CN111850425A - Ultrahigh-strength super martensitic stainless steel and preparation method thereof - Google Patents
Ultrahigh-strength super martensitic stainless steel and preparation method thereof Download PDFInfo
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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
- 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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- 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
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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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- 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
- C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
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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
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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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
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
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Abstract
The invention relates to the field of third-generation advanced high-strength steel for oil pipes, and discloses ultrahigh-strength super martensitic stainless steel and a preparation method thereof, wherein the stainless steel comprises the following chemical components in percentage by mass: c: less than or equal to 0.03 percent, Cr: 12.2% -13.7%, Ni: 4.5% -5.5%, Mo: 0.65% -0.75%, Mn: 0.3% -0.5%, Si: 0.25% -0.35%, P: < 0.01%, S: < 0.01%, N: 0.3% -0.4%, V: 0.05 to 0.07 percent of the total weight of the iron and the impurities. According to the invention, on the basis of the components of the traditional super martensitic stainless steel, N and V elements are added, and a room temperature quenching-partitioning process is adopted, so that the super martensitic stainless steel with the tensile strength of 1480-1690 MPa, the yield strength of 800-1000 MPa and the uniform elongation of 15% -17% is finally obtained.
Description
Technical Field
The invention relates to the field of third-generation advanced high-strength steel for oil pipes, in particular to ultrahigh-strength super martensitic stainless steel and a preparation method thereof.
Background
The use of stainless steel is very common in people's daily life, and also has a very important proportion in the industrial field. Stainless steels are classified into many groups, and the present invention relates to a stainless steel which is a super martensitic stainless steel. The concept of super martensitic stainless steels was proposed in the 50's of the 20 th century, mainly by reducing the carbon content to below 0.03% by mass and adding a certain amount of nickel. Due to the ultralow carbon, the corrosion resistance and the welding performance of the super martensitic stainless steel are greatly improved, and the super martensitic stainless steel is gradually well applied to the field of oil and gas conveying pipelines in recent years.
With the development of times, the demand on energy sources is greatly increased, so that oil and gas exploration and exploitation in China are continuously developed to oil and gas fields of deep wells and ultra-deep wells, and the common super martensitic stainless steel cannot meet the requirements of steel for pipelines of the deep wells and the ultra-deep wells. On the premise of ensuring the good weldability and corrosion resistance of the super martensitic stainless steel, the invention aims to improve the toughness of the super martensitic stainless steel.
The quench-split process (i.e., Q & P process) was the first proposed in 2003 by the professor Speer of american scholars, and is an effective heat treatment means for improving the toughness of low carbon steels. However, because the existing super martensitic stainless steel has extremely low carbon content, if the Q & P process is adopted, the toughness of the super martensitic stainless steel cannot be obviously improved, and therefore, the super martensitic stainless steel capable of improving the toughness by utilizing the Q & P process is necessary to be provided.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide an ultrahigh-strength super martensitic stainless steel and a preparation method thereof, wherein the toughness of the super martensitic stainless steel can be improved through a Q & P process.
The technical scheme adopted by the invention is as follows:
the ultrahigh-strength super martensitic stainless steel comprises the following chemical components in percentage by mass: c: less than or equal to 0.03 percent, Cr: 12.2% -13.7%, Ni: 4.5% -5.5%, Mo: 0.65% -0.75%, Mn: 0.3% -0.5%, Si: 0.25% -0.35%, P: < 0.01%, S: < 0.01%, N: 0.3% -0.4%, V: 0.05 to 0.07 percent of the total weight of the alloy, and the balance of iron.
Preferably: the yield strength of the super martensitic stainless steel is 800-1000 MPa, the tensile strength is 1480-1690 MPa, and the uniform elongation is 15-17%.
A preparation method of the ultra-high strength super martensitic stainless steel comprises the following steps:
smelting the components of the ultrahigh-strength super martensitic stainless steel, and then performing pressure processing to obtain a hot rolled plate, wherein the pressure processing adopts a hot rolling processing mode after forging;
carrying out quenching-partition heat treatment on a hot rolled plate to obtain the ultrahigh-strength super martensitic stainless steel;
when quenching-partition heat treatment is carried out, the temperature of a hot rolled plate is raised to 1000-1100 ℃, heat preservation is carried out for 300-600 s, then the temperature is reduced to room temperature through water quenching, then the hot rolled plate is heated to 300-500 ℃, heat preservation is carried out for 2-40 min, and finally air cooling is carried out to the room temperature.
Preferably: before forging, heating the smelted blank to 1100-1200 ℃, and forging after keeping the temperature for 60-90 min.
Preferably: before hot rolling, the temperature of the forged piece obtained by forging is raised to 1200-1300 ℃, heat preservation is carried out for 60-90 min, and then hot rolling is carried out.
Preferably: the thickness of the hot-rolled plate is 4-5 mm.
The invention has the following advantages:
in the components of the ultrahigh-strength super martensitic stainless steel, in order to ensure that the toughness of the ultrahigh-strength super martensitic stainless steel can be improved through a quenching-partitioning process, 0.3-0.4% of nitrogen and 0.05-0.07% of vanadium are added into the components of the ultrahigh-strength super martensitic stainless steel, so that the partitioning effect of replacing carbon with nitrogen can be realized when a Q & P process is carried out, and nitrogen can be diffused into residual austenite and a martensite/austenite boundary from martensite under the driving force of a partitioning temperature. A high content of nitrogen at the boundary leads to the formation of reversed austenite, so that the toughness is increased. The content of C in the ultra-high strength super martensitic stainless steel is less than or equal to 0.03 percent, wherein the content of carbon is still maintained at an ultra-low level, so the ultra-high strength super martensitic stainless steel also has excellent weldability and good corrosion resistance.
According to the preparation method of the ultrahigh-strength super martensitic stainless steel, the blank obtained by smelting is forged and then is subjected to hot rolling, so that as-cast porosity generated in the smelting process is eliminated, the microstructure is optimized, the adverse effect of internal defects of steel on mechanical properties is prevented, and good tissue conditions are provided for quenching-partitioning heat treatment; and when quenching-partitioning heat treatment is carried out, heating the blank to 1000-1100 ℃, preserving heat for 300-600 s, and then cooling to room temperature through water quenching, wherein the structure is lath martensite and retained austenite. And then heating to 300-500 ℃ and carrying out heat preservation for 2-40 min, wherein the diffusion rate of nitrogen in martensite is greater than that in austenite, so that nitrogen can be enriched in a martensite-austenite interface at the temperature, and a high local driving force is provided for the formation of reverse austenite. And finally, water quenching is carried out to room temperature, and the structure in the steel is lath martensite, residual austenite and reversed austenite. The nitrogen distribution in the invention replaces the traditional carbon distribution process, so that the Q & P process is applied to the super martensitic stainless steel, and the toughness of the super high strength super martensitic stainless steel can be improved through the Q & P process.
Furthermore, in order to enable the forge piece to be easy to process and not to crack, the blank obtained by smelting is heated to 1100-1200 ℃, and is forged after heat preservation is carried out for 60-90 min.
Furthermore, before hot rolling, the temperature of the forged piece obtained by forging is raised to 1200-1300 ℃, and after heat preservation is carried out for 60-90 min, the purpose is to refine crystal grains of the steel and eliminate defects in the steel, so that the steel structure is compact.
Drawings
FIG. 1 is a process flow diagram of the quenching-partitioning heat treatment steps of the present invention.
FIG. 2 shows EBSD structure photographs of example 1 of the present invention.
FIG. 3 is a photograph of EBSD structure in example 2 of the present invention.
FIG. 4 is a photograph of EBSD structure of example 3 of the present invention.
Detailed Description
The present invention is described in detail below with reference to the drawings and examples, but the scope of the present invention is not limited by the examples.
The invention carries out N alloying on the basis of the components of the conventional super martensitic stainless steel, takes N as an element for expanding an austenite phase region, and adopts nitrogen distribution to replace the traditional carbon distribution, thereby leading the super martensitic stainless steel to have excellent strength and good toughness, and good weldability and corrosion resistance.
The invention relates to an ultrahigh strength super martensitic stainless steel, which comprises the following chemical components in percentage by mass: c: less than or equal to 0.03 percent, Cr: 12.2% -13.7%, Ni: 4.5% -5.5%, Mo: 0.65% -0.75%, Mn: 0.3% -0.5%, Si: 0.25% -0.35%, P: < 0.01%, S: < 0.01%, N: 0.3% -0.4%, V: 0.05 to 0.07 percent of the total weight of the alloy, and the balance of iron.
The preparation method of the ultrahigh-strength super martensitic stainless steel comprises the following steps:
smelting chemical components of the ultrahigh-strength super martensitic stainless steel, forging, hot rolling to obtain a hot rolled plate, quenching-partitioning heat treatment of the hot rolled plate to obtain the ultrahigh-strength super martensitic stainless steel, wherein during the quenching-partitioning heat treatment, the temperature of a blank is raised to 1000-1100 ℃, the temperature is kept for 300-600 s, then the blank is cooled to room temperature through water quenching, then the blank is heated to 300-500 ℃ and kept for 2-40 min, and finally air cooling is carried out to the room temperature.
The pressure processing mode of the invention is hot rolling after forging, before forging, the smelted blank is heated to 1100-1200 ℃, and is kept warm for 60-90 min, and then forging is carried out; before hot rolling, the temperature of the forge piece is increased to 1200-1300 ℃, the temperature is kept for 60-90 min, and then the forge piece is hot rolled to a plate with the thickness of 4-5 mm.
The chemical compositions of the ultra-high strength super martensitic stainless steel of each embodiment of the invention are shown in table 1, and the quenching-partitioning heat treatment steps are shown in fig. 1.
TABLE 1
Example 1
Smelting according to the chemical components shown in the table 1, heating the smelted blank to 1100 ℃, keeping the temperature for 90min, and forging the blank into a forged plate with the thickness of 35 mm. Then the temperature is raised to 1200 ℃, and hot rolling is carried out after heat preservation is carried out for 90min, and finally, plates with the thickness of 4.0mm are rolled.
Carrying out quenching heat treatment on the rolled plate: and (3) heating the steel plate to 1000 ℃, preserving heat for 600s, and then performing water quenching to room temperature. Then preserving the heat for 40min at 300 ℃, and finally cooling to room temperature in air.
FIG. 2 is an EBSD phase diagram of the steel structure of example 1, wherein the gray area is a martensite structure and the white area is an austenite structure. After quenching-partitioning, the inverse austenite with fine grains begins to form in the structure, as shown in the black circle. The reversed austenite recovered in the structure is uniformly distributed among the martensite laths, so that in the mechanical stretching process, cracks can be prevented from permeating into another martensite grain from the martensite grain, and the toughness of the martensite lath is effectively improved. The tensile strength of the material reaches 1480MPa, the yield strength reaches 810MPa, and the elongation after fracture reaches 15.9 percent.
Example 2
Smelting according to the chemical components shown in the table 1, heating the smelted blank to 1150 ℃, keeping the temperature for 80min, and forging the blank into a forged plate with the thickness of 35 mm. Then the temperature is raised to 1250 ℃, and hot rolling is carried out after heat preservation is carried out for 70min, and finally, plates with the thickness of 4.4mm are rolled.
Carrying out quenching heat treatment on the rolled plate: and (3) heating the steel plate to 1050 ℃, preserving the temperature for 450s, and then performing water quenching to room temperature. Then preserving the heat for 20min at 400 ℃, and finally cooling to room temperature in air.
FIG. 3 is an EBSD phase diagram of the steel structure of example 2, wherein the gray area is a martensite structure and the white area is an austenite structure. After quenching-partitioning, the inverse austenite with fine grains begins to form in the structure, as shown in the black circle. The reversed austenite recovered in the structure is uniformly distributed among the martensite laths, so that in the mechanical stretching process, cracks can be prevented from permeating into another martensite grain from the martensite grain, and the toughness of the martensite lath is effectively improved. The tensile strength of the material reaches 1690MPa, the yield strength reaches 980MPa, and the elongation after fracture reaches 15.2 percent.
Example 3
Smelting according to the chemical components shown in the table 1, heating the smelted blank to 1200 ℃, keeping the temperature for 60min, and forging the blank into a forged plate with the thickness of 35 mm. Then heating to 1300 ℃, preserving heat for 60min, and then carrying out hot rolling to finally roll into a plate with the thickness of 5.0 mm.
Carrying out quenching heat treatment on the rolled plate: heating the steel plate to 1100 ℃, preserving heat for 300s, and then quenching the steel plate to room temperature. Then preserving the heat for 2min at 500 ℃, and finally cooling to room temperature in air.
FIG. 4 is an EBSD phase diagram of the steel structure of example 3, wherein the gray region is a martensite structure and the white region is an austenite structure. After quenching-partitioning, the inverse austenite with fine grains begins to form in the structure, as shown in the black circle. The reversed austenite recovered in the structure is uniformly distributed among the martensite laths, so that in the mechanical stretching process, cracks can be prevented from permeating into another martensite grain from the martensite grain, and the toughness of the martensite lath is effectively improved. The tensile strength of the material reaches 1560MPa, the yield strength reaches 890MPa, and the elongation after fracture reaches 16.8 percent.
Claims (6)
1. The ultrahigh-strength super martensitic stainless steel is characterized by comprising the following chemical components in percentage by mass: c: less than or equal to 0.03 percent, Cr: 12.2% -13.7%, Ni: 4.5% -5.5%, Mo: 0.65% -0.75%, Mn: 0.3% -0.5%, Si: 0.25% -0.35%, P: < 0.01%, S: < 0.01%, N: 0.3% -0.4%, V: 0.05 to 0.07 percent of the total weight of the alloy, and the balance of iron.
2. The ultra-high strength, super martensitic stainless steel of claim 1, wherein: the tensile strength of the super martensitic stainless steel is 1480-1690 MPa, the yield strength is 800-1000 MPa, and the uniform elongation is 15-17%.
3. A preparation method of the ultra-high strength super martensitic stainless steel is characterized by comprising the following steps:
smelting the components of the ultrahigh-strength super martensitic stainless steel according to claim 1, and then performing pressure processing to obtain a hot rolled plate, wherein the pressure processing adopts a processing mode of hot rolling after forging;
carrying out quenching-partition heat treatment on a hot rolled plate to obtain the ultrahigh-strength super martensitic stainless steel;
when quenching-partition heat treatment is carried out, the temperature of a hot rolled plate is raised to 1000-1100 ℃, heat preservation is carried out for 300-600 s, then the temperature is reduced to room temperature through water quenching, then the hot rolled plate is heated to 300-500 ℃, heat preservation is carried out for 2-40 min, and finally air cooling is carried out to the room temperature.
4. The method of manufacturing an ultra-high strength, super martensitic stainless steel as claimed in claim 3 wherein: before forging, heating the smelted blank to 1100-1200 ℃, and forging after keeping the temperature for 60-90 min.
5. The method of manufacturing an ultra-high strength, super martensitic stainless steel as claimed in claim 4 wherein: before hot rolling, the temperature of the forged piece obtained by forging is raised to 1200-1300 ℃, heat preservation is carried out for 60-90 min, and then hot rolling is carried out.
6. The method of manufacturing an ultra-high strength, super martensitic stainless steel as claimed in claim 5 wherein: the thickness of the hot rolled plate is 4-5 mm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113355494A (en) * | 2021-05-14 | 2021-09-07 | 西安文理学院 | Method for improving corrosion resistance of martensitic stainless steel |
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| US5167731A (en) * | 1990-07-30 | 1992-12-01 | Nkk Corporation | Martensitic stainless steel for an oil well |
| CN103320707A (en) * | 2013-06-20 | 2013-09-25 | 宝山钢铁股份有限公司 | High-strength stainless steel tube with excellent toughness and manufacturing method thereof |
| CN108517471A (en) * | 2018-03-29 | 2018-09-11 | 太原钢铁(集团)有限公司 | Oil well corrosion-resistant super martensitic stain less steel pipe and its manufacturing method |
| CN111363983A (en) * | 2020-04-13 | 2020-07-03 | 西安建筑科技大学 | Super martensitic stainless steel with ultrahigh strength and toughness and preparation method thereof |
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2020
- 2020-07-31 CN CN202010760791.3A patent/CN111850425A/en active Pending
Patent Citations (4)
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|---|---|---|---|---|
| US5167731A (en) * | 1990-07-30 | 1992-12-01 | Nkk Corporation | Martensitic stainless steel for an oil well |
| CN103320707A (en) * | 2013-06-20 | 2013-09-25 | 宝山钢铁股份有限公司 | High-strength stainless steel tube with excellent toughness and manufacturing method thereof |
| CN108517471A (en) * | 2018-03-29 | 2018-09-11 | 太原钢铁(集团)有限公司 | Oil well corrosion-resistant super martensitic stain less steel pipe and its manufacturing method |
| CN111363983A (en) * | 2020-04-13 | 2020-07-03 | 西安建筑科技大学 | Super martensitic stainless steel with ultrahigh strength and toughness and preparation method thereof |
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| 吕香等: "V对超级马氏体不锈钢组织及力学性能的影响", 《材料热处理学报》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113355494A (en) * | 2021-05-14 | 2021-09-07 | 西安文理学院 | Method for improving corrosion resistance of martensitic stainless steel |
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Application publication date: 20201030 |