CN113774280A - 2400 MPa-grade high-ductility high-corrosion-resistance maraging stainless steel and preparation method thereof - Google Patents
2400 MPa-grade high-ductility high-corrosion-resistance maraging stainless steel and preparation method thereof Download PDFInfo
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/02—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling heavy work, e.g. ingots, slabs, blooms, or billets, in which the cross-sectional form is unimportant ; Rolling combined with forging or pressing
- B21B1/026—Rolling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
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- B21J5/002—Hybrid process, e.g. forging following casting
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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
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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Abstract
The invention discloses 2400 MPa-grade high-ductility high-corrosion-resistance maraging stainless steel and a preparation method thereof, wherein the stainless steelThe composition of the steel is as follows: the alloy material comprises, by mass, 2.0-4.0% of Co, 6.0-8.0% of Ni, 11.0-16.0% of Cr, 0.3-1.5% of Ti, 4.0-7.0% of Mo, 0.08-1.0% of Mn, 0.08-0.5% of Si, less than or equal to 0.02% of C, less than or equal to 0.003% of P, less than or equal to 0.003% of S, and the balance of Fe. The method comprises the following steps: proportioning alloy elements, carrying out vacuum electrode smelting in a vacuum induction smelting furnace, carrying out vacuum consumable remelting, carrying out high-temperature tempering treatment, forging or hot rolling cogging, carrying out cold rolling deformation and carrying out heat treatment. The elongation of the stainless steel can reach more than 13 percent, and the tensile strength reaches 2490 MPa; and the pitting potential Epit can reach 0.17V at mostSCE。
Description
Technical Field
The invention relates to 2400MPa grade high-ductility high-corrosion-resistance maraging 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 corrosion-resistant steel has the strength of the maraging strengthening steel and the corrosion resistance of the stainless steel. Due to excellent comprehensive mechanical properties, the material is often used in the fields of critical high-end equipment such as aviation, aerospace, navigation and the like.
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 main reason for the corrosion resistance is that the addition of Cr and Mo forms a passive film on the surface, thereby providing the corrosion resistance. 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 addition of Co to martensitic stainless steel promotes spinodal decomposition of Cr, and the higher the content of Co, the greater the spinodal decomposition degree of Cr, which reduces the corrosion resistance of the substrate. Therefore, an appropriate amount of Co is added. The innovation of the invention is that the alloy components, the thermal mechanical treatment process and the cold deformation process control the transformation of the high-dislocation density martensite, and improve the precipitation kinetics of the nano-phase and the nucleation and growth kinetics of the reversed transformed austenite, thereby realizing the cooperative control strengthening of the nano-phase precipitation and the martensite matrix and the toughening of the reversed transformed austenite, and realizing the improvement of the mechanical property. Meanwhile, on one hand, carbon strengthening is replaced by nano-phase strengthening, so that the carbon content is greatly reduced, and on the other hand, the pitting corrosion resistance equivalent of the alloy is improved through component optimization. The extremely low carbon content and high pitting corrosion resistance equivalent design ensures excellent corrosion resistance of the stainless steel of the present invention. Therefore, compared with the existing stainless steel, the mechanical property and the corrosion resistance of the stainless steel are improved.
The invention patent application with publication number CN 102031459 a discloses a W-containing high-strength high-toughness secondary hardening stainless steel, which comprises (by mass percent) C0.10-0.20%, Cr 11.0-13.0%, Ni 2.0-3.5%, Mo 3.5-5.5%, Co 12-15%, W0.8-3.0%, V0.1-0.6%, Nb 0.01-0.06%, Si ≤ 0.2%, Mn ≤ 0.2%, S ≤ 0.01%, P ≤ 0.01%, O ≤ 30PPm, N ≤ 30PPm, and the balance Fe; the yield strength is 1300-1600 MPa, the tensile strength is 1920-2030 MPa, and the plasticity is 10-13.5%. U.S. patent 7160399 invented ultra-high strength corrosion resistant steel; the nominal composition of the alloy named as Fernium S53 is: 14.0Co, 10.0Cr, 5.5Ni, 2.0Mo, 1.0W, 0.30V, 0.21C, and the balance Fe; the room temperature ultimate tensile strength of the Fernium S53 alloy is approximately 1980MPa and the room temperature 0.2% yield stress is approximately 1560 MPa. 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 (by mass percent), 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%. Although the three technical schemes have the performance of high-strength stainless steel, the raw material cost is high due to the high addition of Co; the content of Co is increased, so that the scroll of Cr can be decomposed, a Cr-poor area and a Cr-rich area are further generated, and the corrosion resistance of the Cr-poor area and the Cr-rich area is reduced; the carbon content is also high, the corrosion resistance is seriously deteriorated by high carbon, the existing size, form and distribution of carbide in a matrix are difficult to control, and the mechanical property is seriously deteriorated when the size is large and appears on a grain boundary; the production process of the publication No. CN 110358983A and Ferrium S53 needs two times of aging and two times of deep cooling treatment, the process is complex, and the strength is still far lower than that of the invention under the condition that the carbon content is obviously higher than that of the invention.
The patent application of the invention with the publication number of CN 107653421A discloses an ultrahigh-strength maraging stainless steel with seawater corrosion resistance, wherein the specific chemical components of the stainless steel (expressed by mass percent) are that C is less than or equal to 0.03 percent, Cr is 13.0-14.0 percent, Ni is 5.5-7.0 percent, Co is 5.5-7.5 percent, Mo is 3.0-5.0 percent, Ti is 1.9-2.5 percent, Si is less than or equal to 0.1 percent, Mn is less than or equal to 0.1 percent, P is less than or equal to 0.01 percent, S is less than or equal to 0.01 percent, and the balance is Fe. The tensile strength is 1926-2032 MPa, the yield strength is 1538-1759 MPa, the elongation is 7.5-13.0%, and the pitting potential Epit is more than or equal to 0.15V. Although the strengthening mechanism of the invention is a precipitation strengthening mechanism, the types of precipitation phases are different from those of the invention, compared with the invention, the mechanical property, the corrosion resistance and the like of the invention are far lower than those of the invention, and the strengthening mechanism, the toughening mechanism and the corrosion resistance of the two inventions are completely different.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems of high raw material cost, complex preparation process, low corrosion resistance and mechanical property and the like of the existing ultrahigh-strength stainless steel, the invention provides a 2400MPa grade high-ductility high-corrosion-resistance maraging stainless steel and a preparation method thereof.
The technical scheme is as follows: the invention relates to 2400MPa grade high-ductility high-corrosion-resistance maraging stainless steel and a preparation method thereof, wherein the stainless steel comprises the following components: according to the mass percent, the Co is 2.0-4.0%, the Ni is 6.0-8.0%, the Cr is 11.0-16.0%, the Ti is 0.3-1.5%, the Mo is 4.0-7.0%, the Mn is 0.08-1.0%, the Si is 0.08-0.5%, the C is less than or equal to 0.02%, the P is less than or equal to 0.003%, the S is less than or equal to 0.003%, and the balance is Fe.
The invention principle and the component design basis of the 2400MPa grade high-ductility high-corrosion-resistance maraging stainless steel are as follows:
the invention principle is as follows: the stainless steel of the invention is not reinforced by carbon, the carbon is controlled at a very low level, and the toughness and the corrosion resistance of the stainless steel can be simultaneously improved. But the greatest problem with ultra-low carbon is low strength. According to the invention, the nano-strip structures with different dislocation densities in the martensite matrix are controlled through composition design, creative thermal mechanical treatment and different cold rolling deformation, the fine martensite strips can provide nucleation sites for precipitation phase and membranous metastable reverse transformation austenite by ice water quenching and large cold rolling deformation, meanwhile, element distribution channels are added for the reverse transformation austenite by high dislocation density, the reverse transformation austenite generated by the method is more prone to generate TRIP (transformation Induced plasticity) effect when being loaded, and the plasticity and strength are obviously improved by utilizing unique nano-phase strengthening and TRIP effect. The precipitated phase of the invention is formed by adjusting the contents of Ni, Ti, Mo and Si to form Mo-rich R' phase and Ni3The strength of the (Ti, Mo) nano-phase is improved through cooperative strengthening, the two nano-strengthening phases are mainly represented by a cooperative precipitation relation, Ni-Ti-Mo-Si clusters which are fine in size and distributed in a dispersion mode are formed in the martensite laths or on dislocation at the early stage of aging, Mo and Si are gradually eliminated from the clusters along with the prolonging of aging time, and nano-sized Ni is formed first3The (Ti, Mo) strengthening phase, after a period of heat preservation, Mo and Si are completely removed from the surface of Ni3Ti to form Mo-rich R 'phase, and Ni is wrapped by the Mo-rich R' phase3The growth of Ti is inhibited, the fine dispersion of precipitated phase is ensured, and the newly formed Mo-rich R' phase and Ni3Together, Ti provides the matrix with higher strength. The fine dispersed precipitated phases can be used as dislocation sources in the plastic deformation process, so that the dislocation is continuously added in the deformation process, and the plasticity is further increased. Simultaneously, Ni of DO24 structure is dispersed and distributed3The reverse transformed austenite with a film-shaped structure and dispersed distribution can be formed by the climb of edge dislocation and the diffusion of Fe atoms by taking coherent strain energy of a matrix interface as driving force of Ti, the energy required by reverse austenite nuclei is greatly reduced by high dislocation density and fine martensite laths, and a diffusion channel is provided for the growth of the reverse austenite by high dislocation density. The invention has the important innovation that the content of the expensive alloying element Co is greatly reduced, and the cost can be obviously reduced while the corrosion resistance is improved. Although the low Co content design reduces the forming capability of the Ni-Ti cluster, the precipitation of the Mo-rich R' phase and the metastable state film-like reverse austenite is realized through creative components and process optimization design, so that the strength and the ductility and toughness are remarkably improved. According to the invention, on the basis of innovations in the aspects of strengthening mechanism, corresponding components, thermal mechanical treatment design, heat treatment, cold deformation and the like, the mechanical property and the corrosion resistance are effectively improved on the basis of simple and controllable process and cost reduction.
The basis of component design is as follows: co is one of important elements to be considered in the invention, can improve Ms point and ensure that the matrix is martensite, but is a double-edged sword for martensite precipitation strengthening stainless steel. The addition of Co can reduce the solubility of Ti and Mo in the martensite matrix, form precipitates containing Mo or Ti, and further improve the strength. Co also hinders the recovery of dislocations, reduces the size of the precipitate phase and the matrix, and can produce a higher secondary hardening. However, addition of Co to martensitic stainless steel promotes spinodal decomposition of Cr, and the higher the content of Co, the greater the spinodal decomposition degree of Cr, which lowers the pitting corrosion resistance of the substrate. Meanwhile, the Co element is expensive, the content of Co is high, and the cost of the raw materials of the ultrahigh-strength stainless steel is high. Comprehensively considering that the mass percentage of Co is controlled to be 2.0-5.0%.
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; in addition, Ni can strengthen the matrix and provide certain ductility and toughness for the stainless steel; ni also improves the hardenability of martensite. Meanwhile, Ni is also a main element for forming reverse austenite, but too high content of Ni promotes the formation of residual austenite in the matrix, thereby affecting the strength of the stainless steel. Comprehensively considering that the mass percentage of Ni is controlled to be 6.0-10.0%.
Mo is an important precipitation strengthening element. Mo is formed as Mo-R' rich phase and Ni3One of the main elements of (Ti, Mo). The Mo-R' rich phase is formed after long-time aging and is wrapped by Ni3Ti forms a core-shell structure with fine dispersion distribution, and the strength can be effectively improved. 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 3.0-7.0%.
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 11.0-16.0%.
Si is one of important elements of the novel stainless steel, Si is one of main forming elements of the Mo-R 'rich phase, and the addition of Si can effectively promote the formation of the Mo-R' rich phase; si can also 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 0.08-0.50%.
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 too large, the tendency of precipitation of the precipitated phase at the boundary of the martensite lath becomes large, and when the content of the precipitated phase at the boundary of the martensite lath is too large, the precipitated phase is liable to develop into a crack source and propagate along the interface of the martensite lath, thereby initiating a quasi-cleavage crack. Comprehensively considering, the mass percentage of Ti should be controlled to be 0.3-2.0%.
Mn is mainly participated in the precipitation of nano-phase to form Ni (Mn, Ti, Mo) intermetallic compounds, thereby replacing Ti and Mo elements in a small amount and reducing the cost. Mn is a main 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 should be controlled to be 0.08-1.0%.
C exists in the matrix as an impurity element in the stainless steel, and when the content of C is too high, MX or M is formed23C6Form carbides (M ═ Cr, Ti) which seriously retard the formation of reverse austenite, offset the gain of high dislocation density by cold rolling, and seriously deteriorate the toughness and corrosion resistance of steel when the size is too large, so that the C content is strictly controlled to 0.02% or less; p and S are impurity elements, and the performance of the stainless steel is seriously damaged by increasing the content of P and S, so the content is strictly controlled.
The 2400MPa grade high-ductility high-corrosion-resistance maraging stainless steel and the preparation method thereof comprise the following steps:
(1) proportioning alloy elements;
(2) carrying out vacuum smelting on the electrode by using a vacuum induction smelting furnace;
(3) vacuum consumable remelting;
(4) carrying out high-temperature flame equalizing treatment;
(5) forging or hot rolling cogging;
(6) cold rolling deformation;
(7) 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. The structure with uniform and fine size can be obtained through hot rolling cogging, cold rolling deformation and heat treatment, so that the structure has higher strength, toughness and corrosion resistance.
In the step (1), the alloy elements are proportioned, according to the mass percentage of each element in the stainless steel, metal chromium, metal nickel, metal manganese, metal molybdenum, metal cobalt, metal titanium and iron silicon are selected, and the balance is pure iron and inevitable impurities.
In the step (2), the vacuum induction smelting furnace is adopted for vacuum smelting of the electrode, high vacuum smelting is adopted in the whole process, and the vacuum degree is below 0.1 Pa; adding pure iron, metallic nickel, metallic molybdenum and metallic cobalt into the furnace, adding metallic chromium and metallic titanium into the furnace from a high-level bin, and adding industrial silicon and metallic manganese into the furnace from an alloy bin. Adding materials along with the furnace, melting down, adding high-level bin metal, completely melting, performing deoxidation alloying, and finally adding alloy bin metal. In the smelting period, the refining temperature reaches 1550-1650 ℃, the refining time is not less than 60 minutes, and the stirring time is not less than 10 minutes; sampling in front of the furnace to analyze smelting components, and then adjusting the components according to the target designed by the claim 1; and after the target components are adjusted, pouring at the temperature of 1530-1550 ℃, and carrying out ordinary heat preservation on a riser.
In the step (3), the vacuum consumable remelting is carried out at a melting speed of 100-260 Kg/h, and the vacuum degree is kept at 10 in the remelting process-2Pa and below.
In the step (4), the high-temperature homogenizing treatment is carried out, heating is carried out in air, vacuum or protective atmosphere, the heating mode is furnace heating, the heating rate is 100-180 ℃/h, heat preservation is carried out for 4-8 h at 600-900 ℃, then the temperature is raised to 1100-1300 ℃, heat preservation is carried out for 20-50 h, and furnace cooling, air cooling or oil cooling is carried out until the room temperature is reached.
In the step (5), 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 then discharging for rolling; the forging or hot rolling starting temperature is more than or equal to 1100 ℃, the finish forging or rolling temperature is more than or equal to 950 ℃, the total hot rolling load of the plate is not less than 50%, the forging ratio of a forging billet is not less than 6, and after the forging or rolling deformation, the ice-water mixture is cooled.
In the step (6), the cold rolling deformation is performed, wherein the total reduction of the plate is 40-60%, and the pipes, rods, wires and sections are subjected to cold deformation by adopting a reciprocating pipe rolling, hole pattern rolling, universal rolling or drawing method, so as to obtain the required size and specification of the product.
In the step (7), the heat treatment process includes: and (6) bipolar aging treatment.
Further, in step (7), the bipolar aging treatment: the method is characterized in that the method comprises the steps of bipolar aging treatment, wherein the temperature of the first aging treatment is 450-600 ℃, the aging time is 0.5-500h, air cooling or quenching is carried out until the temperature is room temperature, the temperature of the second aging treatment is 650-900 ℃, and air cooling or quenching is carried out for 1-60min until the temperature is room temperature.
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) compared with other high-strength stainless steel, the high-strength stainless steel has the advantages that the content of noble metal is low, and the cost of raw materials is low;
(2) the stainless steel of the invention contains no carbon or extremely low carbon content;
(3) the preparation method of the 2400MPa grade high-plasticity high-corrosion-resistance maraging stainless steel is simple, the high-strength stainless steel can be obtained through different heat treatment processes, the process controllability is strong, and the industrial production is easy to realize. Finally, the stainless steel with good corrosion resistance and excellent mechanical property is obtained, the elongation of the martensitic stainless steel reaches 13.1%, and the tensile strength reaches 2490 MPa; and the pitting potential Epit can reach 0.31VSCE。
Drawings
FIG. 1 TEM image of example 1 after aging;
FIG. 2 metallographic morphology after aging of example 1;
figure 3 stress strain curve after aging for example 2.
Detailed Description
The 2000MPa grade high ductility high corrosion resistant maraging stainless steel and the method for making the same according to the present invention will be further explained and illustrated with reference to the accompanying drawings and the specific examples, which, however, should not be construed to unduly limit the technical solutions of the present invention.
Example 1
Selecting pure iron, chromium metal, nickel metal, manganese metal, molybdenum metal, cobalt metal, titanium metal and iron silicon as raw materials, wherein the stainless steel comprises the following components in percentage by mass: co 3.0, Cr 11.0, Mn 0.8, Mo 4.0, Ni 7.0, Si 0.08, Ti 0.8, and the balance Fe.
And preparing a billet by adopting vacuum melting in the whole process.
And (3) carrying out high-temperature flame equalizing treatment, heating in air in a mode of heating along with a furnace, keeping the temperature at 700 ℃ for 4h at the heating rate of 180 ℃/h, then heating to 1150 ℃ and keeping the temperature for 25h, and cooling to room temperature along with the furnace.
The technological conditions of hot rolling and cogging are as follows: heating the casting blank to 1200 ℃, preserving heat for 10 hours, and then discharging and rolling; the starting temperature of hot rolling is 1150 +/-20 ℃, the finishing temperature is more than or equal to 950 ℃, the total rolling reduction of the plate is 60 percent, and the ice-water mixture is cooled.
The sheet was cold rolled with a total reduction of 60%.
Carrying out bipolar aging treatment on the cold-rolled sheet, wherein the first aging temperature is 480 ℃, the aging time is 5 hours, and air cooling to room temperature; the second aging temperature is 650 ℃, the aging time is 5min, and the air cooling is carried out to the room temperature.
The mechanical properties of example 1 are shown in Table 1, the average hardness is 541.2HV, the yield strength is 2160MPa, the tensile strength is 2320MPa, the elongation is 9.2%, and the pitting potential is 0.16VSCE. FIG. 1 is an aged TEM image of example 1, from which it can be seen that there are a large number of dislocations in the martensite laths. FIG. 2 is the metallographic morphology after aging of example 1.
Example 2
Selecting pure iron, chromium metal, nickel metal, manganese metal, molybdenum metal, cobalt metal, titanium metal and iron silicon as raw materials, wherein the stainless steel comprises the following components in percentage by mass: co 4.0, Cr 13.0, Mn 0.5, Mo 6.0, Ni 8.0, Si 0.5, Ti 1.5, and the balance Fe.
And preparing a billet by adopting vacuum melting in the whole process.
And (3) carrying out high-temperature flame equalizing treatment, heating in air in a mode of heating along with a furnace, keeping the temperature at 700 ℃ for 5h at the heating rate of 180 ℃/h, then heating to 1200 ℃ and keeping the temperature for 30h, and cooling to room temperature along with the furnace.
The technological conditions of hot rolling and cogging are as follows: heating the casting blank to 1200 ℃, preserving heat for 20 hours, and then discharging and rolling; the starting temperature of hot rolling is 1150 +/-20 ℃, the finishing temperature is more than or equal to 950 ℃, the total rolling reduction of the plate is 70 percent, and the ice-water mixture is cooled.
The sheet was cold rolled with a total reduction of 60%.
Carrying out bipolar aging treatment on the cold-rolled sheet, wherein the first aging temperature is 550 ℃, the aging time is 40h, and air cooling to room temperature; the second aging temperature is 650 ℃, the aging time is 5min, and the air cooling is carried out to the room temperature.
The mechanical properties of example 2 are shown in Table 1, the average hardness is 549.2HV, the yield strength is 2080MPa, the tensile strength is 2490MPa, the elongation is 13.1%, and the pitting potential is 0.17VSCE. FIG. 3 is a stress-strain curve of example 2 after aging.
The test methods for the corrosion resistance, the hardness and the tensile mechanical property of the 2400MPa grade high-ductility high-corrosion-resistance maraging stainless steel in the above examples are as follows.
(1) Hardness: the hardness test was carried out using an HVS-50 Vickers hardness tester with a load of 1Kg, and 5 points were hit and averaged, as shown 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 resin2The test was performed by sanding the surface to 2000# and wiping off the oil with alcoholAnd cleaning dirt with deionized water, and blow-drying for later use. The experimental solution was 0.1MNa2SO4+ 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 C, P, S and the like in the examples in Table 1 correspond to the elemental composition of stainless steel
In summary, the following steps: the invention discloses 2400MPa grade high-ductility high-corrosion-resistance maraging stainless steel and a preparation method thereof, wherein the stainless steel comprises the following components: the alloy material comprises, by mass, 2.0-4.0% of Co, 6.0-8.0% of Ni, 11.0-16.0% of Cr, 0.3-1.5% of Ti, 4.0-7.0% of Mo, 0.08-1.0% of Mn, 0.08-0.5% of Si, less than or equal to 0.02% of C, less than or equal to 0.003% of P, less than or equal to 0.003% of S, and the balance of Fe. The preparation method of the 2400MPa grade high-ductility high-corrosion-resistance maraging stainless steel comprises the following steps: (1) alloy element proportioning (2) carrying out vacuum smelting on an electrode in a vacuum induction smelting furnace; (3) vacuum consumable remelting; (4) carrying out high-temperature flame equalizing treatment; (5) forging or hot rolling cogging; (6) cold rolling deformation; (7) and (6) heat treatment. The stainless steel of the invention can obtain different high dislocation densities by optimizing alloy elements, corresponding thermal mechanical treatment process and adjusting different cold rolling deformation quantities, so that precipitated phases and inversions are realizedThe austenite is distributed uniformly and finely, and the distribution efficiency of the inversion austenite forming elements is higher. The elongation of the stainless steel can reach more than 13 percent, and the tensile strength reaches 2490 MPa; and the pitting potential Epit can reach 0.17V at mostSCE. The 2400MPa grade high-plasticity high-corrosion-resistance maraging stainless steel can be used as key structures of bearing members of aircraft engines, valves for ships, pump parts and the like.
Claims (10)
1. The 2400 MPa-grade high-ductility high-corrosion-resistance maraging stainless steel is characterized by comprising the following components: according to mass percent, Co is 2.0-4.0%, Ni is 6.0-8.0%, Cr is 11.0-16.0%, Ti is 0.3-1.5%, Mo is 4.0-7.0%, Mn is 0.08-1.0%, Si is 0.08-0.5%, C is less than or equal to 0.02%, P is less than or equal to 0.003%, S is less than or equal to 0.003%, and the balance is Fe; the preparation method comprises the following steps: (1) alloy element proportioning (2) carrying out vacuum smelting on an electrode in a vacuum induction smelting furnace; (3) vacuum consumable remelting; (4) carrying out high-temperature flame equalizing treatment; (5) forging or hot rolling cogging; (6) cold rolling deformation; (7) and (6) heat treatment.
2. The preparation method of the 2400MPa grade high ductility and high corrosion resistance maraging stainless steel of claim 1, characterized by comprising the following steps:
(1) proportioning alloy elements;
(2) carrying out vacuum smelting on the electrode by using a vacuum induction smelting furnace;
(3) vacuum consumable remelting;
(4) carrying out high-temperature flame equalizing treatment;
(5) forging or hot rolling cogging;
(6) cold rolling deformation;
(7) and (6) heat treatment.
3. The preparation method of the 2400MPa grade high ductility and high corrosion resistance maraging stainless steel according to claim 2, characterized in that in the step (1), the alloy element proportion is that according to the mass percentage of each element in the stainless steel, metal chromium, metal nickel, metal manganese, metal molybdenum, metal cobalt, metal titanium and iron silicon are selected, and the balance is pure iron and unavoidable impurities.
4. The preparation method of the 2400MPa grade high-ductility high-corrosion-resistance maraging stainless steel according to claim 2, wherein in the step (2), the vacuum induction smelting furnace is adopted for vacuum smelting of the electrode, high vacuum smelting is adopted in the whole process, and the vacuum degree is up to below 0.1 Pa; adding pure iron, metallic nickel, metallic molybdenum and metallic cobalt into a furnace, adding metallic chromium and metallic titanium into a high-position stock bin, adding industrial silicon and metallic manganese into an alloy stock bin, adding the high-position stock bin metal into the furnace after the industrial silicon and the metallic manganese are melted down, performing deoxidation alloying after the high-position stock bin metal is completely melted, and finally adding the alloy stock bin metal into the furnace, wherein the smelting period is that the refining temperature reaches 1550-1650 ℃, the refining time is not less than 60 minutes, and the stirring time is not less than 10-15 minutes; sampling in front of the furnace, analyzing smelting components, and then adjusting the components; after the target components are adjusted, pouring is carried out at the temperature of 1530-1550 ℃, and ordinary heat preservation is adopted for a riser.
5. The preparation method of 2400MPa grade high-ductility high-corrosion-resistance maraging stainless steel according to claim 2, wherein in the step (3), the vacuum consumable remelting is carried out at a melting speed of 100-260 Kg/h, and the vacuum degree is kept at 10 during the remelting process-2Pa and below.
6. The preparation method of the 2400MPa grade high-ductility high-corrosion-resistance maraging stainless steel according to claim 2, characterized in that in the step (4), the high-temperature tempering treatment is carried out, heating is carried out in air, vacuum or protective atmosphere, the heating mode is furnace heating, the heating rate is 100-180 ℃/h, the temperature is kept at 600-900 ℃ for 4-8 h, then the temperature is increased to 1100-1300 ℃ for 20-50 h, and furnace cooling, air cooling or oil cooling is carried out until the room temperature is reached.
7. The method for preparing 2400MPa grade high ductility high corrosion resistant maraging stainless steel according to claim 2, wherein in step (5), the forging or rolling may 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 1100 ℃, the finish forging or rolling temperature is more than or equal to 950 ℃, the total hot rolling load of the plate is not less than 50%, the forging ratio of a forging billet is not less than 6, and after the forging or rolling deformation, the ice-water mixture is cooled.
8. The preparation method of the 2400MPa grade high-ductility high-corrosion-resistance maraging stainless steel according to claim 2, characterized in that in the step (6), the cold rolling deformation is carried out, the total reduction of the cold rolling of the plate is 40-60%, and the cold deformation is carried out on the pipe, the rod, the wire and the section by adopting a reciprocating tube rolling method, a groove rolling method, a universal rolling method or a drawing method, so as to obtain the required size and specification of the product.
9. The method for preparing 2400MPa grade high ductility and high corrosion resistant maraging stainless steel according to claim 2, wherein in step (7), the heat treatment process comprises: and (6) bipolar aging treatment.
10. The method for preparing 2400MPa grade high-ductility high-corrosion-resistance maraging stainless steel according to claim 9, characterized in that the temperature of the first aging treatment is 450-600 ℃, the aging time is 0.5-500h, the steel is air-cooled or quenched to room temperature, and the temperature of the second aging treatment is 650-900 ℃, and the steel is air-cooled or quenched to room temperature for 1-60 min.
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