CN114959191B - Method for improving corrosion resistance of super austenitic stainless steel by regulating sigma phase - Google Patents
Method for improving corrosion resistance of super austenitic stainless steel by regulating sigma phase Download PDFInfo
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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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
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- 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
- C21D7/00—Modifying the physical properties of iron or steel by deformation
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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
- 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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- 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
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- 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
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- 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
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a method for improving corrosion resistance of super austenitic stainless steel by regulating sigma phase, and relates to the technical field of austenitic stainless steel. The method comprises the steps of casting super austenitic stainless steel liquid into steel ingots, carrying out hot rolling after solution treatment, carrying out surface deformation treatment by a surface large plastic deformation method within the temperature range of 25-300 ℃, heating, and carrying out air cooling or water spraying cooling to complete sigma phase regulation and control. Aiming at the problem that the corrosion resistance of the super austenitic stainless steel is reduced due to the existence of a coarse precipitated phase, the surface of a workpiece is treated by utilizing large plastic deformation of the surface and aging treatment at a lower temperature to obtain a special microstructure state, so that the corrosion resistance is improved, and the corrosion resistance of the super austenitic stainless steel is greatly improved.
Description
Technical Field
The invention relates to the technical field of austenitic stainless steel, in particular to a method for improving corrosion resistance of super austenitic stainless steel by regulating sigma phase.
Background
Super austenitic stainless steel generally refers to austenitic stainless steel with ultra-low carbon and alloying element content as high as more than 50%. The austenitic stainless steel has excellent conventional mechanical property and corrosion resistance, so that the austenitic stainless steel is widely applied to halogen-containing and high-temperature severe corrosion environments.
The superaustenitic stainless steel has high content of alloying elements and is very easy to precipitate harmful second phases under the conditions of solidification and subsequent heating. In order to improve the corrosion resistance of super austenitic stainless steel, homogenization, reduction of precipitation of secondary phases in steel, and adjustment of grain boundary conditions are important methods. The patent publication No. CN113802064A, entitled "a method for improving grain boundary second phase precipitation of super austenitic stainless steel by regulating and controlling grain boundary boron redistribution" proposes that the combination treatment of step solid solution and low temperature heat preservation is utilized to make higher content of boron in the steel to be segregated in the grain boundary, so that the precipitation amount of the grain boundary and the second phase in the crystal is obviously reduced while the size of the crystal grain is not changed, and further the corrosion resistance of the steel is improved. The patent publication No. CN113881830A, entitled "method for improving intergranular corrosion resistance of super austenitic stainless steel", proposes that the amount of coherent twin crystal boundaries can be effectively increased and intergranular corrosion of super austenitic steel can be reduced by boron microalloying, low-temperature aging and crystal boundary engineering treatment, thereby improving the corrosion resistance of super austenitic stainless steel. The patent publication No. CN106636858A, entitled "method for producing high corrosion resistance high nitrogen austenitic stainless steel", proposes that a super austenitic stainless steel with high nitrogen content, low segregation and high purity is obtained by controlling smelting process parameters, and the excellent corrosion resistance benefits from nitrogen alloying and homogenization of components. It is easy to see that, in the preparation process of the super austenitic stainless steel, the microstructure state of the steel is improved by a certain process method, and the purpose of improving the corrosion resistance of the steel is achieved.
However, since the content of the alloying elements of the super austenitic stainless steel is extremely high, particularly the high-molybdenum super austenitic stainless steel, sigma phases generated during solidification are difficult to remove even through subsequent high-temperature homogenization treatment, and the sigma phases distributed in grain boundaries and crystal grains cause great damage to the corrosion resistance of the super austenitic stainless steel. Therefore, it is necessary to improve the state of precipitated phases in super austenitic stainless steel in a targeted manner for the purpose of improving corrosion resistance.
Disclosure of Invention
The invention aims to provide a method for improving the corrosion resistance of super austenitic stainless steel by regulating and controlling sigma phase, so as to solve the problems in the prior art and achieve the purpose of improving the corrosion resistance by improving the state of precipitated phase in the super austenitic stainless steel.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a method for improving corrosion resistance of super austenitic stainless steel by regulating sigma phase, which comprises the following steps:
(1) Pouring the super austenitic stainless steel liquid with qualified chemical components into an ingot;
(2) Carrying out solid solution treatment on the cast ingot to eliminate component segregation and harmful precipitated phases in the cast ingot to obtain an austenite structure with uniform components, and cogging and hot rolling the cast ingot to obtain austenite grains with fine and uniform grain sizes; the initial rolling temperature of hot rolling is 1200 ℃, the final rolling temperature is not lower than 1000 ℃, and the deformation is not lower than 50%;
(3) Carrying out deformation treatment on the surface layer of the working surface of the super austenitic stainless steel obtained in the step (2) by utilizing a surface large plastic deformation method within the temperature range of 25-300 ℃ so as to obtain nano crystals within the range of the depth of the surface layer being 0.5 mm;
(4) And heating the super austenitic stainless steel subjected to deformation treatment, and then performing air cooling or water spraying cooling to finish the sigma phase regulation and control, thereby obtaining a microstructure state with uniformly distributed superfine precipitated phases and austenite phases at the surface layer.
The super austenitic stainless steel is high-Mo high-N austenitic stainless steel (such as 654SMO and 254SMO, the Mo content is 6-7 wt%, and the N content is about 0.45 wt%), or other super austenitic stainless steel containing sigma harmful second phase.
Further, the super austenitic stainless steel liquid comprises the following main chemical components in percentage by mass: c:0.005-0.009, si:0.04-0.09, mn:3.1-5.9, cr:24.2-25.7, ni:19.2-19.7, mo:7.1-7.2, N:0.43-0.48, cu:0.41-0.45, P:0.004-0.006, S:0.004.
furthermore, the temperature of the solution treatment is 1200-1250 ℃, and the time is 20-24h.
Further, the surface large plastic deformation method includes shot peening deformation, impact deformation, surface grinding or friction stir deformation.
Further, the strain amount of the deformation treatment in the step (3) is controlled to be 2.5 to 3.5.
Further, the heating temperature in the step (4) is 800-1000 ℃, and the heating time is 15-60 min.
The invention also provides the super austenitic stainless steel prepared by the method.
The invention discloses the following technical effects:
(1) Aiming at the problem that the corrosion resistance of the super austenitic stainless steel is reduced due to the existence of a coarse precipitated phase, the surface of a workpiece is treated by utilizing large plastic deformation of the surface and aging treatment at a lower temperature, and a special microstructure state is obtained by regulating and controlling a sigma phase, so that the corrosion resistance is improved;
(2) The invention does not depend on the composition change of steel and a special and complex smelting process, but utilizes the later processing to change the microstructure state, thereby having stronger universality on different compositions of super austenitic stainless steel;
(3) The invention only changes the surface structure state of the super austenitic stainless steel and does not change the core structure state, thereby ensuring that the overall performance characteristics of the workpiece are not changed;
(4) After the treatment by the process technology, the corrosion resistance of the super austenitic stainless steel is greatly improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a microstructure of rolled steel sheets of groups 1 and 2 in example 1 of the present invention;
FIG. 2 is a microstructure of rolled steel sheets of groups 1 and 2 in example 2 of the present invention;
FIG. 3 shows microstructures of 1 and 2 groups of rolled steel sheets in example 3 of the present invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the documents are cited. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
Utilizing an Electric Arc Furnace (EAF), an argon oxygen refining furnace (AOD) and a vacuum refining furnace (VOD) to make steel, and obtaining a steel product with chemical components of wt.% C:0.007, si:0.09, mn:5.9, cr:25.7, ni:19.2, mo:7.1, N:0.48, cu0.43, P:0.004, S:0.004 molten steel, the casting temperature is 1580 ℃, and square cast ingots are cast. Carrying out solution treatment on the cast ingot at 1200 ℃ for 20h to obtain a uniform austenite structure state, then discharging the cast ingot from a furnace, and carrying out hot rolling to obtain a steel plate with the thickness of 10mm, wherein the initial rolling temperature is 1200 ℃, the final rolling temperature is 1060 ℃, the deformation amount is 60%, and the grain size is about 80 mu m. Dividing hot rolled steel plates into two groups, and directly carrying out aging treatment at 900 ℃ for 30min and then carrying out water cooling on 1 group; the 2 groups of hot rolled plates firstly carry out large plastic deformation on the surface of the steel plate by utilizing surface mechanical grinding, the local strain is 3, and then the steel plate is heated to 900 ℃ for aging treatment for 30min and then cooled by water. And observing surface layer microstructures of the 1 group of steel plates and the 2 group of steel plates, testing electrochemical parameters in an acid environment, and evaluating the corrosion resistance. A large amount of elongated sigma phases are generated in grain boundaries and in grains after aging treatment of 1 group of hot rolled steel sheets, while fine equiaxed sigma phases having a size of about 0.5 μm are obtained after aging treatment of 2 groups of hot rolled steel sheets and are uniformly distributed around austenite grains having a size of 1 μm, as shown in FIG. 1 (A, B are microstructures of 1 group and 2 groups of rolled steel sheets, respectively). The test shows that the corrosion current density of 1 group of hot rolled steel plate surface samples is 8.1 multiplied by 10 -8 A/cm 2 The corrosion potential is-0.18V; and the corrosion current density of the surface test piece of 2 groups of hot rolled steel plates is 2.9 multiplied by 10 -8 A/cm 2 The corrosion potential is-0.11V, and the corrosion resistance is obviously improved.
Example 2
Utilizing an Electric Arc Furnace (EAF), an argon oxygen refining furnace (AOD) and a vacuum refining furnace (VOD) to make steel, and obtaining a steel product with chemical components of wt.% C:0.009, si:0.04, mn:3.1, cr:24.2, ni:19.3, mo:7.2, N:0.45, cu0.45, P:0.006, S:0.004 molten steel, the casting temperature is 1560 ℃, and the molten steel is cast into a round cast ingot. Carrying out solution treatment at 1250 ℃ for 24h on the cast ingot to obtain a uniform austenite structure state, then discharging the cast ingot out of a furnace and carrying out hot rolling to obtain the thicknessThe steel plate with the temperature of 30mm has the beginning rolling temperature of 1200 ℃, the finishing rolling temperature of 1030 ℃, the deformation of 55 percent and the grain size of about 86 mu m. Dividing hot rolled steel plates into two groups, and directly carrying out aging treatment at 1000 ℃ for 15min and then carrying out water cooling on 1 group; the 2 groups of hot rolled plates are firstly heated to 300 ℃, after the temperature is uniform, the shot blasting is utilized to carry out large plastic deformation on the surface of the steel plate, the local strain is 2.5, and then the steel plate is heated to 1000 ℃ for aging treatment for 15min and then is cooled by water. And observing surface layer microstructures of the 1 group of steel plates and the 2 group of steel plates, testing electrochemical parameters in an acid environment, and evaluating the corrosion resistance. A large amount of strip-like sigma phases were generated in grain boundaries and in grains after aging treatment of 1 group of hot rolled steel sheets, while 2 groups of hot rolled steel sheets obtained after aging treatment of fine equiaxed sigma phases having a size of about 0.2 μm and uniformly distributed in the vicinity of austenite grains having a size of 0.5 μm as shown in FIG. 2 (A, B are microstructures of 1 group and 2 groups of rolled steel sheets, respectively). The test shows that the corrosion current density of the surface layer test sample of 1 group of hot rolled steel plate is 7.5 multiplied by 10 -8 A/cm 2 The corrosion potential is-0.15V; and the corrosion current density of the surface layer sample of 2 groups of hot rolled steel plates is 3.1 multiplied by 10 -8 A/cm 2 The corrosion potential is-0.10V, and the corrosion resistance is obviously improved.
Example 3
Utilizing an Electric Arc Furnace (EAF), an argon oxygen refining furnace (AOD) and a vacuum refining furnace (VOD) to make steel, and obtaining a steel with chemical components of wt.% C:0.005, si:0.06, mn:3.9, cr:24.5, ni:19.7, mo:7.1, N:0.43, cu0.41, P:0.006, S:0.004 molten steel, the casting temperature is 1590 ℃, and the molten steel is cast into a circular cast ingot. Carrying out solution treatment on the cast ingot at 1250 ℃ for 20h to obtain a uniform austenite structure state, then discharging the cast ingot from a furnace, and carrying out hot rolling to obtain a steel plate with the thickness of 20mm, wherein the initial rolling temperature is 1200 ℃, the final rolling temperature is 1070 ℃, the deformation is 65%, and the grain size is about 85 μm. Dividing the hot rolled steel plate into two groups, and directly carrying out aging treatment at 800 ℃ for 60min on 1 group and then carrying out water cooling; the 2 groups of hot rolled plates are firstly heated to 200 ℃, after the temperature is uniform, the surface of the steel plate is subjected to large plastic deformation by using an impact electric pick, the local strain is 3.5, and then the steel plate is heated to 800 ℃ for aging treatment for 60min and then is cooled by water. Observing surface layer microstructures of 1 group and 2 groups of steel plates, testing electrochemical parameters in an acid environment, and evaluating corrosion resistanceIt is also good. A large number of strip-like and band-like sigma phases were generated in grain boundaries and in grains after aging treatment of 1 group of hot rolled steel sheets, while a fine equiaxed sigma phase having a size of about 0.6 μm was obtained after aging treatment of 2 groups of hot rolled steel sheets and uniformly distributed in the vicinity of austenite grains having a size of 1.5 μm as shown in FIG. 3 (A, B are microstructures of 1 group and 2 groups of rolled steel sheets, respectively). The test shows that the corrosion current density of the surface layer sample of 1 group of hot rolled steel plates is 4.5 multiplied by 10 -7 A/cm 2 The corrosion potential is-0.25V; and the corrosion current density of the surface layer sample of the 2 groups of hot rolled steel plates is 3.5 multiplied by 10 -8 A/cm 2 The corrosion potential is-0.07V, and the corrosion resistance is obviously improved.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (2)
1. A method for improving corrosion resistance of super austenitic stainless steel by regulating sigma phase is characterized by comprising the following steps:
(1) Casting the super austenitic stainless steel liquid into an ingot;
(2) Carrying out solution treatment on the cast ingot, and then carrying out hot rolling;
(3) Carrying out deformation treatment on the surface layer of the working surface of the super austenitic stainless steel obtained in the step (2) by utilizing a surface large plastic deformation method within the temperature range of 25-300 ℃;
(4) Heating the super austenitic stainless steel subjected to deformation treatment, and then performing air cooling or water spraying cooling to finish sigma phase regulation and control;
the super austenitic stainless steel liquid comprises the following chemical components in percentage by mass: c:0.005-0.009, si:0.04-0.09, mn:3.1-5.9, cr:24.2-25.7, ni:19.2-19.7, mo:7.1-7.2, N:0.43-0.48, cu:0.41-0.45, P:0.004-0.006, S:0.004;
the temperature of the solution treatment is 1200-1250 ℃, and the time is 20-24h;
the surface large plastic deformation method comprises shot blasting deformation, impact deformation, surface grinding or stirring friction deformation;
controlling the deformation treatment strain amount to be 2.5-3.5 in the step (3);
in the step (4), the heating temperature is 800-1000 ℃, and the heating time is 15-60 min.
2. The super austenitic stainless steel produced according to the method of claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106893831A (en) * | 2017-03-13 | 2017-06-27 | 东北大学 | A kind of super austenitic stainless steel high temperature homogenization processing method |
| CN113637830A (en) * | 2021-07-21 | 2021-11-12 | 广州大学 | Method for accelerating sigma phase nucleation and growth of high-carbon austenitic heat-resistant steel |
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| JP4450701B2 (en) * | 2004-09-01 | 2010-04-14 | 日新製鋼株式会社 | High strength stainless steel strip excellent in delayed fracture resistance and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106893831A (en) * | 2017-03-13 | 2017-06-27 | 东北大学 | A kind of super austenitic stainless steel high temperature homogenization processing method |
| CN113637830A (en) * | 2021-07-21 | 2021-11-12 | 广州大学 | Method for accelerating sigma phase nucleation and growth of high-carbon austenitic heat-resistant steel |
Non-Patent Citations (2)
| Title |
|---|
| 王锐坤.表面喷丸细晶化对Super304H不锈钢晶间腐蚀敏感性和脱敏特性的影响.《中国博士学位论文全文数据库 工程科技Ⅰ辑》.2018,(第07期),第24-25页. * |
| 表面喷丸细晶化对Super304H不锈钢晶间腐蚀敏感性和脱敏特性的影响;王锐坤;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20180715(第07期);第24-25页 * |
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