CN113046654A - High-plasticity high-strength high-corrosion-resistance stainless steel and preparation method thereof - Google Patents
High-plasticity high-strength high-corrosion-resistance 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
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
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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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
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- C21D6/00—Heat treatment of ferrous alloys
- C21D6/007—Heat treatment of ferrous alloys containing Co
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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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/04—Hardening by cooling below 0 degrees Celsius
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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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
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- 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
- C22C33/06—Making ferrous alloys by melting using master alloys
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
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Abstract
The invention discloses high-plasticity high-strength high-corrosion-resistance stainless steel and a preparation method thereof, wherein the high-plasticity high-strength high-corrosion-resistance stainless steel comprises, by mass, 8.0-11.0% of Co and 8.0-11.0% of Ni6.0-9.0%, 12.0-15.0% of Cr, 0.4-1.5% of Ti, 4.0-7.0% of Mo, 0.08-1.0% of Mn, 0.08-0.2% of Si, less than or equal to 0.05% of C, less than or equal to 0.035% of P, less than or equal to 0.030% of S and the balance of Fe. The method comprises the following steps: (1) smelting and casting stainless steel; (2) forging or hot rolling cogging; (3) and (6) heat treatment. The elongation percentage of the stainless steel of the invention is up to 22.8 percent, the yield strength can reach 1700MPa, the tensile strength can reach 2000MPa, and the fracture toughness is higher than 100 MPa.m1/2And the pitting potential Epit is greater than 0.42VSCE。
Description
Technical Field
The invention relates to high-plasticity high-strength high-corrosion-resistance stainless steel and a preparation method thereof, belonging to the field of martensitic stainless steel.
Background
The martensite precipitation strengthened stainless steel is a new steel bell developed in the 60's of the 20 th century. The strength of the maraging strengthening stainless steel and the corrosion resistance of the stainless steel are both provided. Due to its excellent comprehensive mechanical properties, it is commonly used in the fields of high-end equipment such as aviation, aerospace and navigation.
The main reason why the martensite precipitation strengthening stainless steel can realize the ultrahigh strength is that the martensite phase transformation strengthening and the aged precipitation strengthening are superposed; the corrosion resistance is mainly caused by the fact that a passive film is formed on the surface of the stainless steel due to the addition of Cr and Mo, and the stainless steel has rustproof performance. Table 1 shows the composition and properties of commercially available high-strength stainless steels. It can be seen that the current high-strength stainless steel has the following problems: firstly, the ductility and toughness are poorer when the strength is higher; secondly, when the mechanical property is excellent, the corrosion resistance is poor; it is difficult to unify the strength, ductility and toughness and corrosion resistance to obtain excellent comprehensive performance. Therefore, how to improve the obdurability of the stainless steel on the premise of ensuring the corrosion resistance of the stainless steel so as to meet higher requirements of engineering application on the comprehensive performance of the stainless steel is a research hotspot and difficulty in the field of stainless steel, and therefore, the research on novel ultrahigh-strength maraging stainless steel with independent intellectual property rights is urgent.
Table 1 commercial high strength stainless steel compositions and properties thereof currently on the market
The high content of Co ensures that the mechanical property of the high-strength stainless steel is excellent. When the content of Co is low or 0, the comprehensive mechanical property performance is low. The Co is added into the high-strength stainless steel to form a double-edged sword, the Co can reduce the solubility of Ti and Mo in the martensite matrix, and a precipitate phase containing Mo or Ti is formed, so that the strength is improved. Meanwhile, Co can also hinder the recovery of dislocation, reduce the size of a precipitated phase and stabilize a martensite matrix, can generate higher secondary hardening, and is a guarantee for better mechanical properties such as strength and the like. Therefore, to obtain excellent mechanical properties, a large amount of Co element is inevitably added. However, the spinodal decomposition of Cr is promoted by the addition of Co to the martensitic stainless steel, and the higher the content of Co, the greater the spinodal decomposition degree of Cr, which lowers the pitting corrosion resistance of the substrate. Therefore, an appropriate amount of Co is added. The design of the invention reduces the content of Co, reverse transformation austenite is introduced by adjusting the content of Co and Ni and applying a proper heat treatment process, and the reverse transformation austenite in the metastable state generates a TRIP effect in the deformation process, thereby providing great guarantee for the plasticity and toughness of the material.
The invention patent application with publication number CN 101205595A discloses a strong toughness ultrahigh strength stainless steel and a manufacturing method thereof, wherein the stainless steel comprises the following components (wt.%), C is less than or equal to 0.03%, Mn is less than or equal to 0.10%, Si is less than or equal to 0.10%, Cr is 12-14%, Ni is 2-6%, Co is 11-13%, Mo is 3.5-5.5%, V is 0.15-0.25%, Nb is less than or equal to 0.15%, W is 0.8-1.2%, N is less than or equal to 0.005%, and the balance is Fe; the yield strength can reach 1400MPa, the tensile strength can reach 1800MPa, and the plasticity is 11-28%. The alloy has excellent mechanical properties, but the alloy has more noble metal elements such as Co, V, W and the like, the cost and the price of raw materials are high, and Co can promote the spoke decomposition of Cr and reduce the corrosion resistance of the alloy; although Cr and Mo were added, the corrosion resistance was not evaluated in the present invention.
The invention patent application with publication number CN 110358983A discloses a precipitation hardening martensitic stainless steel and a preparation method thereof, wherein the stainless steel comprises the following specific chemical components (wt.%), 0.14-0.20% of C, 13.0-16.0% of Cr, 0.5-2.0% of Ni, 12.0-15.0% of Co, 4.5-5.5% of Mo, 0.4-0.6% of V, less than or equal to 0.1% of Si, less than or equal to 0.5% of Mn, less than or equal to 0.01% of P, less than or equal to 0.01% of S, less than or equal to 0.10% of N, and the balance of Fe. The tensile strength is 1840-1870 MPa, the yield strength is 780-820 MPa, and the elongation is 12.5-14%. The Co content of the invention is high, so that the raw material cost is high; the increased content of Co promotes the decomposition of Cr swaths, further creating Cr-poor regions and Cr-rich regions, which have poor corrosion resistance. The C content is high, Cr-rich carbide is easily formed in the aging process, and the corrosion resistance is reduced. The heat treatment process adopts a double-time aging process, the process is complex, and the plasticity and toughness of the material are insufficient.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems of higher cost of raw materials, lower corrosion resistance, plasticity and toughness and the like of the traditional ultrahigh-strength stainless steel, the invention provides a high-plasticity high-strength high-corrosion resistance stainless steel and a preparation method of the martensitic stainless steel.
The purpose of the invention is realized as follows:
the invention relates to a stainless steel with high plasticity, high strength and high corrosion resistance and a preparation method thereof, wherein the stainless steel comprises the following components: the alloy comprises, by mass, 8.0-11.0% of Co, 6.0-9.0% of Ni, 12.0-15.0% of Cr, 0.4-1.5% of Ti, 4.0-7.0% of Mo, 0.08-1.0% of Mn, 0.08-0.2% of Si, less than or equal to 0.05% of C, less than or equal to 0.035% of P, less than or equal to 0.030% of S, and the balance of Fe.
The invention principle and the component design basis of the high-strength high-plasticity high-corrosion-resistance stainless steel are as follows:
the invention principle is as follows: compared with the stainless steel of other inventions, the stainless steel of the invention has lower Co content, and forms a Mo-rich phase and Ni phase by adjusting the contents of Ti, Mo and Si3(Ti, Mo) to improve the strength. At the same time, the contents of Co, Ni and Mn are also adjusted to ensure that reverse austenite is precipitated in the matrix mainly through Ni3Ti is converted into reverse transformed austenite and membranous reverse austenite precipitated among laths, and the metastable reverse austenite enables the material to generate a TRIP (transformation Induced plasticity) effect in the deformation process, so that the strength and the plasticity are further improved; meanwhile, the reversed austenite can also effectively hinder the expansion of cracks in the process of fatigue or impact, fully release stress concentration and improve the plasticity and toughness of the material.
The basis of component design is as follows: co is one of the important elements of the invention, can improve Ms point and ensure that the matrix is martensite. Co is an austenite stabilizing element. Co can improve the mechanical property of the material and can also reduce the corrosion resistance of the material. And Co is also expensive. Comprehensively considering that the mass percentage of Co is controlled to be 8.0-11.0%.
Ni is an important element for forming intermetallic compounds, and is formed by forming B2-Ni (Ti, Mn) and eta-Ni in the early stage3(Ti, Mo) for strengthening matrix, eta-Ni3(Ti, Mo) is also the core of the Mo-R' rich phase nucleation; ni is an austenite stabilizing element, can promote the formation of reversed austenite in the aging process, and improves the plasticity and toughness of the material. However, too high a Ni content will result in too great a sacrifice in material strength. Comprehensively considering that the mass percentage of Ni is controlled to be 6.0-9.0%.
Mo is an important precipitation strengthening element. Mo is formed as Mo-rich phase and Ni3One of the main elements of (Ti, Mo). Mo is also an effective corrosion-resistant element, and the corrosion resistance of the material can be obviously improved by adding Mo. Meanwhile, Mo is also a forming element of ferrite, and the excessive content of Mo increases the precipitation tendency of delta ferrite, so that the content of Mo is increased, and the performance of the material is deteriorated. The mass percentage of Mo is comprehensively considered to be controlled to be 4.0-7.0%.
Cr is an important element in stainless steel. In order to ensure the corrosion resistance of the stainless steel, the mass percentage of the stainless steel is generally more than 10 percent. However, Cr is a ferrite-forming element, and the content thereof is too high, so that the content of delta ferrite in the matrix is increased, and the toughness and corrosion resistance of the material are affected. Therefore, the mass percentage of Cr is controlled to be 12.0-15.0%.
Si can effectively inhibit the precipitation and growth of carbides in the martensite matrix in the tempering process, thereby preventing the occurrence of a Cr-poor area to reduce the corrosion resistance; however, too high a content of Si may seriously deteriorate the plasticity of the material. Comprehensively considering, the mass percentage of Si is controlled to be 0.08-0.20%.
Ti is a main strengthening phase forming element, which can form Ni-Ti clusters at the initial stage in preparation for the subsequent precipitation of a strengthening phase. When the content of Ti is excessive, the tendency of precipitation phase at the boundary of the martensite lath is increased, and when the precipitation phase at the half-edge boundary of the martensite is excessive, the precipitation phase is easy to be changed into a crack source and expands along the boundary of the martensite lath to initiate quasi-cleavage cracking. Comprehensively considering, the mass percentage of Ti should be controlled to be 0.40-1.5%.
Mn mainly participates in the precipitation of a nano phase to form an Ni (Mn, Ti, Mo) intermetallic compound, so that a small amount of elements of Ti and Mo can be replaced; mn is an austenite stabilizing element and is an important element affecting reverse austenite. However, too high Mn content causes serious segregation of the steel slab, large thermal stress and structural stress, and deterioration of weldability. Comprehensively considering, the mass percentage of Mn is controlled to be 0.08-1.00%.
C exists in the stainless steel as an impurity element, and when the content of C is too high, MX or M is formed23C6Since the carbide (M ═ Cr, Ti) seriously deteriorates the toughness and corrosion resistance of steel, the C content is strictly controlled to 0.02% or less.
The invention relates to high-plasticity high-strength high-corrosion-resistance stainless steel and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) selecting raw materials of pure iron, metal chromium, metal nickel, metal manganese, metal molybdenum, metal cobalt, metal titanium, iron silicon and iron carbon blocks according to the mass percentage of each element in the stainless steel, smelting and casting to form an alloy ingot;
(2) forging or hot rolling cogging;
(3) and (6) heat treatment.
After the alloy is smelted, cooling and forming to room temperature, cutting off a riser, removing the skin, and then entering a thermal mechanical treatment process. Hot rolling and cogging are carried out, and then heat treatment is carried out, so that a structure with uniform and fine size can be obtained, and the structure has higher strength and corrosion resistance.
In the step (1), smelting and casting processes are carried out in vacuum or argon protection, and stirring technology is utilized to uniformly mix metal solution in the smelting process.
In the step (2), the forging or rolling may be performed by casting or rolling into a square ingot or a round ingot; the technological conditions of forging or hot rolling cogging are as follows: heating the casting blank to 1100-1300 ℃, preserving heat for 10-24 h, and discharging for forging or rolling; the forging or hot rolling starting temperature is more than or equal to 1050 ℃, the finish forging or finish rolling temperature is more than or equal to 900 ℃, the total hot rolling load of the plate is more than or equal to 40%, and the plate is cooled in the air after hot rolling deformation. Hot forging, pass rolling or universal rolling can be used for cogging.
Further, in the step (3), the process conditions of the heat treatment are as follows: cooling in air after forging or hot rolling deformation; preserving heat at 1050-1200 ℃, quenching and cooling in an ice-water mixture at 0 ℃ after the heat preservation time is 60-120 min, then carrying out liquid nitrogen cryogenic treatment for 8h, and recovering to room temperature after the cryogenic treatment; according to the performance requirement, the steel plate is aged for 1-500 h at 450-600 ℃, and then air-cooled or quenched to room temperature.
Compared with the prior art, the invention has the beneficial effects that:
(1) the volume fraction of the inverted austenite is controlled by adjusting the contents of Co, Ni and Mn, and high strength, high plasticity and high corrosion resistance are obtained, the elongation of the stainless steel is as high as 22.8 percent, the yield strength can reach 1700MPa, the tensile strength can reach 2000MPa, and the fracture toughness is higher than 100 MPa.m1/2And the pitting corrosion point Epit is more than 0.42VSCE. (2) The preparation method of the high-strength high-plasticity high-corrosion-resistance stainless steel is simple, the process controllability is strong, and the industrial production is easy to realize.
Drawings
FIG. 1 is an engineering stress-strain curve of example 1;
FIG. 2 EBSD map of example 2;
FIG. 3 is the metallographic morphology of example 3 after the corrosion resistance test;
fig. 4 shows XRD curves and reversed austenite contents for different examples 4 and 3.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Example 1
Selecting pure iron, chromium metal, nickel metal, manganese metal, molybdenum metal, cobalt metal, titanium metal, iron silicon and iron carbon block as raw materials, wherein the stainless steel comprises the following components in percentage by mass: co 8.0, Cr 12.0, Mn 1.0, Mo 7.0, Ni 9.0, Si 0.1, Ti 0.4, C0.02, and the balance Fe.
Casting into alloy cast ingots through arc melting or induction melting; smelting is carried out in vacuum or under the protection of argon, and stirring technology is utilized to uniformly mix the metal solution in the smelting process; casting under vacuum or argon protection to form square ingot or round ingot;
the ingot is hot-rolled and cogging by adopting a rolling mill, the hot-rolling scheme is that the casting blank is heated to 1150 +/-10 ℃, the temperature is kept for 24 hours, then the casting blank is discharged from a furnace for rolling, the hot-rolling starting temperature is 1150 +/-20 ℃, the finish rolling temperature is more than or equal to 950 ℃, the total hot-rolling amount of the plate is more than or equal to 70 percent, and the ingot is cooled in the air after hot-rolling deformation; the ingot casting can be cogging by hot forging, pass rolling or universal rolling;
the plate is subjected to heat preservation at 1200 ℃, the heat preservation time is 60min, and protective gas is not needed during heating; after heat preservation, cooling the mixture in ice water at 0 ℃, then carrying out liquid nitrogen cryogenic treatment for 8 hours, and recovering the temperature to room temperature after cryogenic treatment; aging at 480 deg.C for 500h, and air cooling to room temperature.
The properties of example 1 are shown in Table 1, yield strength 1650MPa, tensile strength 2000MPa, elongation 18.3%, and fracture toughness 115MPa m1/2Pitting potential of 0.47VSCE. FIG. 1 is a graph showing the mechanical properties of example 1, which is high in strength and good in plasticity.
Example 2
Selecting pure iron, chromium metal, nickel metal, manganese metal, molybdenum metal, cobalt metal, titanium metal, iron silicon and iron carbon block as raw materials, wherein the stainless steel comprises the following components in percentage by mass: co 9.0, Cr 12.0, Mn 0.8, Mo 5.0, Ni 8.0, Si 0.1, Ti 1.0, C0.02, and the balance Fe.
Casting into alloy cast ingots through arc melting or induction melting; smelting is carried out in vacuum or under the protection of argon, and stirring technology is utilized to uniformly mix the metal solution in the smelting process; casting under vacuum or argon protection to form square ingot or round ingot;
the ingot is hot-rolled and cogging by adopting a rolling mill, the hot-rolling scheme is that the casting blank is heated to 1150 +/-10 ℃, the temperature is kept for 24 hours, then the casting blank is discharged from a furnace for rolling, the hot-rolling starting temperature is 1150 +/-20 ℃, the finish rolling temperature is more than or equal to 950 ℃, the total hot-rolling amount of the plate is more than or equal to 80 percent, and the ingot is cooled in the air after hot-rolling deformation; the ingot casting can be cogging by hot forging, pass rolling or universal rolling;
the plate is subjected to heat preservation at 1050 ℃, the heat preservation time is 60min, and protective gas is not needed during heating; after heat preservation, cooling the mixture in ice water at 0 ℃, then carrying out liquid nitrogen cryogenic treatment for 8 hours, and recovering the temperature to room temperature after cryogenic treatment; aging at 500 deg.C for 100h, and air cooling to room temperature. FIG. 2 is an EBSD (Electron Back stress diffraction) diagram of the high-strength high-plasticity high-corrosion-resistance stainless steel prepared in example 2, wherein the EBSD diagram shows that blocks and sub-blocks are arranged in the prior austenite and are accompanied by a large number of small-angle grain boundaries, and the EBSD diagram is a typical martensite hierarchical structure, and shows that the material can obtain a full martensite structure without retained austenite after the heat treatment process.
The properties of example 2 are shown in Table 1, with a yield strength of 1440MPa, a tensile strength of 1680MPa, an elongation of 23.5% and a fracture toughness of 105MPa m1/2Pitting potential of 0.42VSCE。
Example 3
Selecting pure iron, chromium metal, nickel metal, manganese metal, molybdenum metal, cobalt metal, titanium metal, iron silicon and iron carbon block as raw materials, wherein the stainless steel comprises the following components in percentage by mass: co 11.0, Cr 14.0, Mn 0.1, Mo 6.0, Ni 7.0, Si 0.2, Ti 0.7, C0.02, and the balance Fe.
Casting into alloy cast ingots through arc melting or induction melting; smelting is carried out in vacuum or under the protection of argon, and stirring technology is utilized to uniformly mix the metal solution in the smelting process; casting under vacuum or argon protection to form square ingot or round ingot;
the ingot is hot-rolled and cogging by adopting a rolling mill, the hot-rolling scheme is that the casting blank is heated to 1150 +/-10 ℃, the temperature is kept for 24 hours, then the casting blank is discharged from a furnace for rolling, the hot-rolling starting temperature is 1150 +/-20 ℃, the finish rolling temperature is more than or equal to 950 ℃, the total hot-rolling amount of the plate is more than or equal to 40 percent, and the ingot is cooled in the air after hot-rolling deformation; the ingot casting can be cogging by hot forging, pass rolling or universal rolling;
the plate is subjected to heat preservation at 1050 ℃, the heat preservation time is 60min, and protective gas is not needed during heating; after heat preservation, cooling the mixture in ice water at 0 ℃, then carrying out liquid nitrogen cryogenic treatment for 8 hours, and recovering the temperature to room temperature after cryogenic treatment; aging at 480 deg.C for 500h, and air cooling to room temperature.
The properties of example 3 are shown in Table 1, with a yield strength of 1700MPa, a tensile strength of 2000MPa, an elongation of 19.5% and a fracture toughness of 104MPa m1/2Pitting potential of 0.46VSCE. Fig. 3 is a gold phase diagram of the corrosion surface of the high-strength, high-plasticity and high-corrosion-resistance stainless steel prepared in example 3 after a corrosion resistance test, and it can be seen that the corrosion surface is smooth, has no corrosion products, and has strong corrosion resistance.
Example 4
Selecting pure iron, chromium metal, nickel metal, manganese metal, molybdenum metal, cobalt metal, titanium metal, iron silicon and iron carbon block as raw materials, wherein the stainless steel comprises the following components in percentage by mass: co 11.0, Cr 15.0, Mn 1.0, Mo 4.0, Ni 6.0, Si 0.2, Ti 1.5, C0.02, and the balance Fe.
Casting into alloy cast ingots through arc melting or induction melting; smelting is carried out in vacuum or under the protection of argon, and stirring technology is utilized to uniformly mix the metal solution in the smelting process; casting under vacuum or argon protection to form square ingot or round ingot;
the ingot is hot-rolled and cogging by adopting a rolling mill, the hot-rolling scheme is that the casting blank is heated to 1150 +/-10 ℃, the temperature is kept for 24 hours, then the casting blank is discharged from a furnace for rolling, the hot-rolling starting temperature is 1150 +/-20 ℃, the finish rolling temperature is more than or equal to 950 ℃, the total hot-rolling amount of the plate is more than or equal to 60 percent, and the ingot is cooled in the air after hot-rolling deformation; the ingot casting can be cogging by hot forging, pass rolling or universal rolling;
the plate is subjected to heat preservation at 1050 ℃, the heat preservation time is 60min, and protective gas is not needed during heating; after heat preservation, cooling the mixture in ice water at 0 ℃, then carrying out liquid nitrogen cryogenic treatment for 8 hours, and recovering the temperature to room temperature after cryogenic treatment; aging at 500 deg.C for 100h, and air cooling to room temperature.
The properties of example 4 are shown in Table 1, the yield strength is 1490MPa, the tensile strength is 1710MPa, the elongation is 22.8%, and the fracture toughness is 117MPa m1/2Pitting potential of 0.51VSCE. FIG. 4 shows an embodimentThe XRD curves and the reversed austenite contents of example 4 and example 3 show that no reversed austenite appears after 100h aging and Ni appears after 500h aging3The transformation of Ti into the inverted austenite. The soft phases generate TRIP effect when being deformed, and can effectively improve the plasticity and toughness.
The test methods for the corrosion resistance, hardness and tensile mechanical properties of the high-strength, high-plasticity and high-corrosion-resistance stainless steel in the above examples are as follows.
(1) Fracture toughness: in-plane strain fracture toughness K of metal materials according to GB/T4161-2007ITest method C tests are performed and are listed in table 1.
(2) Tensile mechanical properties: an electronic universal tester is adopted for carrying out a tensile test, a rectangular sample with the nominal section size of 2-3 multiplied by 4 multiplied by 20.6mm is taken, and the average values of the tensile strength, the yield strength and the elongation of 3 samples treated in the same way are listed in table 1.
(3) Corrosion resistance
The molded product is processed into a specification of 10mm x 2mm, and is exposed by 1cm after being packaged by epoxy resin2And (4) performing a test, polishing the surface to 2000# with sand paper, scrubbing with alcohol to remove oil stains, cleaning with deionized water, and drying for later use. The experimental solution was 0.1M Na2SO4+ xnacal (PH 3) experimental temperature 25 ℃. Electrochemical testing was performed using the CHI660E electrochemical workstation. A common three-electrode system is adopted for carrying out electrochemical experiments, the experiment of ultrahigh-strength stainless steel is taken as a working electrode, a Pt sheet is taken as an auxiliary electrode, and a Saturated Calomel Electrode (SCE) is taken as a reference electrode. Prior to the electrochemical experiments, the pattern was first applied with-1.2VSECThe applied potential of (2) is polarized for 5min at constant potential so as to remove the oxide film formed on the surface of the sample in the air. The system was stable for 30min and recording was started. The potentiodynamic polarization test has a scanning rate of 0.5mV/S and a scanning potential area of-0.3V (vs. open circuit potential E)OC) 1.5V (vs. reference electrode potential E)R) The test was stopped after the current change was stable. The average value was obtained after 3 measurements and is shown in Table 1.
TABLE 1 compositions and hardness, tensile properties and pitting points of the examples
Note: the contents of P, S and other components in the examples in Table 1 correspond to the elemental composition of stainless steel, with Fe being the balance, not listed in Table 1
In summary, the following steps: the invention discloses a high-plasticity high-strength high-corrosion-resistance stainless steel and a preparation method thereof, wherein the stainless steel comprises the following components: the alloy comprises, by mass, 8.0-11.0% of Co, 6.0-9.0% of Ni, 12.0-15.0% of Cr, 0.4-1.5% of Ti, 4.0-7.0% of Mo, 0.08-1.0% of Mn, 0.08-0.2% of Si, less than or equal to 0.05% of C, less than or equal to 0.035% of P, less than or equal to 0.030% of S, and the balance of Fe. The preparation method of the high-plasticity high-strength high-corrosion-resistance stainless steel comprises the following steps: (1) smelting and casting stainless steel; (2) forging or hot rolling cogging; (3) and (6) heat treatment. The stainless steel of the invention controls the volume fraction of the reversed austenite by adjusting the contents of Co, Ni and Mn, and obtains high plasticity, high strength and excellent corrosion resistance. The elongation percentage of the stainless steel is up to 22.8 percent, the yield strength can reach 1700MPa, the tensile strength can reach 2000MPa, and the fracture toughness is higher than 100 MPa.m1/2And the pitting potential Epit is greater than 0.42VSCE. The high-plasticity high-strength high-corrosion-resistance stainless steel can be used in the field of manufacturing of high-end equipment such as aviation, aerospace and navigation.
Claims (8)
1. The stainless steel with high plasticity, high strength and high corrosion resistance is characterized by comprising the following components: the alloy comprises, by mass, 8.0-11.0% of Co, 6.0-9.0% of Ni, 12.0-15.0% of Cr, 0.4-1.5% of Ti, 4.0-7.0% of Mo, 0.08-1.0% of Mn, 0.08-0.2% of Si, less than or equal to 0.05% of C, less than or equal to 0.035% of P, less than or equal to 0.030% of S, and the balance of Fe.
2. A method for preparing the high-plasticity high-strength high-corrosion-resistance stainless steel according to claim 1, which comprises the following steps:
(1) selecting raw materials of pure iron, metal chromium, metal nickel, metal manganese, metal molybdenum, metal cobalt, metal titanium, iron silicon and iron carbon blocks according to the mass percentage of each element in the stainless steel, smelting and casting to form an alloy ingot;
(2) forging or hot rolling cogging;
(3) and (6) heat treatment.
3. The method for preparing the high-plasticity high-strength high-corrosion-resistance stainless steel according to claim 2, wherein in the step (1), the smelting and casting processes are carried out in vacuum or under the protection of argon, and a stirring technology is utilized to uniformly mix the metal solution in the smelting process.
4. The method for preparing a high-plasticity high-strength high-corrosion-resistance stainless steel according to claim 2, wherein in the step (2), the forging or rolling can be cast or rolled into a square ingot or a round ingot in size; the technological conditions of forging or hot rolling cogging are as follows: heating the casting blank to 1100-1300 ℃, preserving heat for 10-24 h, and then discharging for rolling; the forging or hot rolling starting temperature is more than or equal to 1050 ℃, the finish forging or finish rolling temperature is more than or equal to 900 ℃, the total hot rolling load of the plate is more than or equal to 40%, and the plate is cooled in the air after hot rolling deformation.
5. The method for preparing a high-plasticity high-strength high-corrosion-resistance stainless steel according to claim 2, wherein in the step (3), the heat treatment process comprises the following steps: high-temperature quenching treatment, cryogenic treatment and aging treatment.
6. The method for preparing the high-plasticity high-strength high-corrosion-resistance stainless steel according to claim 5, wherein the temperature is kept at 1050-1200 ℃, and after the temperature is kept for 60-120 min, the steel is quenched and cooled in an ice-water mixture at 0 ℃.
7. The method for preparing the high-plasticity high-strength high-corrosion-resistance stainless steel according to claim 5, wherein the high-plasticity high-strength high-corrosion-resistance stainless steel is subjected to liquid nitrogen cryogenic treatment for 4-10 hours, and is returned to the room temperature after the cryogenic treatment.
8. The method for preparing the high-plasticity high-strength high-corrosion-resistance stainless steel according to claim 5, wherein the aging treatment temperature is 450-600 ℃, the aging time is 1-500 h, and the stainless steel is air-cooled or quenched to room temperature.
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