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CN112831640A - Production method of austenitic stainless steel with yield strength of more than or equal to 980MPa - Google Patents

Production method of austenitic stainless steel with yield strength of more than or equal to 980MPa Download PDF

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CN112831640A
CN112831640A CN202011624871.2A CN202011624871A CN112831640A CN 112831640 A CN112831640 A CN 112831640A CN 202011624871 A CN202011624871 A CN 202011624871A CN 112831640 A CN112831640 A CN 112831640A
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stainless steel
temperature
nitriding
annealing
austenitic stainless
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CN112831640B (en
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万响亮
柯睿
甘晓龙
胡丞杨
吴开明
赵杰
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Nanjing Dongjin Enterprise Management Group Co.,Ltd.
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Wuhan University of Science and Engineering WUSE
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    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236Cold rolling
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0257Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment with diffusion of elements, e.g. decarburising, nitriding
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0273Final recrystallisation annealing
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/24Nitriding
    • C23C8/26Nitriding of ferrous surfaces
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/001Austenite

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)

Abstract

A production method of austenitic stainless steel with yield strength more than or equal to 980MPa comprises the following steps: cold rolling a stainless steel hot rolled plate with the thickness of 3mm at room temperature, wherein the rolling pass is not less than 4; nitriding, wherein the nitriding temperature is controlled to be 456-628 ℃; and (3) carrying out high-temperature annealing: the annealing temperature is 989-1113 ℃; cooling to room temperature at a cooling rate of 3-24 ℃/s. The invention not only has a metallographic structure of full austenite, but also has a stainless steel plate with a thickness of 0.39-0.6 mm, a yield strength of 980-1290 MPa, a tensile strength of 1112-1452 MPa and an elongation of 13.0-15.5%; cold rolling is carried out at room temperature, and nitriding is carried out under the condition of keeping a body-centered cubic martensite structure to ensure that the nitrogen content is highest; high temperature annealing shears the martensite structure into a fully austenitic structure while still maintaining the ultrafine structure.

Description

Production method of austenitic stainless steel with yield strength of more than or equal to 980MPa
Technical Field
The invention relates to a production method of stainless steel, in particular to a production method of austenitic stainless steel with yield strength more than or equal to 980 MPa.
Background
The austenitic stainless steel accounts for more than 70 percent of the total production of the stainless steel in the world, and the austenitic stainless steel has good corrosion resistance and high ductility and toughness. However, the grains are coarse face-centered cubic structures, so that the deformation is easy to occur under the action of stress, and the yield strength is only 200-300 MPa. With the increasing prominence of the problems of world resource consumption and the like, the development of ultra-high strength austenitic stainless steel is urgently needed, and the ultra-high strength austenitic stainless steel with thin specification replaces a thick steel plate with low strength grade, which becomes a development trend and is also an inevitable choice for social development.
Currently, there are few effective methods for improving the strength of stainless steel while maintaining the austenitic structure and high ductility, toughness and corrosion resistance. The solid solution of interstitial nitrogen can effectively improve the strength of austenitic stainless steel and simultaneously keep high ductility, toughness and corrosion resistance, however, nitrogen is difficult to add during smelting of austenitic stainless steel, nitrogen element is very slowly diffused in a face-centered cubic structure during nitriding of austenitic stainless steel, the content of nitrogen in the prepared nitrogen-added austenitic stainless steel is mostly below 0.6%, and the yield strength of the nitrogen-added austenitic stainless steel is usually less than 450 MPa.
The combination of large cold deformation and annealing process is also an effective method for improving the strength of austenitic stainless steel, and the ultra-fine grained austenitic stainless steel is obtained by utilizing large cold deformation to generate deformed martensite and then annealing to generate reverse phase transformation. The fine grain strengthening can improve the strength and simultaneously maintain good ductility, toughness and corrosion resistance. However, it is difficult to obtain both ultra-high strength and fully austenitic structures in stainless steels prepared by large cold deformation combined with annealing processes. This is because stainless steel, which is annealed for a short time to obtain ultra-fine grains, has an ultra-high strength, but also retains a part of the martensite structure; the annealing time is prolonged to promote the martensite to be completely reversed to austenite, and then the crystal grains are gradually grown, the corresponding yield strength is rapidly reduced, and the yield strength of the fine-grained stainless steel with the full austenite structure obtained by the method is difficult to exceed 700 MPa. The stainless steel with the yield strength grade of over 900MPa, an all-austenite structure, high ductility and toughness and high corrosion resistance can not be prepared.
Chinese patent publication No. CN104451082 discloses a method for preparing 304 austenitic stainless steel with grain size less than 100 nm. In the document, three-stage cold rolling-annealing treatment is adopted, cold rolling is carried out at the reduction of 25-35%, and then after heat preservation is carried out at the temperature of 800-900 ℃ for 5-20min, 304 stainless steel with the grain size smaller than 100nm is prepared after repeated for multiple times. The stainless steel prepared by the method has the yield strength of 1100-1200MPa and the tensile strength of 1250-1350 MPa. However, after the process is subjected to heat preservation at the temperature of 900 ℃ of 800-. If the martensite structure is eliminated by the continuous annealing, the austenite grains are inevitably coarse during the annealing, the yield strength is sharply reduced, and the stainless steel with the total austenite structure and the yield strength of more than 980MPa is difficult to obtain.
Chinese patent publication No. CN103088283A discloses a method for promoting infiltration of austenitic stainless steel by staged pressurization and solid solution nitriding. In the document, austenitic stainless steel is subjected to nitriding pretreatment at 500-700 ℃ for 5-10 hours, and then is subjected to solid solution nitriding treatment at 900-1200 ℃ for 1-20 hours to obtain austenitic stainless steel with a nitriding layer thickness of about 90-311 microns. However, the product produced by this process does not give data on N content, strength and plasticity. According to the process, the structure of the austenitic stainless steel before nitriding is coarse austenite grains, and nitriding is carried out in the range of 500-700 ℃, so that the nitrogen content in the steel is not too high due to too small diffusion coefficient of nitrogen in the austenitic structure; in addition, the method also needs to carry out heat preservation on the stainless steel at 900-1200 ℃ for 1-20 hours, the long-time annealing under the high-temperature condition can cause the grain size of the austenitic stainless steel to be extremely large, the yield strength and the tensile strength of the material can be rapidly reduced, and the stainless steel with the full-austenitic structure and the yield strength of more than 980MPa is difficult to obtain.
Disclosure of Invention
The invention aims to solve the defects that the strength grade and the stainless steel are all austenitic structures which can not meet the requirements simultaneously and the strength grade is low in the prior art, and provides a production method of austenitic stainless steel, wherein the thickness of the austenitic stainless steel is 0.39-0.60 mm, the yield strength is 980-1290 MPa, the tensile strength is 1112-1452 MPa and the elongation percentage is 13.0-15.5%.
The measures for realizing the aim are as follows:
a production method of austenitic stainless steel with yield strength more than or equal to 980MPa comprises the following steps:
1) cold rolling a stainless steel hot rolled plate with the thickness of 3mm at room temperature, wherein the rolling pass is not less than 4, and the thickness of the stainless steel hot rolled plate is 0.39-0.6 mm; the reduction rate of each pass is controlled to be 33-43%;
2) nitriding, wherein the nitriding temperature is controlled to be 456-628 ℃, the nitriding time is 22-60 min, and the nitriding atmosphere is 10% NH3+60%N2+30%H2The flow rate of the mixed gas is 1.6-2.3L/min;
3) and (3) carrying out high-temperature annealing: the annealing temperature is 989-1113 ℃, and the temperature is kept for 28-58 seconds at the temperature;
4) cooling the mixture to room temperature at a cooling rate of 3-24 ℃/s.
Preferably: the nitriding temperature is controlled to be 496-592 ℃, the nitriding time is 29-53 min, and the flow rate of the mixed gas is 1.8-2.1L/min.
Preferably: the high-temperature annealing temperature is controlled to be 989-1016 ℃, and the annealing time is 38-58 seconds.
Mechanism and action of the main process of the invention
The reduction rate of each pass of cold rolling is controlled to be 33-43%, because the reduction rate in the cold rolling process and the thickness after the cold rolling are controlled, if the reduction rate of each pass is too small, a cold-rolled plate consisting of a large amount of deformed martensite is difficult to obtain, so that the nitrogen atom infiltration amount in the subsequent annealing process is low, and the austenitic stainless steel with ultrafine grains is difficult to obtain after annealing; if the reduction rate of each pass is too large, equipment is easily damaged; if the reduction ratio of each pass is not uniform, deformed martensite generated in a cold-rolled sheet is easily distributed unevenly, and martensite or austenite grains are easily remained in a partial area of a stainless steel structure in the subsequent annealing process or are coarse.
The nitriding is performed by the present invention, and the nitriding temperature is controlled to 456-628 ℃, the nitriding time is controlled to 22-60 min, and the nitriding atmosphere is 10% NH3+60%N2+30%H2The flow rate of the mixed gas is 1.6-2.3L/min, preferably controlling the nitriding temperature to be 496-592 ℃, and controlling the flow rate of the mixed gas to be 1.8-2.1L/min when the nitriding time is 29-53 min, because if the nitriding adopts low temperature, the diffusion coefficient of nitrogen in steel is small, and high nitriding amount is difficult to obtain; if high temperatures are used for nitriding, the martensitic structure may be transformed into an austenitic structure by reverse phase transformation, and the nitrogen diffusion coefficient in austenite is too small, so that nitrogen is difficult to penetrate into steel. If the nitriding is performed in a short time, the static recrystallization effect in martensite and austenite is not obvious; if nitriding is carried out for a long time, the growth of crystal grains is easily caused after recrystallization is finished, and the obtained crystal grains are quickly coarsened. If NH is in the nitriding atmosphere3The volume percentage content of the nitrogen-containing compound is less than 10 percent, and the optimal nitriding effect is difficult to achieve; if NH is in the nitriding atmosphere3The volume percentage content of the nitrogen-containing compound is more than 10 percent, the nitriding effect has small change range, and the nitrogen-containing compound is not economical and environment-friendly. This is disadvantageous for obtaining high nitrogen contents and ultra-fine austenitic structures. The proper nitriding process enables austenitic stainless steels to achieve high nitrogen contents.
The method of the invention carries out high temperature annealing, and the temperature is controlled to be 989-1113 ℃, the annealing time is 28-58 seconds, preferably the annealing temperature is controlled to be 989-1016 ℃, the annealing time is 38-58 seconds, and the annealing at the temperature can enable the deformed martensite structure to be rapidly reversed into the superfine austenite structure through a shear mechanism. If the annealing temperature is too low, the steel is difficult to be rapidly transformed into austenite through a shear mechanism; if the annealing temperature is too high or the heat preservation time is too long, the obtained austenite grains are easily coarsened quickly. This is disadvantageous in that a steel sheet having a structure of ultrafine fully austenitic grains is obtained.
Compared with the prior art, the invention has the characteristics that: not only the metallographic structure is fully austenitic, but also the thickness of the stainless steel plate is 0.39-0.6 mm, the yield strength is 980-1290 MPa, the tensile strength is 1112-1452 MPa, and the elongation is 13.0-15.5%, and the method also comprises the following steps:
1. the cold rolling is carried out at room temperature, but the cold rolling-annealing process is used for preparing the nano-scale austenitic stainless steel at home and abroad at present, and the cold rolling is mostly carried out at low temperature or ultralow temperature. The invention is easier for industrialized production.
2. The invention adopts the medium-temperature nitriding process, nitriding is carried out under the condition of keeping the body-centered cubic martensite structure, the nitrogen atom diffusion coefficient in the body-centered cubic martensite structure in the medium-temperature stage is large, the diffusion speed is high, and the nitrogen content in the stainless steel can be increased to the maximum.
3. The high-temperature annealing process of the invention has the advantages that the deformed martensite is subjected to recovery recrystallization in the medium-temperature nitriding process, the dislocation in martensite crystal grains is reduced, a large amount of subgrain boundaries are formed, and a superfine structure with the grain size of submicron grade is obtained; subsequent high temperature annealing causes the martensitic structure to be cut into a fully austenitic structure while still maintaining the ultra-fine structure.
Drawings
FIG. 1 is a structural morphology of stainless steel after nitriding by the present invention;
FIG. 2 is a structural morphology diagram of stainless steel after high temperature annealing.
Detailed Description
The invention is further described below with reference to specific examples:
table 1 shows the control list of the main parameters of the processes of the examples and comparative examples of the present invention;
table 2 is a table of mechanical property testing conditions of each example and comparative example of the present invention.
The preparation method comprises the following steps:
1) cold rolling the stainless steel hot rolled plate at room temperature, wherein the rolling pass is not less than 4, and the thickness of the rolled plate is 0.39-0.6 mm; the reduction rate of each pass is controlled to be 33-43%;
2) nitriding, wherein the nitriding temperature is controlled to be 456-628 ℃, the nitriding time is 22-60 min, and the nitriding atmosphere is 10% NH3+60%N2+30%H2The flow rate of the mixed gas is 1.6-2.3L/min;
3) and (3) carrying out high-temperature annealing: the annealing temperature is 989-1113 ℃, and the temperature is kept for 28-58 seconds at the temperature;
4) cooling the mixture to room temperature at a cooling rate of 3-24 ℃/s.
TABLE 1 Main parameter control List of the inventive and comparative examples
Figure BDA0002879061920000051
TABLE 2 Table of mechanical property test conditions of examples and comparative examples of the present invention
Figure BDA0002879061920000052
Figure BDA0002879061920000061
As can be seen from the above Table 2, the austenitic stainless steel hot rolled plate blank in the embodiment of the present invention is subjected to a series of rolling heat treatments, and the products in the embodiments 1 to 6 of the present invention have good performances in terms of yield strength and tensile strength relative to the comparative example 7 with different cold rolling reduction, the comparative example 8 with the annealing temperature changing process and the comparative example 9 with the annealing time changing process, and particularly the yield strength, tensile strength and the like are obviously higher than those of the comparative examples, and the products in the embodiments 1 to 6 of the present invention have yield strength of 980 to 1290MPa, tensile strength of 1112 to 1452MPa, elongation of 13.0 to 15.5% and finished product thickness of 0.39 to 0.48 mm.
The embodiments of the present invention are merely preferred examples, and are not intended to limit the scope of the claims.

Claims (3)

1. A production method of austenitic stainless steel with yield strength more than or equal to 980MPa comprises the following steps:
1) cold rolling a stainless steel hot rolled plate with the thickness of 3mm at room temperature, wherein the rolling pass is not less than 4, and the thickness of the stainless steel hot rolled plate is 0.39-0.6 mm; the reduction rate of each pass is controlled to be 33-43%;
2) nitriding, wherein the nitriding temperature is controlled to be 456-628 ℃, the nitriding time is 22-60 min, and the nitriding atmosphere is 10% NH3+60%N2+30%H2The flow rate of the mixed gas is 1.6-2.3L/min;
3) and (3) carrying out high-temperature annealing: the annealing temperature is 989-1113 ℃, and the temperature is kept for 28-58 seconds at the temperature;
4) cooling the mixture to room temperature at a cooling rate of 3-24 ℃/s.
2. The method for producing an ultra-high strength, high plasticity, high nitrogen austenitic stainless steel as claimed in claim 1, wherein: the nitriding temperature is controlled to be 496-592 ℃, the nitriding time is 29-53 min, and the flow rate of the mixed gas is 1.8-2.1L/min.
3. The method for producing an ultra-high strength, high plasticity, high nitrogen austenitic stainless steel as claimed in claim 1, wherein: the high-temperature annealing temperature is controlled to be 989-1016 ℃, and the annealing time is 38-58 seconds.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114622074A (en) * 2022-05-12 2022-06-14 中北大学 Austenitic stainless steel, heat treatment process thereof and application of heat treatment process

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JP2006070313A (en) * 2004-09-01 2006-03-16 Nisshin Steel Co Ltd Surface-nitrided high-strength stainless steel strip superior in delayed-fracture resistance, and manufacturing method therefor
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CN106048409A (en) * 2016-06-27 2016-10-26 武汉科技大学 Method for improving mechanical properties of 301LN austenitic stainless steel
CN110241364A (en) * 2019-07-19 2019-09-17 东北大学 High-strength 304 stainless steel band of modeling nano/submicron grained cold rolling of one kind and preparation method thereof

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114622074A (en) * 2022-05-12 2022-06-14 中北大学 Austenitic stainless steel, heat treatment process thereof and application of heat treatment process

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