CN114517273B - 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
- Publication number
- CN114517273B CN114517273B CN202210364148.8A CN202210364148A CN114517273B CN 114517273 B CN114517273 B CN 114517273B CN 202210364148 A CN202210364148 A CN 202210364148A CN 114517273 B CN114517273 B CN 114517273B
- Authority
- CN
- China
- Prior art keywords
- stainless steel
- temperature
- corrosion
- carried out
- ductility
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 72
- 239000010935 stainless steel Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000007797 corrosion Effects 0.000 claims description 38
- 238000005260 corrosion Methods 0.000 claims description 38
- 230000032683 aging Effects 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000010936 titanium Substances 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 22
- 229910045601 alloy Inorganic materials 0.000 claims description 19
- 239000000956 alloy Substances 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 19
- 239000011651 chromium Substances 0.000 claims description 18
- 238000005242 forging Methods 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- 238000005096 rolling process Methods 0.000 claims description 17
- 238000003723 Smelting Methods 0.000 claims description 16
- 238000005098 hot rolling Methods 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000005097 cold rolling Methods 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 230000006698 induction Effects 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 238000005275 alloying Methods 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005496 tempering Methods 0.000 claims description 2
- 238000009785 tube rolling Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims 1
- 229910000734 martensite Inorganic materials 0.000 description 23
- 238000005728 strengthening Methods 0.000 description 19
- 238000001556 precipitation Methods 0.000 description 17
- 239000011159 matrix material Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910001566 austenite Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910001105 martensitic stainless steel Inorganic materials 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000001330 spinodal decomposition reaction Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000005482 strain hardening Methods 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 208000035475 disorder Diseases 0.000 description 2
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical class [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 206010003591 Ataxia Diseases 0.000 description 1
- -1 C 6 Form carbides Chemical class 0.000 description 1
- 206010010947 Coordination abnormal Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910017305 Mo—Si Inorganic materials 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 208000016290 incoordination Diseases 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004881 precipitation hardening Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J5/00—Methods for forging, hammering, or pressing; Special equipment or accessories therefor
- B21J5/002—Hybrid process, e.g. forging following casting
-
- 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
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
-
- 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
- B21B2001/028—Slabs
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Heat Treatment Of Steel (AREA)
- Heat Treatment Of Sheet Steel (AREA)
Abstract
The invention discloses 2400MPa grade high-ductility toughness high-corrosion-resistance maraging stainless steel and a preparation method thereof, wherein the stainless steel comprises the following components: by mass percent, co = 2.0-4.0, ni = 6.0-8.0, cr = 11.0-16.0, ti = 0.3-1.5, mo = 4.0-7.0, mn = 0.08-1.0, si = 0.08-0.5, C ≤ 0.02, P ≤ 0.003, S ≤ 0.003, and the balance of Fe. The stainless steel has the tensile strength as high as 2400MPa, the elongation as high as 13 percent and the pitting potential as high as 0.17V under the conditions that C is less than or equal to 0.02 percent and Co is not more than 4 percent SCE (ii) a The bearing component of the aircraft engine, the valve for the ship, the pump component and other key structures can be used.
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
Martensitic precipitation strengthened stainless steels were a new steel that developed in the 60's of the 20 th century. The stainless steel has the strength of maraging reinforced steel and the corrosion resistance of 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 development of 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 solubility of Ti and Mo in the martensite matrix can be reduced by adding the Co, 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 of Cr, which lowers the pitting corrosion resistance of the substrate. Therefore, an appropriate amount of Co is added. The innovation of the invention is that a special structure is formed by combining optimized alloy elements, double vacuum melting and corresponding thermal mechanical treatment processes, the structure consists of martensite laths and an amorphous layer modified by lath boundaries, wherein the martensite laths contain a plurality of precipitation phases with nanometer sizes in dispersed distribution. The ultrahigh strength is obtained by the cooperative reinforcement of a plurality of nano phases; meanwhile, the amorphous decorated lath boundary promotes the dislocation multiplication and absorbs the dislocation, thereby obtaining large plasticity and huge work hardening capacity. Meanwhile, the existence of the reversed austenite also provides contribution to the plasticity and toughness of the material. On one hand, the stainless steel of the invention replaces carbon strengthening 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 by 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 of publication No. CN 102031459A discloses a W-containing high-strength high-toughness secondary hardening stainless steel, which comprises (in mass percent) C = 0.10-0.20%, cr = 11.0-13.0%, ni = 2.0-3.5%, mo = 3.5-5.5%, co = 12-15%, W = 0.8-3.0%, V = 0.1-0.6%, 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 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 1560MPa. The invention patent application of publication No. CN 110358983A discloses a precipitation hardening martensitic stainless steel and a preparation method thereof, the specific chemical components of the stainless steel (expressed by mass percent) are that C = 0.14-0.20%, cr = 13.0-16.0%, ni = 0.5-2.0%, co = 12.0-15.0%, mo = 4.5-5.5%, V = 0.4-0.6%, si is less than or equal to 0.1%, mn is less than or equal to 0.5%, P is less than or equal to 0.01%, S is less than or equal to 0.01%, N is less than or equal to 0.10%, and the balance is 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 the Ferrium S53 needs two times of aging and two times of deep cooling treatment, and the process is complex.
The patent application of the publication No. CN 107653421A discloses an ultra-high strength maraging stainless steel with seawater corrosion resistance, the specific chemical components of the stainless steel (expressed by mass percent) are less than or equal to 0.03 percent of C, 13.0-14.0 percent of Cr, 5.5-7.0 percent of Ni, 5.5-7.5 percent of Co, 3.0-5.0 percent of Mo, 1.9-2.5 percent of Ti, less than or equal to 0.1 percent of Si, less than or equal to 0.1 percent of Mn, less than or equal to 0.01 percent of P, less than or equal to 0.01 percent of S, and the balance of 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 type of the precipitation phase is different from that of the invention, compared with the invention, the invention has no higher mechanical property and corrosion resistance, and the strengthening mechanism and the corrosion resistance of the two inventions are completely different.
Disclosure of Invention
The invention aims to: aiming at the problems of high raw material cost, complex preparation process, low corrosion resistance and mechanical property thereof 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 2400MPa grade high-ductility, toughness and corrosion resistance maraging stainless steel comprises the following components: according to the mass percent, the alloy comprises, by mass percent, co = 2.0-4.0%, ni = 6.0-8.0%, cr = 11.0-16.0%, ti = 0.3-1.5%, mo = 4.0-7.0%, mn = 0.08-1.0%, si = 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 2400MPa grade high-ductility, toughness and corrosion-resistant maraging stainless steel is designed according to the following inventive principles and components:
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. By optimizing alloy elements, double vacuum melting and corresponding thermal mechanical treatment processes, a special structure is formed, and the structure consists of martensite laths and an amorphous layer modified by lath boundaries, wherein the martensite laths contain a plurality of nano-size dispersed precipitation phases. Ice water quenching and large cold rolling deformation can make the size of martensite laths fine and the dislocation density increased, and the fine martensite laths with high dislocation density can provide nucleation sites for precipitation phase bodies; at the same time, the high density of dislocations and defects between these nanoslabs lamellar structures concentrates a large amount of lattice strain, which generates a large amount of elastic strain energy due to the incoordination between atoms. In order to release the elastic strain energy between the atoms, they must interact with each other. Then, local crystal lattices are broken to disorder the atomic arrangement, and a nucleation region of an amorphous structure is generated. The attraction capacity of the lath boundary to atoms is strong, and elements are distributed to the lath boundary in the aging process, so that the disorder degree of the lath boundary is further increased, and the forming capacity of amorphous on the lath boundary is increased. During the deformation process of the composite structure, the extremely high yield strength is contributed by precipitation strengthening of multiple nano phases, on one hand, the nano-sized amorphous phase at the interface after yielding can promote dislocation proliferation to provide plasticity and strength, and simultaneously, the dislocation can be absorbed, the fracture caused by excessive dislocation entanglement and hardening is avoided, and the work hardening is further provided, so that the ultrahigh strength and the large plasticity can be obtained. During the thermomechanical treatment, reverse transformation austenite is also precipitated in the matrix, and the precipitated phases can delay the stress concentration of the material in the deformation process and ensure the plasticity.
The precipitated phase of the invention is formed by adjusting the contents of Ni, ti, mo and Si to form an R 'phase rich in Mo, alpha' -Cr and Ni 3 The strength of the (Ti, mo) nano-phase is improved by cooperative strengthening, the three nano-strengthening phases are mainly represented by the relationship of cooperative precipitation, ni-Ti-Mo-Si clusters which are fine in size and distributed in a dispersion manner are formed in the martensite laths or on dislocation at the initial stage of aging, mo and Si are gradually eliminated from the clusters along with the extension of aging time, and the nano-sized Ni is formed first 3 The (Ti, mo) strengthening phase, after a period of heat preservation, mo and Si are completely removed from Ni 3 The surface of Ti forms a Mo-rich R' phase to wrap it, ni 3 The growth of Ti is inhibited, so that fine dispersion of a precipitated phase is ensured, and meanwhile, nano-sized alpha' -Cr is generated in the martensite lath; newly formed Mo-rich R' phase, ni 3 Ti and alpha' -Cr together provide the matrix with higher strength. Ni of dispersed DO24 structure 3 Ti can form reverse transformed austenite with nanometer size by the climbing of edge dislocation and the diffusion of Fe atoms by taking coherent strain energy of the interface of the Ti and the matrix as driving force, is uniformly distributed in the matrix, is easy to generate TRIP effect, and can effectively relieve stress concentration.
Meanwhile, in the process of distributing high-alloying elements such as Fe, cr, co, ni and Mo to the lath boundary, the composition of the lath boundary is changed into a near-eutectic composition, the amorphous forming capability is improved, and the interface is changed from segregation to amorphousness. The amorphous phase can promote dislocation propagation to provide plasticity and strength on one hand during uniform deformation, and can absorb dislocations to avoid fracture caused by excessive dislocation entanglement hardening, so that work hardening is further provided, and ultrahigh strength and large plasticity can be obtained.
The invention has the important innovation that the content of an expensive alloy element Co is greatly reduced, and the cost can be obviously reduced while the corrosion resistance is improved. Although the content of Co is designed at a lower level, the formation of Ni-Ti clusters is reduced, but the ultrahigh strength is obtained by combining the optimized alloy elements, double vacuum melting and corresponding thermal mechanical treatment processes and utilizing the cooperative reinforcement of various nanophase; meanwhile, an amorphous layer is introduced into the lath boundary, and the lath boundary decorated by the amorphous layer promotes the dislocation multiplication and absorbs the dislocation, so that the large plasticity and the large processing hardening capacity are obtained. On the basis of innovation in the aspects of a strengthening mechanism, corresponding components, thermal mechanical treatment design and the like, the method is simple and controllable in process and effectively improves the mechanical property and the corrosion resistance.
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 dislocation recovery, reduces the size of the precipitate phase and matrix, and produces 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. The mass percentage of Co is comprehensively considered to be controlled to be 2.0-4.0%. E.g., 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, etc.
Ni is an important element for forming intermetallic compounds by forming B2-Ni (Ti, mn) and eta-Ni in the early stage 3 (Ti, mo) for strengthening matrix, eta-Ni 3 (Ti, mo) is also the core of the Mo-R' rich phase nuclei; in addition, ni can strengthen the matrix and provide certain ductility and toughness for the stainless steel; ni also increases 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. The mass percentage of Ni is controlled between 6.0 and 8.0 percent in comprehensive consideration. E.g., 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, etc.
Mo is an important precipitation strengthening element. Mo is formed richMo-R' phase and Ni 3 One of the main elements of (Ti, mo). The Mo-R' rich phase is formed after long-time aging and is wrapped by Ni 3 Ti 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 4.0-7.0%. E.g., 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0%, etc.
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 of the Cr is too high, so that the content of delta ferrite in the matrix is increased, and the obdurability and corrosion resistance of the material are influenced. Therefore, the mass percentage of Cr is controlled to be 11.0-16.0%. For example, 11.0%, 11.5%, 12.0%, 12.5%, 13.0%, 13.5%, 14.0%, 14.5%, 15.0%, 15.5%, 16.0%, etc.
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 content of Si is controlled between 0.08 and 0.50 percent. For example, 0.08%, 0.10%, 0.15%, 0.20%, 0.25%, 0.30%, 0.35%, 0.40%, 0.45%, 0.50%, etc.
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 content of Ti should be controlled between 0.3 and 1.5 percent. E.g., 0.3%, 0.5%, 1.0%, 1.5%, etc.
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 is controlled to be 0.08-1.0%. For example, 0.08%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, etc.
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 formed 23 C 6 Form carbides (M = Cr, ti) which seriously retard and reverse the formation of austenite, offset the benefit of high dislocation density brought by cold rolling, and seriously deteriorate the toughness and corrosion resistance of steel when the size is too large, so that the content of C is strictly controlled to be less than 0.02%; 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 invention relates to a preparation method of 2400MPa grade high-ductility, toughness and corrosion resistance maraging stainless steel, which comprises the following steps:
(1) Proportioning alloy elements;
(2) Carrying out vacuum smelting on the electrode by using a vacuum induction smelting furnace;
(3) Remelting at vacuum consumable;
(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, iron silicon, and the balance of pure iron and inevitable impurities are selected, wherein the metals are high-purity metals and do not contain industrial waste metals.
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 stock bin metal, performing deoxidation alloying after complete melting, and finally adding alloy stock 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; 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.
In the step (3), the vacuum consumable remelting is carried out at the melting speed of 100-260 Kg/h, and the vacuum degree is kept at 10 in the remelting process -2 Pa 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, the temperature is kept at 600-900 ℃ for 4-8 h, then the temperature is increased to 1100-1300 ℃ and kept for 20-50 h, and furnace cooling, air cooling or oil cooling are 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 the heat for 10-24 h, and then discharging and 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 amount of the plate cold rolling is 40-60%, and the tubes, rods, wires and sections are subjected to cold deformation by adopting a reciprocating tube rolling, hole pattern rolling, universal rolling or drawing method 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, and 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 beneficial effects that: compared with the prior art, the invention has the advantages that: compared with other high-strength stainless steel, the precious metal content in the invention is lower, the cost of raw materials is lower (2) the stainless steel of the invention does not contain carbon or contains extremely low carbon (3) the 2400MPa grade high-ductility high-corrosion-resistance maraging stainless steel of the invention has simple preparation method, can obtain the high-strength stainless steel through different heat treatment processes, has strong process controllability, and is easy to realize industrial production. Finally, the stainless steel with good corrosion resistance and excellent mechanical property is obtained.
Drawings
FIG. 1 TEM image of example 1 after aging;
FIG. 2 is a metallographic morphology map of example 1 after aging;
FIG. 3 stress strain plot after aging for example 2; in the figure, the abscissa represents engineering strain, and the ordinate represents engineering stress;
FIG. 4 high resolution electron diffraction pattern of transmission electron microscopy after aging in example 2.
Detailed Description
The 2400MPa grade high ductility and high corrosion resistance maraging stainless steel and the method for manufacturing the same according to the present invention will be further explained and illustrated with reference to the drawings and the specific examples, which, however, should not be construed as unduly limiting the technical solution 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, C ≦ 0.02%, P ≦ 0.003%, S ≦ 0.003%, and Fe as a balance. C. P and S are inevitable impurities.
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 product is cooled to room temperature by air.
The mechanical properties of example 1 are shown in Table 2, 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 0.16V SCE . 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 a metallographic morphology graph after aging in example 1.
Example 2
Selecting pure iron, metal chromium, metal nickel, metal manganese, metal molybdenum, metal cobalt, metal titanium 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, C ≦ 0.02%, P ≦ 0.003%, S ≦ 0.003%, and Fe as a balance. C. P and S are inevitable impurities.
And preparing a billet by adopting vacuum melting in the whole process.
And (3) carrying out high-temperature homogenizing treatment, heating in air in a furnace manner, 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 in 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, cooling the cold-rolled sheet to room temperature, wherein the first aging temperature is 550 ℃, and the aging time is 40 h; 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 2, the average hardness is 549.2HV, the yield strength is 2080MPa, the tensile strength is 2490MPa, the elongation is 13.1 percent, and the pitting potential is 0.17V SCE . FIG. 3 is a stress-strain curve of example 2 after aging. FIG. 4 is a transmission electron micrograph of the aged TEM sample of example 2, wherein amorphous diffraction rings are formed at the martensite lath interfaces.
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 the average value was taken after beating 5 points and is shown in Table 2.
(2) Tensile mechanical properties: an electronic universal tester is used for 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 2.
(3) Corrosion resistance
The test specimen was processed into a size of 10mm x 2mm and exposed to 1cm after being encapsulated with epoxy resin 2 And (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 test solution was 0.1M Na 2 SO 4 + xnacal (PH = 3), experimental temperature 25 ℃. Electrochemical testing was performed using the CHI660E electrochemical workstation. A common three-electrode system is adopted for 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 (SC)E) As a reference electrode. Prior to the electrochemical experiments, the samples were subjected to-1.2V SEC The 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 2.
TABLE 2 composition and hardness, tensile properties and pitting points of the examples
Note: the contents of the components C, P, S, etc. in each example in Table 2 correspond to the elemental composition of stainless steel. Wherein 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%, which is not shown in Table 2. Bal denotes the balance.
In summary, the invention discloses 2400MPa grade high-ductility high-corrosion-resistance maraging stainless steel and a preparation method thereof, and the stainless steel comprises the following components: by mass percent, co = 2.0-4.0, ni = 6.0-8.0, cr = 11.0-16.0, ti = 0.3-1.5, mo = 4.0-7.0, mn = 0.08-1.0, si = 0.08-0.5, C ≤ 0.02, P ≤ 0.003, S ≤ 0.003, and the balance of Fe. According to the stainless steel, through the combination of optimization of alloy elements, double vacuum melting and corresponding thermal mechanical treatment processes, ultrahigh strength is obtained by utilizing the synergistic strengthening of multiple nanophase; meanwhile, an amorphous layer is introduced into the lath boundary, and the lath boundary decorated by the amorphous layer promotes the dislocation multiplication and absorbs the dislocation, so that the large plasticity and the large processing hardening capacity are obtained. The stainless steel has tensile strength up to 2400MPa, elongation up to 13 percent and pitting potential up to 0.17V under the conditions that C is less than or equal to 0.02 percent and Co is not more than 4 percent SCE (ii) a The valve can be used for key structures such as force bearing components of aircraft engines, valves for ships, pump components and the like.
Claims (8)
1. A2400 MPa-grade high-ductility high-corrosion-resistance maraging stainless steel is characterized by comprising the following components: according to mass percent, co = 2.0-4.0%, ni = 6.0-8.0%, cr = 11.0-13.5%, ti = 0.3-1.5%, mo = 4.0-7.0%, mn = 0.08-1.0%, si = 0.3-0.5%, 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 of the 2400MPa grade high-ductility high-corrosion-resistance maraging stainless steel comprises the following steps: (1) proportioning alloy elements; (2) carrying out vacuum smelting electrode in a vacuum induction smelting furnace; (3) vacuum consumable remelting; (4) high-temperature tempering treatment; (5) forging or hot rolling cogging; (6) cold rolling deformation; (7) heat treatment;
the heat treatment process in the step (7) comprises the following steps: performing two-stage aging treatment;
and in the two-stage aging treatment, the temperature of the first aging treatment is 450-600 ℃, the aging time is 0.5-500h, the air cooling or quenching is carried out to the room temperature, the temperature of the second aging treatment is 650-900 ℃, and the air cooling or quenching is carried out for 1-60min to the room temperature.
2. A method for preparing 2400MPa grade high ductility, high corrosion resistant maraging stainless steel according to claim 1, consisting of 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) Heat treatment;
the heat treatment process in the step (7) comprises the following steps: performing two-stage aging treatment;
and in the two-stage aging treatment, the temperature of the first aging treatment is 450-600 ℃, the aging time is 0.5-500h, the air cooling or quenching is carried out to the room temperature, the temperature of the second aging treatment is 650-900 ℃, and the air cooling or quenching is carried out for 1-60min to the room temperature.
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 bin, adding industrial silicon and metallic manganese into an alloy bin, adding the high-position bin metal into the furnace after the materials are completely melted, performing deoxidation alloying, and finally adding the alloy bin metal into the furnace, wherein the smelting period is that the refining temperature reaches 1550 to 1650 ℃, the refining time is not less than 60 minutes, and the stirring time is not less than 10 to 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 carried out on a riser.
5. The method for preparing 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 to 260kg/h, and the vacuum degree is kept at 10 in the remelting process -2 Pa and below.
6. The method for preparing the 2400MPa grade high-ductility high-corrosion-resistance maraging stainless steel according to claim 2, wherein in the step (4), the high-temperature soaking 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 to 180 ℃/h, the temperature is kept at 600 to 900 ℃ for 4 to 8h, then the temperature is kept at 1100 to 1300 ℃ for 20 to 50h, and furnace cooling, air cooling or oil cooling is carried out until the temperature reaches the room temperature.
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 hot rolling is forging 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 10-24h, and then discharging and 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 hot rolling total reduction of the plate is not less than 50%, the forging ratio of the forging billet is not less than 6, and after the forging or rolling deformation, the ice-water mixture is cooled.
8. The method for preparing the 2400MPa grade high-ductility-toughness high-corrosion-resistance maraging stainless steel according to claim 2, wherein in the step (6), the cold rolling deformation is carried out, the total reduction of the cold rolling of the plate is 40 to 60 percent, 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 pass rolling method, a universal rolling method or a drawing method, so as to obtain the size and the specification required by the product.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2021109843633 | 2021-08-25 | ||
| CN202110984363.3A CN113774280A (en) | 2021-08-25 | 2021-08-25 | 2400 MPa-grade high-ductility high-corrosion-resistance maraging stainless steel and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114517273A CN114517273A (en) | 2022-05-20 |
| CN114517273B true CN114517273B (en) | 2023-02-14 |
Family
ID=78839074
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110984363.3A Pending CN113774280A (en) | 2021-08-25 | 2021-08-25 | 2400 MPa-grade high-ductility high-corrosion-resistance maraging stainless steel and preparation method thereof |
| CN202210364148.8A Active CN114517273B (en) | 2021-08-25 | 2022-04-07 | 2400 MPa-grade high-ductility high-corrosion-resistance maraging stainless steel and preparation method thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110984363.3A Pending CN113774280A (en) | 2021-08-25 | 2021-08-25 | 2400 MPa-grade high-ductility high-corrosion-resistance maraging stainless steel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN113774280A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113774288A (en) * | 2021-08-25 | 2021-12-10 | 哈尔滨工程大学 | Ultra-high-strength high-performance medium plate maraging stainless steel and preparation method thereof |
| CN114574765B (en) * | 2022-03-04 | 2023-07-14 | 中国原子能科学研究院 | Preparation method of high-performance fastener for lead-based pile |
| CN114934240B (en) * | 2022-04-25 | 2023-10-10 | 中国科学院金属研究所 | Preparation method of ultra-high-strength high-corrosion-resistance high-nitrogen austenitic stainless steel |
| CN117230376B (en) * | 2023-11-10 | 2024-03-05 | 钢铁研究总院有限公司 | Electrode for producing 300M steel and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0257780A2 (en) * | 1986-08-21 | 1988-03-02 | Crucible Materials Corporation | Age-hardenable stainless steel |
| KR920006529A (en) * | 1990-09-21 | 1992-04-27 | 이상수 | High strength, high toughness, high corrosion resistance stainless maraging steel and manufacturing method |
| CN101886228A (en) * | 2009-05-13 | 2010-11-17 | 中国科学院金属研究所 | Low carbon martensite aged stainless steel with high strength high toughness and high decay resistance performances |
| CN101994066A (en) * | 2009-08-27 | 2011-03-30 | 中国科学院金属研究所 | Deformation induced maraging stainless steel and machining process thereof |
| CN102492894A (en) * | 2011-12-30 | 2012-06-13 | 重庆材料研究院 | High-dimension stable corrosion-resistant martensite steel and preparation method of steel structural material |
| WO2018022261A1 (en) * | 2016-07-26 | 2018-02-01 | The Boeing Company | Ultra-high strength maraging stainless steel with salt-water corrosion resistance |
| CN113046642A (en) * | 2021-03-11 | 2021-06-29 | 哈尔滨工程大学 | Low-cost high-strength high-corrosion-resistance stainless steel and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105838862A (en) * | 2016-05-26 | 2016-08-10 | 中国科学院金属研究所 | Method for refining grains of maraging stainless steel by cyclic phase transformation |
| CN105838861A (en) * | 2016-05-26 | 2016-08-10 | 中国科学院金属研究所 | Heat treatment method for maraging stainless steel |
| CN107974642A (en) * | 2017-01-17 | 2018-05-01 | 上海落日新材料科技有限公司 | A kind of cutter precipitation-hardening stainless steel and its manufacture method |
| CN110358983A (en) * | 2019-07-04 | 2019-10-22 | 中国科学院金属研究所 | A kind of precipitation hardening of martensitic stainless steel and preparation method thereof |
| CN110846588A (en) * | 2019-12-13 | 2020-02-28 | 南京金科特钢有限公司 | Maraging antibacterial stainless steel and preparation method thereof |
| CN113046654B (en) * | 2021-03-11 | 2023-12-08 | 哈尔滨工程大学 | High-plasticity high-strength high-corrosion-resistance stainless steel and preparation method thereof |
-
2021
- 2021-08-25 CN CN202110984363.3A patent/CN113774280A/en active Pending
-
2022
- 2022-04-07 CN CN202210364148.8A patent/CN114517273B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0257780A2 (en) * | 1986-08-21 | 1988-03-02 | Crucible Materials Corporation | Age-hardenable stainless steel |
| KR920006529A (en) * | 1990-09-21 | 1992-04-27 | 이상수 | High strength, high toughness, high corrosion resistance stainless maraging steel and manufacturing method |
| CN101886228A (en) * | 2009-05-13 | 2010-11-17 | 中国科学院金属研究所 | Low carbon martensite aged stainless steel with high strength high toughness and high decay resistance performances |
| CN101994066A (en) * | 2009-08-27 | 2011-03-30 | 中国科学院金属研究所 | Deformation induced maraging stainless steel and machining process thereof |
| CN102492894A (en) * | 2011-12-30 | 2012-06-13 | 重庆材料研究院 | High-dimension stable corrosion-resistant martensite steel and preparation method of steel structural material |
| WO2018022261A1 (en) * | 2016-07-26 | 2018-02-01 | The Boeing Company | Ultra-high strength maraging stainless steel with salt-water corrosion resistance |
| CN107653421A (en) * | 2016-07-26 | 2018-02-02 | 中国科学院金属研究所 | A kind of superhigh intensity martensite aged stainless steel of seawater corrosion resistance |
| CN113046642A (en) * | 2021-03-11 | 2021-06-29 | 哈尔滨工程大学 | Low-cost high-strength high-corrosion-resistance stainless steel and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113774280A (en) | 2021-12-10 |
| CN114517273A (en) | 2022-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114517273B (en) | 2400 MPa-grade high-ductility high-corrosion-resistance maraging stainless steel and preparation method thereof | |
| CN113046642B (en) | Low-cost high-strength high-corrosion-resistance stainless steel and preparation method thereof | |
| CN109628836B (en) | High-strength anti-seismic fire-resistant steel for building structure and preparation method thereof | |
| CN114717487B (en) | 2700 MPa-grade high-ductility high-corrosion-resistance maraging stainless steel and preparation method thereof | |
| CN114921732B (en) | Multiphase reinforced ultra-high strength maraging stainless steel and preparation method thereof | |
| CN111218618B (en) | Hydrogen embrittlement resistant, high strength and toughness stainless steel bar for fastener and method of making same | |
| CN114717488A (en) | 1800MPa grade high-ductility high-corrosion-resistance maraging stainless steel and preparation method thereof | |
| CN114921717A (en) | 2000 MPa-grade high-ductility high-corrosion-resistance maraging stainless steel and preparation method thereof | |
| CN114921730B (en) | Ultra-high-strength high-performance sheet maraging stainless steel and preparation method thereof | |
| CN113046654B (en) | High-plasticity high-strength high-corrosion-resistance stainless steel and preparation method thereof | |
| CN113249645B (en) | High-ductility and ultrahigh-strength ductile steel and preparation method thereof | |
| CN112195402B (en) | Precipitation-strengthened high-strength and high-toughness medium manganese steel plate and preparation method thereof | |
| CN114717486B (en) | Ultra-high-strength high-performance maraging stainless steel and warm rolling preparation method thereof | |
| CN114517276A (en) | Ultra-low carbon high-performance maraging stainless steel and preparation method thereof | |
| CN108690939B (en) | High-forming nitrogen-containing austenitic stainless steel and manufacturing method thereof | |
| CN115044838A (en) | Composite reinforced type ultrahigh-strength and high-toughness martensitic stainless steel and preparation method thereof | |
| CN114807772A (en) | Aging-strengthened high-strength high-toughness light steel and manufacturing method thereof | |
| CN113106356B (en) | High-strength martensite precipitation hardening stainless steel and preparation method thereof | |
| CN114921731B (en) | Maraging stainless steel for ultra-high-strength high-performance medium plate and preparation method thereof | |
| CN115522126B (en) | Medium manganese steel with good wear resistance and production method thereof | |
| JP2008013812A (en) | High toughness and high tensile strength thick steel plate and its production method | |
| CN114058960B (en) | High-strength high-toughness easy-welding nano steel with thickness of 25-60 mm and thickness of 1000MPa and preparation method thereof | |
| CN115537658A (en) | High manganese steel with good wear resistance and production method thereof | |
| CN114875318A (en) | Dispersed delta phase strengthened low-density high-strength and high-toughness steel and manufacturing method thereof | |
| CN110846594B (en) | Copper-containing ultra-low carbon bainite steel and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |