the balance is iron. On the premise of ensuring the strength and plasticity of the alloy, the amount of Cr and Ni is reduced, further reducing the production cost.
(2)本发明还提供了一种高强度高塑性高熵奥氏体不锈钢的制备过程，简化了热处理工艺，减少了生产成本，制备工艺简单，具有广阔的应用前景。本发明中的固溶处理方法可使合金元素充分溶入奥氏体基体中，使合金成分更加均匀，采用高温短时间的再结晶处理，在获得均匀且较粗大的等轴晶，保证合金良好塑性的同时，可大大提高生产效率，节约成本。(2) The present invention also provides a preparation process of a high-strength, high-plasticity high-entropy austenitic stainless steel, which simplifies the heat treatment process, reduces production costs, has a simple preparation process, and has broad application prospects. The solid solution treatment method in the present invention can fully dissolve the alloy elements into the austenite matrix, making the alloy composition more uniform, adopting high-temperature and short-time recrystallization treatment, and obtaining uniform and relatively coarse equiaxed crystals to ensure that the alloy is good At the same time of plasticity, it can greatly improve production efficiency and save costs.
在本发明的一个优选方案中采用热轧后冷轧的轧制工艺，有助于解决大铸锭轧制困难的问题，热轧可在初期消除轧制带来的裂纹，为后续冷轧做准备并降低危险性。通过后续的时效处理，有助于纳米析出强化相的沉淀析出，从而提升不锈钢的强度与塑性。本发明制备方法制备的不锈钢由于其良好的强度、塑性的综合，其力学性能发面优于大部分的商用不锈钢，适用于大部分不锈钢的服役领域。In a preferred solution of the present invention, the rolling process of cold rolling after hot rolling is adopted, which helps to solve the problem of difficult rolling of large ingots. Hot rolling can eliminate the cracks caused by rolling at the initial stage, and make a good job for subsequent cold rolling. Prepare and reduce risk. Subsequent aging treatment will help the precipitation of nano-precipitation strengthening phase, thereby improving the strength and plasticity of stainless steel. Due to its good combination of strength and plasticity, the stainless steel prepared by the preparation method of the present invention has better mechanical properties than most commercial stainless steels, and is suitable for most stainless steel service fields.
附图说明Description of drawings
图1为高熵奥氏体不锈钢Fe 47Cr 16Ni 26Ti 6Al 5的X射线衍射图； Figure 1 is the X-ray diffraction pattern of high-entropy austenitic stainless steel Fe 47 Cr 16 Ni 26 Ti 6 Al 5 ;
图2为高熵奥氏体不锈钢Fe 47Cr 16Ni 26Ti 6Al 5的透射电子显微镜图及元素分布图； Figure 2 is the transmission electron microscope image and element distribution map of high-entropy austenitic stainless steel Fe 47 Cr 16 Ni 26 Ti 6 Al 5 ;
图3为高熵奥氏体不锈钢在室温下测得的工程应力-应变曲线图；Fig. 3 is the engineering stress-strain curve figure measured at room temperature of high entropy austenitic stainless steel;
图4为现有技术下商用不锈钢性能与本发明高熵奥氏体不锈钢力学性能的屈服强度R eL与断裂延伸率E的对比图； Fig. 4 is the comparative figure of yield strength R eL and elongation at break E of commercial stainless steel performance under the prior art and high entropy austenitic stainless steel mechanical performance of the present invention;
图5为现有技术下商用不锈钢性能与本发明高熵奥氏体不锈钢力学性能的抗拉强度R m与断裂延伸率E的对比图； Fig. 5 is the comparative figure of the tensile strength Rm and elongation at break E of commercial stainless steel performance under the prior art and high entropy austenitic stainless steel mechanical performance of the present invention;
图6为现有技术下商用不锈钢性能与本发明高熵奥氏体不锈钢力学性能的屈服强度与强塑积(抗拉强度×断裂延伸率)的对比图。Fig. 6 is a comparison chart of the yield strength and the strength-plastic product (tensile strength × elongation at break) of the commercial stainless steel performance under the prior art and the mechanical performance of the high-entropy austenitic stainless steel of the present invention.
具体实施方式Detailed ways
为了更清楚地理解本发明，现参照下列实施例及附图进一步描述本发明。实施例仅用于解释而不以任何方式限制本发明。实施例中，各原始试剂材料均可商购获得，未注明具体条件的实验方法为所属领域熟知的常规方法和常规条件，或按照仪器制造商所建议的条件。In order to understand the present invention more clearly, the present invention will now be further described with reference to the following examples and accompanying drawings. The examples are for illustration only and do not limit the invention in any way. In the examples, each original reagent material can be obtained commercially, and the experimental methods without specific conditions are conventional methods and conventional conditions well known in the art, or according to the conditions suggested by the instrument manufacturer.
实施例1Example 1
本实施例提供了一种高熵奥氏体不锈钢，其化学成分为：Fe 47Cr 16Ni 26Ti 6Al 5(原子比)或 Fe 48.56Cr 15.39Ni 28.24Ti 5.32Al 2.5(重量比)，冶炼过程及热处理过程中引入不可避免且含量极少的杂质元素(C、N、O等)对材料性能的影响可忽略。 This embodiment provides a high-entropy austenitic stainless steel, its chemical composition is: Fe 47 Cr 16 Ni 26 Ti 6 Al 5 (atomic ratio) or Fe 48.56 Cr 15.39 Ni 28.24 Ti 5.32 Al 2.5 (weight ratio), smelting The influence of impurity elements (C, N, O, etc.) introduced into the process and heat treatment process with very small content is negligible on the material properties.
上述高熵奥氏体不锈钢的制备步骤如下：The preparation steps of the above-mentioned high-entropy austenitic stainless steel are as follows:
(1)按化学成分的设计比例，称取各原料混合(各原料纯度≥99.9％)，将氩弧炉于5.0×10 -3Pa以下充入氩气使炉内气压达5.0×10 3Pa后，炉内氧含量和氮含量在180min内均低于0.002％时，先熔化30g纯Ti除氧后开始熔炼。经氩弧炉熔炼6次、浇铸得60×10×5mm的片状铸锭，得到的铸锭化学成分与所述高熵奥氏体不锈钢相同。 (1) According to the design ratio of the chemical composition, weigh and mix the raw materials (the purity of each raw material is ≥99.9%), and fill the argon arc furnace with argon below 5.0×10 -3 Pa to make the pressure in the furnace reach 5.0×10 3 Pa Finally, when the oxygen content and nitrogen content in the furnace are both lower than 0.002% within 180 minutes, first melt 30g of pure Ti to remove oxygen and then start smelting. Melting in an argon arc furnace for 6 times and casting to obtain a sheet-shaped ingot of 60×10×5 mm, the chemical composition of the obtained ingot is the same as that of the high-entropy austenitic stainless steel.
(2)将所述铸锭置于炉内进行固溶处理及均匀化处理，以15℃/min的速率升温至1150℃，保温120min，然后水淬。将固溶处理后的铸锭，采用冷轧变形工艺，轧制工艺为：每道次压下量不超过0.2mm，总压下量为66.7％。将轧制完的铸锭，以10℃/min的速率升温至1150℃，保温1.5min完成再结晶。将再结晶完的铸锭，以10℃/min的速率升温至600℃保温1h后水淬，完成时效处理。(2) Place the ingot in a furnace for solution treatment and homogenization treatment, raise the temperature to 1150° C. at a rate of 15° C./min, keep it warm for 120 minutes, and then water quench. The ingot after the solution treatment is subjected to a cold rolling deformation process, and the rolling process is as follows: the reduction in each pass is not more than 0.2mm, and the total reduction is 66.7%. The rolled ingot was heated up to 1150°C at a rate of 10°C/min, and held for 1.5min to complete recrystallization. The recrystallized ingot was heated up to 600°C at a rate of 10°C/min for 1 hour, and then water quenched to complete the aging treatment.
用常规的CuKα辐射为X射线源进行衍射，衍射图谱如图1所示，图中衍射峰可标定为面心结构的(111)，(200)，(220)，(311)，(222)衍射峰，所以所得结构为奥氏体，由于纳米析出相尺寸太小，在X射线衍射图上不显示可见的衍射峰。Use conventional CuKα radiation as the X-ray source for diffraction, and the diffraction pattern is shown in Figure 1. The diffraction peaks in the figure can be marked as (111), (200), (220), (311), (222) of the face-centered structure Diffraction peaks, so the resulting structure is austenite, because the size of the nano-precipitated phase is too small, no visible diffraction peaks are displayed on the X-ray diffraction pattern.
实施例2Example 2
本实施例提供一种高熵奥氏体不锈钢，其化学成分为：Fe 47Cr 16Ni 26Ti 6Al 5(原子比)或Fe 48.56Cr 15.39Ni 28.24Ti 5.32Al 2.5(重量比)，其中冶炼过程及热处理过程中引入不可避免且含量极少的杂质元素(C、N、O等)可忽略对材料性能的影响。 This embodiment provides a high-entropy austenitic stainless steel whose chemical composition is: Fe 47 Cr 16 Ni 26 Ti 6 Al 5 (atomic ratio) or Fe 48.56 Cr 15.39 Ni 28.24 Ti 5.32 Al 2.5 (weight ratio), wherein smelting The impurity elements (C, N, O, etc.) introduced into the process and heat treatment process with a very small content can be ignored and have negligible impact on the material properties.
上述高熵奥氏体不锈钢的制备步骤如下：The preparation steps of the above-mentioned high-entropy austenitic stainless steel are as follows:
(1)按化学成分的设计比例，称取各原料混合(各原料纯度≥99.9％)，将氩弧炉于5.0×10 -3Pa以下充入氩气使炉内气压达5.0×10 3Pa后，炉内氧含量和氮含量在180min内均低于0.002％时，先熔化30g纯Ti除氧后开始熔炼。经氩弧炉熔炼6次、浇铸得60×10×5mm的片状铸锭，铸锭化学成分与所述高熵奥氏体不锈钢相同。 (1) According to the design ratio of the chemical composition, weigh and mix the raw materials (the purity of each raw material is ≥99.9%), and fill the argon arc furnace with argon below 5.0×10 -3 Pa to make the pressure in the furnace reach 5.0×10 3 Pa Finally, when the oxygen content and nitrogen content in the furnace are both lower than 0.002% within 180 minutes, first melt 30g of pure Ti to remove oxygen and then start smelting. Smelted in an argon arc furnace for 6 times and cast to obtain a sheet-shaped ingot of 60×10×5 mm, the chemical composition of the ingot is the same as that of the high-entropy austenitic stainless steel.
(2)将所述铸锭置于炉内进行固溶处理及均匀化处理，以15℃/min的速率升温至1150℃，保温120min，然后在空气中冷却。将固溶处理后的铸锭，采用热轧后冷轧的变形工艺，轧制工艺为：热轧温度为1150℃，热轧过程中保证温度在800～1150℃区间内，若温度降低，可回炉在轧制温度区间内保温5～15min，每道次压下量不超过0.5mm，总压下量至50％后换为冷轧工艺，每道次压下量不超过0.2mm，总下压量为66.7％。将轧制完的铸锭，以15℃/min的速率升温至1140℃，保温1.5min完成再结晶。将再结晶完的铸锭，以15℃/min的速 率升温至550℃保温1.5h后于空气中冷却，完成时效处理。(2) Place the ingot in a furnace for solution treatment and homogenization treatment, raise the temperature to 1150°C at a rate of 15°C/min, keep it warm for 120min, and then cool it in air. The ingot after solid solution treatment is deformed by cold rolling after hot rolling. The rolling process is as follows: the hot rolling temperature is 1150 °C, and the temperature during the hot rolling process is guaranteed to be within the range of 800 to 1150 °C. If the temperature is lowered, it can be Return to the furnace and keep warm for 5 to 15 minutes in the rolling temperature range. The reduction in each pass shall not exceed 0.5mm. After the total reduction reaches 50%, it shall be replaced with a cold rolling process. The reduction in each pass shall not exceed 0.2mm. The pressure is 66.7%. The rolled ingot was heated up to 1140°C at a rate of 15°C/min, and held for 1.5min to complete recrystallization. The recrystallized ingot was heated to 550°C at a rate of 15°C/min and kept for 1.5 hours, then cooled in air to complete the aging treatment.
通过透射电子显微镜对材料进行表征，透射电子显微镜图以及元素分布图如图2所示，不锈钢基体中分布大量的球形纳米析出相，成分为Ni-Ti-Al，晶体结构为面心立方，平均尺寸为14.4nm(直径)，数量密度为1.68×10 22m -3。 The material was characterized by a transmission electron microscope. The transmission electron microscope image and element distribution diagram are shown in Figure 2. There are a large number of spherical nano-precipitated phases distributed in the stainless steel matrix, the composition is Ni-Ti-Al, and the crystal structure is face-centered cubic. The size is 14.4nm (diameter), and the number density is 1.68×10 22 m -3 .
实施例3Example 3
本实施例提供一种高熵奥氏体不锈钢，其化学成分为：Fe 39Cr 20Ni 30Ti 6Al 5(原子比)或Fe 40.33Cr 19.25Ni 32.6Ti 5.32Al 2.5(重量比)，其中冶炼过程及热处理过程中引入不可避免且含量极少的杂质元素(C、N、O等)可忽略对材料性能的影响。 This embodiment provides a high-entropy austenitic stainless steel whose chemical composition is: Fe 39 Cr 20 Ni 30 Ti 6 Al 5 (atomic ratio) or Fe 40.33 Cr 19.25 Ni 32.6 Ti 5.32 Al 2.5 (weight ratio), wherein The impurity elements (C, N, O, etc.) introduced into the process and heat treatment process with a very small content can be ignored and have negligible impact on the material properties.
上述高熵奥氏体不锈钢的制备步骤如下：The preparation steps of the above-mentioned high-entropy austenitic stainless steel are as follows:
(1)按化学成分的设计比例，称取各原料混合(各原料纯度≥99.9％)，将氩弧炉于5.0×10 -3Pa以下充入氩气使炉内气压达5.0×10 3Pa后，炉内氧含量和氮含量在180min内均低于0.002％时，先熔化35g纯Ti除氧后开始熔炼。经氩弧炉熔炼5次、浇铸得60×10×5mm的片状铸锭，铸锭化学成分与所述高熵奥氏体不锈钢相同。 (1) According to the design ratio of the chemical composition, weigh and mix the raw materials (the purity of each raw material is ≥99.9%), and fill the argon arc furnace with argon below 5.0×10 -3 Pa to make the pressure in the furnace reach 5.0×10 3 Pa Finally, when the oxygen content and nitrogen content in the furnace are both lower than 0.002% within 180 minutes, 35g of pure Ti is first melted to remove oxygen and then the smelting starts. Melted in an argon arc furnace for 5 times, and cast to obtain a flake ingot of 60×10×5 mm, the chemical composition of the ingot is the same as that of the high-entropy austenitic stainless steel.
(2)将所述铸锭置于炉内进行固溶处理及均匀化处理，以15℃/min的速率升温至1150℃，保温120min，然后水淬。将固溶处理后的铸锭，采用冷轧变形工艺，轧制工艺为：每道次压下量不超过0.2mm，总压下量为66.7％。将轧制完的铸锭，以18℃/min的速率升温至1145℃，保温1.5min完成再结晶。将再结晶完的铸锭，以12℃/min的速率升温至600℃保温1h后水淬，完成时效处理。(2) Place the ingot in a furnace for solution treatment and homogenization treatment, raise the temperature to 1150° C. at a rate of 15° C./min, keep it warm for 120 minutes, and then water quench. The ingot after the solution treatment is subjected to a cold rolling deformation process, and the rolling process is as follows: the reduction in each pass is not more than 0.2mm, and the total reduction is 66.7%. The rolled ingot was heated up to 1145°C at a rate of 18°C/min, and held for 1.5min to complete recrystallization. The recrystallized ingot was heated up to 600°C at a rate of 12°C/min for 1 hour, and then water quenched to complete the aging treatment.
实施例4Example 4
本发明实施例提供一种高熵奥氏体不锈钢，其化学成分为：Fe 31Cr 24Ni 34Ti 6Al 5(原子比)或Fe 32.08Cr 23.12Ni 36.98Ti 5.32Al 2.5(重量比)，其中冶炼过程及热处理过程中引入不可避免且含量极少的杂质元素(C、N、O等)可忽略对材料性能的影响。 An embodiment of the present invention provides a high-entropy austenitic stainless steel, the chemical composition of which is: Fe 31 Cr 24 Ni 34 Ti 6 Al 5 (atomic ratio) or Fe 32.08 Cr 23.12 Ni 36.98 Ti 5.32 Al 2.5 (weight ratio), wherein The impurity elements (C, N, O, etc.) introduced into the smelting process and heat treatment process with very small content can be neglected and have negligible impact on the material properties.
上述高熵奥氏体不锈钢的制备步骤如下：The preparation steps of the above-mentioned high-entropy austenitic stainless steel are as follows:
(1)按化学成分的设计比例，称取各原料混合(各原料纯度≥99.9％)，将氩弧炉于5.0×10 -3Pa以下充入氩气使炉内气压达5.0×10 3Pa后，炉内氧含量和氮含量在180min内均低于0.002％时，先熔化40g纯Ti除氧后开始熔炼。经氩弧炉熔炼5次、浇铸得60×10×5mm的片状铸锭，铸锭化学成分与所述高熵奥氏体不锈钢相同。 (1) According to the design ratio of the chemical composition, weigh and mix the raw materials (the purity of each raw material is ≥99.9%), and fill the argon arc furnace with argon below 5.0×10 -3 Pa to make the pressure in the furnace reach 5.0×10 3 Pa Finally, when the oxygen content and nitrogen content in the furnace are both lower than 0.002% within 180 minutes, first melt 40g of pure Ti to remove oxygen and then start smelting. Melted in an argon arc furnace for 5 times, and cast to obtain a flake ingot of 60×10×5 mm, the chemical composition of the ingot is the same as that of the high-entropy austenitic stainless steel.
(2)将所述铸锭置于炉内进行固溶处理及均匀化处理，以15℃/min的速率升温至1150℃，保温120min，然后水淬。将固溶处理后的铸锭，采用冷轧变形工艺，轧制工艺为：每道次压下量不超过0.2mm，总压下量为66.7％。将轧制完的铸锭，以10℃/min的速率升 温至1155℃，保温1.5min完成再结晶。将再结晶完的铸锭，以10℃/min的速率升温至600℃保温1h后水淬，完成时效处理。(2) Place the ingot in a furnace for solution treatment and homogenization treatment, raise the temperature to 1150° C. at a rate of 15° C./min, keep it warm for 120 minutes, and then water quench. The ingot after the solution treatment is subjected to a cold rolling deformation process, and the rolling process is as follows: the reduction in each pass is not more than 0.2mm, and the total reduction is 66.7%. The rolled ingot was heated up to 1155°C at a rate of 10°C/min and kept for 1.5min to complete recrystallization. The recrystallized ingot was heated up to 600°C at a rate of 10°C/min for 1 hour, and then water quenched to complete the aging treatment.
实施例5Example 5
本发明实施例提供一种高熵奥氏体不锈钢，其化学成分为：Fe 42Cr 16Ni 28Ti 7Al 7(原子比)或Fe 43.88Cr 15.56Ni 30.75Ti 6.27Al 3.53(重量比)，其中冶炼过程及热处理过程中引入不可避免且含量极少的杂质元素(C、N、O等)可忽略对材料性能的影响。 The embodiment of the present invention provides a high-entropy austenitic stainless steel, its chemical composition is: Fe 42 Cr 16 Ni 28 Ti 7 Al 7 (atomic ratio) or Fe 43.88 Cr 15.56 Ni 30.75 Ti 6.27 Al 3.53 (weight ratio), wherein The impurity elements (C, N, O, etc.) introduced into the smelting process and heat treatment process with very small content can be neglected and have negligible impact on the material properties.
上述高熵奥氏体不锈钢的制备步骤如下：The preparation steps of the above-mentioned high-entropy austenitic stainless steel are as follows:
(1)按化学成分的设计比例，称取各原料混合(各原料纯度≥99.9％)，将氩弧炉于5.0×10 -3Pa以下充入氩气使炉内气压达5.0×10 3Pa后，氧含量和氮含量在180min内均低于0.002％时，先熔化35g纯Ti除氧后开始熔炼。经氩弧炉熔炼6次、浇铸得60×10×5mm的片状铸锭，铸锭化学成分与所述高熵奥氏体不锈钢相同。 (1) According to the design ratio of the chemical composition, weigh and mix the raw materials (the purity of each raw material is ≥99.9%), and fill the argon arc furnace with argon below 5.0×10 -3 Pa to make the pressure in the furnace reach 5.0×10 3 Pa Finally, when the oxygen content and nitrogen content are both lower than 0.002% within 180 minutes, 35g of pure Ti is first melted to remove oxygen and then the smelting starts. Smelted in an argon arc furnace for 6 times and cast to obtain a sheet-shaped ingot of 60×10×5 mm, the chemical composition of the ingot is the same as that of the high-entropy austenitic stainless steel.
(2)将所述铸锭置于炉内进行固溶处理及均匀化处理，以15℃/min的速率升温至1150℃，保温120min，然后水淬。将固溶处理后的铸锭，采用冷轧变形工艺，轧制工艺为：每道次压下量不超过0.2mm，总压下量为66.7％。将轧制完的铸锭，以20℃/min的速率升温至1160℃，保温1.5min完成再结晶。将再结晶完的铸锭，以10℃/min的速率升温至600℃保温1h后水淬，完成时效处理。(2) Place the ingot in a furnace for solution treatment and homogenization treatment, raise the temperature to 1150° C. at a rate of 15° C./min, keep it warm for 120 minutes, and then water quench. The ingot after the solution treatment is subjected to a cold rolling deformation process, and the rolling process is as follows: the reduction in each pass is not more than 0.2mm, and the total reduction is 66.7%. The rolled ingot was heated up to 1160°C at a rate of 20°C/min, and held for 1.5min to complete recrystallization. The recrystallized ingot was heated up to 600°C at a rate of 10°C/min for 1 hour, and then water quenched to complete the aging treatment.
实施例6Example 6
本发明实施例提供一种高熵奥氏体不锈钢，其化学成分为：Fe 49Cr 16Ni 28Ti 4Al 3(原子比)或Fe 49.9Cr 15.17Ni 29.98Ti 3.49Al 1.48(重量比)，其中冶炼过程及热处理过程中引入不可避免且含量极少的杂质元素(C、N、O等)可忽略对材料性能的影响。 An embodiment of the present invention provides a high-entropy austenitic stainless steel, the chemical composition of which is: Fe 49 Cr 16 Ni 28 Ti 4 Al 3 (atomic ratio) or Fe 49.9 Cr 15.17 Ni 29.98 Ti 3.49 Al 1.48 (weight ratio), wherein The impurity elements (C, N, O, etc.) introduced into the smelting process and heat treatment process with very small content can be neglected and have negligible impact on the material properties.
上述高熵奥氏体不锈钢的制备步骤如下：The preparation steps of the above-mentioned high-entropy austenitic stainless steel are as follows:
(1)按化学成分的设计比例，称取各原料混合(各原料纯度≥99.9％)将氩弧炉于5.0×10 -3Pa以下充入氩气使炉内气压达5.0×10 3Pa后，炉内氧含量和氮含量在180min内均低于0.002％时，先熔化30g纯Ti除氧后开始熔炼。经氩弧炉熔炼6次、浇铸得60×10×5mm的片状铸锭，铸锭化学成分与所述高熵奥氏体不锈钢相同。 (1) According to the design ratio of the chemical composition, weigh and mix the raw materials (the purity of each raw material is ≥99.9%), fill the argon arc furnace with argon below 5.0×10 -3 Pa, and make the pressure in the furnace reach 5.0×10 3 Pa. , when the oxygen content and nitrogen content in the furnace are both lower than 0.002% within 180 minutes, first melt 30g of pure Ti to remove oxygen and then start smelting. Smelted in an argon arc furnace for 6 times and cast to obtain a sheet-shaped ingot of 60×10×5 mm, the chemical composition of the ingot is the same as that of the high-entropy austenitic stainless steel.
(2)将所述铸锭置于炉内进行固溶处理及均匀化处理，以15℃/min的速率升温至1150℃，保温120min，然后水淬。将固溶处理后的铸锭，采用冷轧变形工艺，轧制工艺为：每道次压下量不超过0.2mm，总压下量为66.7％。将轧制完的铸锭，以10℃/min的速率升温至1150℃，保温1.5min完成再结晶。将再结晶完的铸锭，以10℃/min的速率升温至600℃保温1h后水淬，完成时效处理。(2) Place the ingot in a furnace for solution treatment and homogenization treatment, raise the temperature to 1150° C. at a rate of 15° C./min, keep it warm for 120 minutes, and then water quench. The ingot after the solution treatment is subjected to a cold rolling deformation process, and the rolling process is as follows: the reduction in each pass is not more than 0.2mm, and the total reduction is 66.7%. The rolled ingot was heated up to 1150°C at a rate of 10°C/min, and held for 1.5min to complete recrystallization. The recrystallized ingot was heated up to 600°C at a rate of 10°C/min for 1 hour, and then water quenched to complete the aging treatment.
实验例Experimental example
将实施例1～6制备的材料中任意取样分析，其屈服强度R eL、抗拉强度R m、断裂延伸率E、屈强比(R eL/R m)统计分析结果如表1所示，其中，表中的每个样品均检测三次，采取随机取样的方式。 The materials prepared in Examples 1-6 were randomly sampled and analyzed, and the statistical analysis results of yield strength ReL , tensile strength Rm , elongation at break E, and yield strength ratio ( ReL / Rm ) are shown in Table 1. Among them, each sample in the table was tested three times, and random sampling was adopted.
表1实施例1～6合金性能数据Table 1 Embodiment 1～6 alloy performance data
Figure PCTCN2022128626-appb-000001
Figure PCTCN2022128626-appb-000001
(1)由表1可以看出，本发明实施例1-3制备的高熵奥氏体不锈钢的屈服强度、抗拉强度更高、断裂延伸率均保持了很高的水平，屈强比位于0.67～0.73合理范围内。实施例4～5由于Ti、Al含量过量，导致形成脆性的金属间化合物，虽然强度有所提升，但塑性损失很多。而实施例6由于Ti、Al含量不足，无法实现析出强化最大化，导致强度较低。(1) It can be seen from Table 1 that the yield strength and tensile strength of the high-entropy austenitic stainless steel prepared in Examples 1-3 of the present invention are higher, and the elongation at break is maintained at a very high level, and the yield ratio is at 0.67 to 0.73 within a reasonable range. In Examples 4 to 5, brittle intermetallic compounds are formed due to the excessive content of Ti and Al. Although the strength is improved, the plasticity is much lost. However, due to insufficient Ti and Al content in Example 6, the maximum precipitation strengthening cannot be achieved, resulting in lower strength.
(2)图3为高熵奥氏体不锈钢在室温下测得的工程应力-应变曲线，所用应变速率为1×10 -3s -1。高熵奥氏体不锈钢的屈服强度、抗拉强度以及断裂延伸率如表1所示，该图表明，具有最优性能的高熵奥氏体不锈钢屈服强度为820MPa，抗拉强度为1220MPa，断裂延伸率为37％。 (2) Fig. 3 shows the engineering stress-strain curve of high-entropy austenitic stainless steel measured at room temperature, and the strain rate used is 1×10 -3 s -1 . The yield strength, tensile strength and elongation at break of high-entropy austenitic stainless steel are shown in Table 1. The elongation was 37%.
(3)图4为现有技术下商用不锈钢性能与本发明高熵奥氏体不锈钢力学性能的屈服强度R eL与断裂延伸率E的对比，该图表明，本发明高熵奥氏体不锈钢的屈服强度高于绝大多数的商用不锈钢且保持了很高的塑性，其屈服强度与断裂延伸率的乘积为14.5～30.3GPa％，高于商用不锈钢的2.62～17.2GPa％。 (3) Fig. 4 is the comparison of the yield strength R eL and the elongation at break E of commercial stainless steel properties under the prior art and the mechanical properties of the high-entropy austenitic stainless steel of the present invention, and this figure shows that the high-entropy austenitic stainless steel of the present invention The yield strength is higher than that of most commercial stainless steels and maintains high plasticity. The product of yield strength and elongation at break is 14.5-30.3GPa%, which is higher than 2.62-17.2GPa% of commercial stainless steels.
(5)图5为现有技术下商用不锈钢性能与本发明高熵奥氏体不锈钢力学性能的抗拉强度R m与断裂延伸率E的对比，该图表明，本发明高熵奥氏体不锈钢在保持高塑性的同时还兼具很高的抗拉强度，其抗拉强度与断裂延伸率的乘积为18.0～46.1GPa％，高于商用不锈钢的2.9～42.8GPa％。 (5) Fig. 5 is the contrast of tensile strength R m and elongation at break E of commercial stainless steel properties under the prior art and high-entropy austenitic stainless steel mechanical properties of the present invention, and this figure shows, high-entropy austenitic stainless steel of the present invention While maintaining high plasticity, it also has high tensile strength. The product of tensile strength and elongation at break is 18.0-46.1GPa%, which is higher than 2.9-42.8GPa% of commercial stainless steel.
(6)图6为现有技术下商用不锈钢性能与本发明高熵奥氏体不锈钢力学性能的屈服强度与强塑积(抗拉强度×断裂延伸率)的对比，该图表明，本发明高熵奥氏体不锈钢的屈服强度及强塑积高于现有技术的不锈钢，在兼具高强度的同时保持了高塑性，综合性能优于现有技术的不锈钢。(6) Fig. 6 is the comparison of the yield strength and the strong-plastic product (tensile strength × elongation at break) of the commercial stainless steel properties under the prior art and the high-entropy austenitic stainless steel mechanical properties of the present invention, and this figure shows that the present invention has high The yield strength and strength-plastic product of the entropic austenitic stainless steel are higher than those of the stainless steel of the prior art, while maintaining high plasticity while having high strength, the comprehensive performance is better than that of the stainless steel of the prior art.
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。Apparently, the above-mentioned embodiments are only examples for clear description, rather than limiting the implementation. For those of ordinary skill in the art, other changes or changes in different forms can be made on the basis of the above description. It is not necessary and impossible to exhaustively list all the implementation manners here. And the obvious changes or changes derived therefrom are still within the scope of protection of the present invention.

Claims (10)

  1. 一种高熵奥氏体不锈钢，其特征在于，按原子百分比含量计，所述不锈钢的元素组分如下：A high-entropy austenitic stainless steel, characterized in that, by atomic percentage, the elemental components of the stainless steel are as follows:
    Cr：5～30％；Ni：5～50％；Ti：1～15％；Al：1～15％；余量为Fe。Cr: 5-30%; Ni: 5-50%; Ti: 1-15%; Al: 1-15%; the balance is Fe.
  2. 如权利要求1所述的高熵奥氏体不锈钢，其特征在于，按原子百分比含量计，所述不锈钢的元素组分如下：The high-entropy austenitic stainless steel according to claim 1, characterized in that, in terms of atomic percentage content, the elemental components of the stainless steel are as follows:
    Cr：5～19％；Ni：5～29％；Ti：6～15％；Al：5～15％；余量为Fe。Cr: 5-19%; Ni: 5-29%; Ti: 6-15%; Al: 5-15%; the balance is Fe.
  3. 如权利要求1所述的高熵奥氏体不锈钢，其特征在于，所述不锈钢中纳米析出相的尺寸≤30nm，纳米析出相的数量密度≥5.0×10 21m -3。 The high-entropy austenitic stainless steel according to claim 1, characterized in that the size of the nano-precipitated phase in the stainless steel is ≤30nm, and the number density of the nano-precipitated phase is ≥5.0×10 21 m -3 .
  4. 一种高熵奥氏体不锈钢的制备方法，其特征在于，具体步骤为：按原子比要求将各原料混合，经真空氩弧炉熔炼和浇注获得铸锭，将铸锭固溶处理后，经(1)冷轧、再结晶后或经(2)热轧、冷轧、再结晶后，进行时效处理，得到高熵奥氏体不锈钢。A method for preparing high-entropy austenitic stainless steel, characterized in that the specific steps are: mixing raw materials according to the atomic ratio requirements, melting and pouring in a vacuum argon arc furnace to obtain an ingot, solid solution treating the ingot, and (1) After cold rolling and recrystallization or (2) after hot rolling, cold rolling and recrystallization, aging treatment is carried out to obtain high-entropy austenitic stainless steel.
  5. 如权利要求4所述的制备方法，其特征在于，所述(1)中冷轧的工艺为：每道次压下量不超过0.2mm，总压下量为60％～70％。The preparation method according to claim 4, characterized in that the cold rolling process in (1) is as follows: the reduction in each pass is no more than 0.2 mm, and the total reduction is 60% to 70%.
  6. 如权利要求4所述的制备方法，其特征在于，所述(2)中热轧、冷轧的工艺为：在800℃～1150℃下热轧，每道次压下量不超过0.5mm，热轧过程中保证温度为800～1150℃区间内，若温度降低，可回炉在轧制温度区间内保温5～15min，总压下量至50％～60％后换为冷轧工艺，冷轧每道次压下量不超过0.2mm，总下压量为60％～70％。The preparation method according to claim 4, characterized in that, the process of hot rolling and cold rolling in (2) is: hot rolling at 800°C-1150°C, the reduction per pass is not more than 0.5mm, During the hot rolling process, the temperature is guaranteed to be within the range of 800-1150 °C. If the temperature drops, it can be returned to the furnace and kept in the rolling temperature range for 5-15 minutes. The amount of reduction in each pass is not more than 0.2mm, and the total amount of reduction is 60% to 70%.
  7. 如权利要求4所述的制备方法，其特征在于，所述再结晶的具体操作为：将(1)或(2)轧制完的铸锭，于1140℃～1160℃下保温1～3min；The preparation method according to claim 4, characterized in that, the specific operation of the recrystallization is: heat the ingot rolled in (1) or (2) at 1140°C-1160°C for 1-3min;
    优选地，所述再结晶的升温速率为10℃/min～20℃/min。Preferably, the heating rate of the recrystallization is 10°C/min-20°C/min.
  8. 如权利要求4所述的制备方法，其特征在于，所述真空氩弧炉熔炼工序具体为：氩弧炉在5.0×10 -3Pa以下充入氩气使炉内气压达5.0×10 3Pa，炉内氧含量和氮含量在180min内均低于0.002％时开始熔炼； The preparation method according to claim 4, characterized in that, the vacuum argon arc furnace smelting process is specifically: the argon arc furnace is filled with argon below 5.0×10 -3 Pa so that the pressure in the furnace reaches 5.0×10 3 Pa , when the oxygen content and nitrogen content in the furnace are both lower than 0.002% within 180 minutes, the smelting starts;
    进一步地，在开始熔炼前还包括用纯Ti去除氧气；Further, it also includes using pure Ti to remove oxygen before starting smelting;
    优选地，所述真空氩弧炉熔炼次数至少四次。Preferably, the vacuum argon arc furnace is smelted at least four times.
  9. 如权利要求4所述的制备方法，其特征在于，所述固溶处理的具体操作为：将浇注后的铸锭在1.0×10 -3Pa以下加热至1140℃～1160℃，保温1h～2.5h， 然后水淬或于空气中冷却； The preparation method according to claim 4, characterized in that the specific operation of the solid solution treatment is: heating the poured ingot below 1.0×10 -3 Pa to 1140°C-1160°C and keeping it warm for 1h-2.5 h, then quenched in water or cooled in air;
    优选地，所述固溶处理的升温速率为10℃/min～20℃/min。Preferably, the heating rate of the solution treatment is 10°C/min˜20°C/min.
  10. 如权利要求4所述的制备方法，其特征在于，所述时效处理具体操作为：将再结晶完的铸锭于500℃～600℃下保温0.5h～1.5h后水淬或空冷；The preparation method according to claim 4, characterized in that, the specific operation of the aging treatment is: heat the recrystallized ingot at 500°C-600°C for 0.5h-1.5h, and then water quench or air cool;
    优选地，所述时效处理的升温速率为5℃/min～15℃/min。Preferably, the heating rate of the aging treatment is 5°C/min˜15°C/min.
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Families Citing this family (6)

* Cited by examiner, † Cited by third party
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CN115141984B (en) * 2021-11-23 2023-02-24 燕山大学 High-entropy austenitic stainless steel and preparation method thereof
CN115491564B (en) * 2022-10-09 2023-06-23 南京工业大学 Iron-rich high-strength and high-toughness duplex high-entropy stainless steel and preparation method thereof
CN115896642B (en) * 2022-12-05 2024-03-19 襄阳金耐特机械股份有限公司 Preparation method of austenitic heat-resistant stainless steel
CN116287818B (en) * 2023-03-24 2024-04-30 西北有色金属研究院 AlCoCrFeNiTi-series high-entropy alloy with high strength and plasticity and preparation method thereof
CN117026109B (en) * 2023-09-05 2024-03-19 燕山大学 High-strength creep-resistant low-specific gravity high/medium-entropy heat-resistant steel and preparation method thereof
CN117987749A (en) * 2024-04-03 2024-05-07 清华大学 Ultrahigh-strength hydrogen embrittlement-resistant austenitic stainless steel and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104694808A (en) * 2015-03-26 2015-06-10 北京科技大学 High-entropy alloy with dispersion nano-sized precipitate strengthening effect and preparing method thereof
KR20170124441A (en) * 2016-05-02 2017-11-10 한국과학기술원 High- strength and heat-resisting high entropy alloy matrix composites and method of manufacturing the same
CN107354391A (en) * 2017-07-27 2017-11-17 安徽工业大学 A kind of multigroup metamember precipitation-hardening stainless steel based on high entropic effect
EP3543368A1 (en) * 2018-03-20 2019-09-25 The Swatch Group Research and Development Ltd High-entropy alloys for covering components
CN110408850A (en) * 2019-07-17 2019-11-05 浙江大学 The super-steel and preparation method thereof of nanocrystalline intermetallics precipitation strength
CN113430343A (en) * 2021-07-05 2021-09-24 陕西科技大学 Novel processing method of nano precipitation strengthening CoCrNi-based high-entropy alloy
CN115141984A (en) * 2021-11-23 2022-10-04 燕山大学 High-entropy austenitic stainless steel and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004107777A (en) * 2002-09-20 2004-04-08 Toshiba Corp Austenitic heat resistant alloy, production method therefor and steam turbine parts
EP3401415A4 (en) * 2016-01-05 2019-08-07 Nippon Steel Corporation Austenitic heat-resistant alloy and method for manufacturing same
CN109252083B (en) * 2018-11-07 2021-04-16 安阳工学院 Multiphase high-entropy alloy and preparation method thereof
CN110735077B (en) * 2019-10-14 2020-08-28 中南大学 AlCrFeNiSiTi high-entropy alloy porous material and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104694808A (en) * 2015-03-26 2015-06-10 北京科技大学 High-entropy alloy with dispersion nano-sized precipitate strengthening effect and preparing method thereof
KR20170124441A (en) * 2016-05-02 2017-11-10 한국과학기술원 High- strength and heat-resisting high entropy alloy matrix composites and method of manufacturing the same
CN107354391A (en) * 2017-07-27 2017-11-17 安徽工业大学 A kind of multigroup metamember precipitation-hardening stainless steel based on high entropic effect
EP3543368A1 (en) * 2018-03-20 2019-09-25 The Swatch Group Research and Development Ltd High-entropy alloys for covering components
CN110408850A (en) * 2019-07-17 2019-11-05 浙江大学 The super-steel and preparation method thereof of nanocrystalline intermetallics precipitation strength
CN113430343A (en) * 2021-07-05 2021-09-24 陕西科技大学 Novel processing method of nano precipitation strengthening CoCrNi-based high-entropy alloy
CN115141984A (en) * 2021-11-23 2022-10-04 燕山大学 High-entropy austenitic stainless steel and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
SCIENCE, vol. 362, 2018, pages 933 - 937
SHI HAO; FETZER RENATE; JIANU ADRIAN; WEISENBURGER ALFONS; HEINZEL ANNETTE; LANG FABIAN; MüLLER GEORG: "Influence of alloying elements (Cu, Ti, Nb) on the microstructure and corrosion behaviour of AlCrFeNi-based high entropy alloys exposed to oxygen-containing molten Pb", CORROSION SCIENCE, OXFORD, GB, vol. 190, 1 July 2021 (2021-07-01), GB , XP086746939, ISSN: 0010-938X, DOI: 10.1016/j.corsci.2021.109659 *

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