CN115044838A - Composite reinforced type ultrahigh-strength and high-toughness martensitic stainless steel and preparation method thereof - Google Patents
Composite reinforced type ultrahigh-strength and high-toughness martensitic stainless steel and preparation method thereof Download PDFInfo
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- 229910001105 martensitic stainless steel Inorganic materials 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
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- 239000010959 steel Substances 0.000 claims abstract description 114
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 229910000734 martensite Inorganic materials 0.000 claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 14
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 86
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- 230000032683 aging Effects 0.000 claims description 45
- 238000005242 forging Methods 0.000 claims description 43
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- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 9
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- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
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- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/007—Heat treatment of ferrous alloys containing Co
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- C21D6/00—Heat treatment of ferrous alloys
- C21D6/02—Hardening by precipitation
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- C21D6/00—Heat treatment of ferrous alloys
- C21D6/04—Hardening by cooling below 0 degrees Celsius
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- 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
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- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
- C22C33/06—Making ferrous alloys by melting using master alloys
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
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- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
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Abstract
The invention belongs to the field of steel preparation, and particularly relates to a composite reinforced type martensite stainless steel with ultrahigh strength and toughness and a preparation method thereof. The martensitic stainless steel comprises the following components: according to the mass percentage: c: 0.1-0.25%, Cr: 11-13%, Ni: 5.0-8.0%, Mo: 1.5-4.0%, Co: 6.5-8.5%, V: 0.2 to 0.4%, Nb: 0.01 to 0.04%, Cu: 0.5-1.5%, Al: 0.3-0.8%, P: less than or equal to 0.02 percent, S: less than or equal to 0.02 percent and the balance of Fe. According to the invention, through the composite reinforcement of the carbide M2C and intermetallic compounds beta-NiAl and epsilon-Cu and the reasonable collocation of each reinforced phase and alloy elements, the martensitic stainless steel has ultrahigh strength and good ductility, toughness and corrosion resistance.
Description
Technical Field
The invention belongs to the field of steel preparation, and particularly relates to a composite reinforced type martensite stainless steel with ultrahigh strength and toughness and a preparation method thereof.
Background
With the continuous development of the technology, advanced structural steels are vital to the modern world, and the continuous innovation of the advanced structural steels is the key for sustainable future. Steelmaking is considered one of the largest industrial sources of carbon dioxide emissions and environmental pollution in the world. With the unprecedented environmental challenges of global warming, haze and other human beings, the development and the use of the ultrahigh-strength stainless steel are of great importance in greatly reducing the number of common low-strength steel used at present; and the advanced ultra-high strength martensitic stainless steel has wide application prospect in the fields of aerospace, ocean development, equipment manufacturing and the like.
The secondary hardening ultrahigh-strength steel is mainly used for parts with higher requirements on strength and toughness, such as submarine shells, aircraft landing gears and the like. 300M and AerMet100 are representative ultra-high strength steels. During the aging process, fine M2C carbide is precipitated, and the strength and the hardness of the steel are improved. The mismatching degree of the carbides and the matrix is small, and fine precipitates can be formed on the martensite matrix; therefore, the secondary hardening exhibits good toughness and plasticity. Ferrium (Ferrium)
The stainless steel is a novel ultra-high strength stainless steel, developed by QuesTek Innovations company in 2003, and aims to solve the problem that toxic cadmium coatings must be used when other steel types are used. In contrast to the aeromet 100, the method,
more Cr and less Ni, higher corrosion resistance, and no reduction in strength and toughness. Typical ultra-high strength stainless steels include 17-4PH, 15-5PH, Custom465, 1RK91 and Ferrium
And the like, the main dispersion precipitation strengthening phases of these typical ultra-high strength steels are mainly single intermetallic compounds such as Cu-rich phases, NiAl phases, Ni3Ti phases, laves phases, and the like, or carbides for precipitation strengthening. The main problem is that single phase strengthening does not allow a good match between the strength and toughness of the steel. The traditional ultrahigh-strength steel 17-4PH and 15-5PH have excellent corrosion resistance, but the strength is low, and the service performance under severe environment cannot be met, wherein the performance is excellent
However, researches show that the too high content of Co can promote the spinodal decomposition of Cr and seriously affect the corrosion resistance of steel; and under the condition of the increasing exhaustion of Co resources nowadays, the price of Co is also increasing,
the production of steel also increases the cost of the steel.
Therefore, it is necessary to develop an ultra-high strength martensitic stainless steel having ultra-high toughness and excellent corrosion resistance, while saving material costs, facilitating production, and being safer. The invention patent application with publication number CN 113699464A discloses a super-high strength and high performance sheet maraging stainless steel, which comprises (by mass percent) Co 2.0-5.0%, Ni 6.0-9.0%, Cr 11.0-17.0%, Ti 0.5-1.8%, Mo 3.0-7.0%, Mn 0.08-1.0%, Si 0.08-0.5%, C0.02% or less, P0.003% or less, S0.003% or less, and the balance Fe. The elongation is 10.8 percent, and the tensile strength is 2713 MPa; the pitting potential Epit was 0.24 VSCE. The strengthening mechanism of the invention is precipitation strengthening and fine grain strengthening, the steel is mainly subjected to fine grain strengthening by adopting a cold rolling technology, the operation is complex, the material cost is high, and for parts which can not use sheet stainless steel, the steel type of the invention has certain limitation and poor plasticity.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims at realizing ultrahigh strength, toughness and high corrosion resistance, and provides maraging stainless steel with ultrahigh strength, toughness and high corrosion resistance and a preparation method thereof, wherein the specific technical scheme is as follows:
a composite reinforced type ultra-high strength and toughness martensitic stainless steel comprises the following components: according to the mass percentage: c: 0.1-0.25%, Cr: 11-13%, Ni: 5.0-8.0%, Mo: 1.5-4.0%, Co: 6.5-8.5%, V: 0.2 to 0.4%, Nb: 0.01 to 0.04%, Cu: 0.5-1.5%, Al: 0.3-0.8%, Mg: 0.002-0.006%, Ce: 0.01-0.08%, P: less than or equal to 0.02 percent, S: less than or equal to 0.02 percent and the balance of Fe.
The complete austenite interval of the martensitic stainless steel alloy system is 1100-1350 ℃. The microstructure of the martensitic stainless steel mainly comprises a lath-shaped martensite structure and a small amount of austenite structure, wherein the lath-shaped martensite structure also comprises M2C carbide which plays a strengthening role, a Cu-rich phase and a NiAl-equal nanometer-size precipitated phase. The proportion of lath-shaped martensite structure is 85-95%, and the proportion of austenite structure is 4-8%.
The hardness of the martensitic stainless steel is more than or equal to 52HRC, the tensile strength is more than or equal to 1900MPa, the elongation is more than or equal to 12%, and the notch impact energy is more than or equal to 25J.
The preparation method of the composite reinforced type ultrahigh-strength and high-toughness martensitic stainless steel comprises the following steps:
step 1, smelting: smelting under the protection of vacuum argon, firstly, adding industrial pure iron, chromium metal, nickel metal, molybdenum metal, cobalt metal and copper metal into a smelting furnace according to the component proportion of the martensitic stainless steel before smelting, and smelting until furnace burden is fully melted, wherein the smelting temperature can adopt 1530 +/-30 ℃; then adding graphite, vacuumizing and carrying out vacuum refining; then, closing the vacuum pump, filling argon, then sequentially adding metal aluminum, metal niobium, metal vanadium, nickel-magnesium alloy and rare earth cerium, and continuously smelting until furnace burden is fully melted, wherein the smelting temperature can adopt 1530 +/-30 ℃; finally, casting into steel ingots, wherein the casting temperature is 1530 +/-30 ℃.
Preferably: the smelting adopts a vacuum induction smelting furnace; the vacuum refining conditions are as follows: keeping the vacuum degree below 20Pa, and keeping the temperature for 20-30 min; the total pressure in the furnace after argon filling is 30000-40000 Pa.
Preferably: the method for carrying out high-temperature homogenization treatment on the steel ingot by furnace heating comprises the following steps: heating with the furnace at a rate of 4-6 ℃/min to 1200-1250 ℃, preserving heat for 8-10 h, and performing high-temperature homogenization treatment; the method for cooling to room temperature comprises the following steps: cooling to 1100-1150 ℃ with the furnace, taking out, and air cooling to room temperature.
Preferably: the furnace heating is furnace heating to 1150-1250 ℃, the forging finish forging temperature is 1150-1250 ℃, and the cooling to room temperature is cooling to room temperature on the asbestos.
In step 4, it is preferable that:
the method for heating and carrying out solution treatment comprises the following steps: instantaneously heating the steel to 1070-1100 ℃, and then preserving heat for 0.5-1 h;
the quenching mode is water cooling;
the subzero treatment is cooling in liquid nitrogen for 4-8 hours;
the method for carrying out aging treatment by raising the temperature to the aging temperature comprises the following steps: raising the temperature to 480 ℃ and 500 ℃ at the heating rate of 450-480 ℃/h, and continuing the aging treatment for 20-25 h;
before the aging treatment, pre-aging treatment at 530-550 ℃ for 30-40 min (the pre-aging treatment also increases the temperature to 530-550 ℃ at a heating rate of 450-480 ℃/h), cooling to room temperature, then increasing the temperature to the aging temperature at a heating rate of 450-480 ℃/h, and performing aging treatment;
the cooling mode to the room temperature is air cooling.
The martensitic stainless steel disclosed by the invention performs cutting strengthening on softer intermetallic compounds and bypassing strengthening on harder carbides through dislocation motion, strengthens steel grades by adopting two mechanisms of cutting and bypassing, reduces the influence of the strengthening on the toughness and plasticity of the steel grades through reasonable element collocation, enables the steel grades to have excellent comprehensive performance, and meets the service requirements of a harsh service environment on the ultrahigh-strength stainless steel. Wherein the main element components have the following functions:
the addition amount of the C element is 0.1-0.25%, the C element is used for forming M2C carbide with elements such as Mo and the like, fine and dispersed carbide is precipitated in the aging treatment process to form a strengthening phase, and excessively high C affects the toughness and plasticity, corrosion resistance and processability of the material, so that the highest content of the C element is controlled to be less than 0.25%.
The Ni and Al elements can form a nano beta-NiAl precipitation strengthening phase in a stainless steel structure, the minimum mismatch of crystal lattices of the precipitation phase and a substrate enables the precipitation phase to have good mechanical properties, the strength of a steel grade is improved, but the toughness of the steel grade is influenced by excessively high content of the precipitation phase, so that the content of Ni and Al is required to be controlled within a proper range.
Cu element can form a Cu-rich phase (mainly an epsilon-Cu phase) in a stainless steel structure for strengthening, but too high Cu content can influence the toughness and plasticity of steel, and the Cu content needs to be controlled within a proper range.
Co element is an element which is usually adopted by ultrahigh-strength steel and can strengthen a steel matrix, and is the existing commercial Furrium
The high-strength steel is strengthened by applying Co element, and has excellent mechanical property. However, the cost of alloy elements such as Co is high, and the Co content of the steel grades is generally about 14 wt%, so that the cost is high, and the high Co content seriously influences the corrosion resistance. Several ultra-high strength steels with low or even zero Co have been developed to date with toughness that is not comparable to that of high Co ultra-high strength steels. The main reason is that the low Co content is not favorable for the dispersion distribution of precipitated phases, the precipitation strengthening effect is weakened, and harmful phases are easily introduced to further deteriorate the toughness of the material simply by increasing the content of elements formed by the precipitated phases. According to the invention, the Co content is limited to 6.5-8.5%, and the high dislocation density of the martensite lath is mainly maintained by using Co element, so that more nucleation positions are provided for precipitation of a precipitation phase, and the dispersion distribution of the precipitation phase is promoted, namely, the reasonable Co content is matched with precipitation strengthening phases such as M2C, a Cu-rich phase and NiAl, so that the damage of the precipitation strengthening phases to the toughness and plasticity of steel is reduced, and the strengthening phases can better play a role.
The content of Cr in the martensitic stainless steel is 11.0-17.0%, Cr is an element for passivating the steel and endowing the steel with good corrosion resistance and rust resistance, the rust resistance and oxidation resistance are obviously improved along with the improvement of the content of the Cr, the seawater corrosion resistance of the steel can be better improved by the cooperation of the Cr and Mo, and the susceptibility of the steel to pitting corrosion is reduced.
Ni is an important element in the martensitic stainless steel, can improve the potential and passivation tendency of the stainless steel, can improve the cavitation resistance and soil corrosion resistance of the martensitic stainless steel, and can balance the proportion of ferrite forming elements and austenite forming elements (chromium-nickel equivalent ratio) in the steel so as to ensure that the designed steel is in an austenite single-phase region in a solution treatment temperature range.
Mo is mainly used for increasing the tempering stability and the secondary hardening effect and improving the strength and the crack resistance of the steel, the mechanism of improving the tempering stability by Mo is that fine close-packed cubic M2X phases are formed by adding the molybdenum, the secondary hardening effect is improved, and the addition amount of Mo is proper to effectively reduce intercrystalline precipitates, so that the molybdenum-containing steel has an excellent strength-plasticity synergistic effect, and the seawater corrosion resistance of the stainless steel can be improved by the molybdenum.
The trace addition of Mg can play a role in deoxidation, and meanwhile, a large amount of trace magnesium-containing composite inclusion particles can be introduced, so that the grain size of the inclusions can be effectively refined, and the dispersion degree can be improved. Magnesium treatment generates a large amount of fine particles in steel, and the fine particles serve as nuclei for nucleation in a cooling process after austenitization, so that a large amount of fine grains are formed in the steel, and the structure of the steel is refined.
The rare earth Ce can play a role in purifying molten steel, and mainly shows that the contents of oxygen and sulfur can be deeply reduced. The Ce added into the steel can also change the property, the form and the distribution of the inclusions, thereby increasing the capability of resisting crack formation and expansion of the inclusions and grain boundaries. The addition of trace amount of rare earth Ce in the steel can improve the hot workability of the steel, eliminate the segregation of sulfur, purify the crystal boundary and improve the thermoplasticity of the steel.
The invention has the beneficial effects that:
the composite reinforced type ultra-high strength and toughness martensitic stainless steel of the invention precipitates fine and dispersed M2C carbide, Cu-rich phase and NiAl phase by adding elements such as C, Cu, Al, Ni and the like in the aging treatment process, and ensures that the steel has ultra-high strength and simultaneously gives consideration to good ductility, toughness and corrosion resistance by virtue of the composite reinforcement of the carbide M2C and intermetallic compounds such as beta-NiAl and epsilon-Cu and the reasonable collocation of each reinforced phase and alloy elements.
The invention also provides a process for preparing the martensitic stainless steel, and the proper forging processing and heat treatment methods promote the generation and dispersion distribution of all strengthening phases, so that the ultrahigh-strength martensitic stainless steel with excellent mechanical property, good corrosion resistance and excellent toughness and plasticity can be obtained, the tensile strength of the obtained martensitic stainless steel is more than or equal to 1900MPa, the hardness is more than or equal to 52HRC, the elongation is more than or equal to 12%, the impact power is more than or equal to 25J, and the corrosion resistance is far better than that of Furrium S53 steel.
Drawings
FIG. 1 is a thermodynamic equilibrium phase diagram of the alloy composition of patent example 1 of the present invention. Wherein: 1-ferrite, 2-austenite, 3-copper rich phase, 4-laves phase, 5-M23C 6.
FIG. 2 is a graph showing the cyclic polarization of samples of the steel of example 1 of the present invention and FerriumS53 steel in a 3.5% NaCl solution in the peak aged state.
FIG. 3 is an age hardening curve for the steel grade of example 1 of the present invention.
FIG. 4 is a graph of engineering stress-strain at peak age for the steel grade of example 1 of the present invention.
FIG. 5 is a graph of engineering stress-strain at peak age for the steel grade of example 2 of the invention.
FIG. 6 is a metallographic microstructure photograph of a sample of a steel grade according to example 1 of the invention in the peak aged condition.
FIG. 7 is a metallographic microstructure photograph of a sample of a steel grade according to example 2 of the invention in the peak aged condition.
FIG. 8 is a metallographic microstructure photograph of a sample of a steel grade according to example 3 of the invention in the peak aged condition.
FIG. 9 is a metallographic microstructure photograph of a sample of a steel grade according to example 4 of the invention in the peak aged condition.
Detailed Description
The scheme and effect of the invention are further illustrated by the following examples:
example 1
The super-high strength and toughness martensitic stainless steel comprises the following chemical components in percentage by mass:
0.18C-11.5Cr-5.8Ni-3.1Mo-7.5Co-0.4V-0.015Nb-1.2Cu-0.55Al-0.005Mg-0.05Ce (wt.%), P: less than or equal to 0.02 percent, S: less than or equal to 0.02 percent and the balance of Fe. The thermodynamic equilibrium phase diagram of the components of the alloy is shown in figure 1, the complete solid solution temperature is over 1070 ℃, the content of stable austenite is lower within 430-530 ℃, and the content of various stable precipitated phases is higher within 400-600 ℃.
The microstructure of the martensitic stainless steel is mainly lath-shaped martensite, accounts for 90 percent, and simultaneously has a small amount of austenite of 5 percent.
The preparation method of the ultra-high strength and toughness martensitic stainless steel comprises the following steps:
step 1, smelting: the smelting is carried out by adopting a vacuum induction smelting furnace under the protection of vacuum argon. Specifically, according to the component proportion of the martensitic stainless steel, before smelting, adding industrial pure iron, metallic chromium, metallic nickel, metallic molybdenum, metallic cobalt and metallic copper into a smelting furnace, smelting at 1530 ℃ until furnace burden is fully molten, then adding graphite, vacuumizing until the vacuum degree reaches below 20Pa, preserving heat for 20min, and carrying out vacuum refining; then, the vacuum pump is closed, argon is filled until the total pressure is 40000Pa, then metal aluminum, metal niobium, metal vanadium, nickel-magnesium alloy and rare earth cerium are sequentially added through an external storage bin, the mixture is continuously smelted at 1535 ℃ until furnace burden is fully melted, and finally, steel ingots with the diameter of 10cm and the length of 30cm are cast at 1530 ℃.
FIG. 2 is a graph showing the cyclic polarization of the steel type specimens of this example and FerriumS53 steel in a 3.5% NaCl solution in the peak aged condition. As can be seen from the graph, the corrosion potential of the steel of the present invention was-141 mV, and the corrosion current density was 0.192. mu.A/cm 2 The corrosion potential of FerriumS53 steel is-226 mV, and the corrosion current density is 536.503 muA/cm 2 The corrosion resistance of the steel of the invention is far better than that of FerriumS53 steel.
FIG. 3 is the age hardening curve of the steel grade of this example, and FIG. 4 is the engineering stress-strain curve of the steel grade at peak age. It can be seen that the steel of the present invention has strength up to 1906MPa and has good elongation of 12%. Through mechanical property test, the obtained martensitic stainless steel has the hardness of 52.3HRC, the tensile strength of 1906MPa, the elongation of 12 percent and the notch impact energy of 27.5J.
The microstructure of the ultra-high strength and toughness martensitic stainless steel prepared in this example in the peak aging state is shown in fig. 6.
Example 2
The super-high strength and toughness martensitic stainless steel comprises the following chemical components in percentage by mass:
0.18C-11.5Cr-5.8Ni-3.1Mo-7.5Co-0.4V-0.015Nb-1.2Cu-0.57Al-0.005Mg-0.06Ce (wt.%), P: less than or equal to 0.02 percent, S: less than or equal to 0.02 percent and the balance of Fe. The microstructure of the martensitic stainless steel is mainly lath martensite, accounts for 88 percent, and simultaneously has a small amount of austenite of 6 percent.
The preparation method of the ultra-high strength and toughness martensitic stainless steel comprises the following steps:
step 1, smelting: the smelting is carried out by adopting a vacuum induction smelting furnace under the protection of vacuum argon. Specifically, according to the component proportion of the martensitic stainless steel, before smelting, adding industrial pure iron, metallic chromium, metallic nickel, metallic molybdenum, metallic cobalt and metallic copper into a smelting furnace, smelting at 1535 ℃ until furnace burden is fully melted, then adding graphite, vacuumizing until the vacuum degree reaches below 20Pa, preserving heat for 20min, and carrying out vacuum refining; then, the vacuum pump is closed, argon is filled until the total pressure is 40000Pa, then, metallic aluminum, metallic niobium, metallic vanadium, nickel-magnesium alloy and rare earth cerium are sequentially added through an external bin, smelting is continued at 1540 ℃ until furnace burden is fully melted, and finally, steel ingots with the diameter of 10cm and the length of 30cm are cast at 1535 ℃.
The engineering stress-strain curve of the steel grade of the embodiment in the peak aging state is shown in FIG. 5, and the microstructure of the prepared ultra-high strength and toughness martensitic stainless steel in the peak aging state is shown in FIG. 7. Through mechanical property test, the hardness of the martensitic stainless steel is 52.23HRC, the tensile strength is 1953MPa, the elongation is 14.5 percent, and the notch impact energy is 25.5J.
Example 3
The super-high strength and toughness martensitic stainless steel comprises the following chemical components in percentage by mass:
0.2C-13Cr-5.6Ni-1.8Mo-8.5Co-0.35V-0.03Nb-0.8Cu-0.52Al-0.004Mg-0.06Ce (wt.%), P: less than or equal to 0.02 percent, S: less than or equal to 0.02 percent and the balance of Fe.
The microstructure of the martensitic stainless steel is mainly lath-shaped martensite, accounts for 90 percent, and simultaneously has a small amount of austenite of 5 percent.
The preparation method of the ultra-high strength and toughness martensitic stainless steel comprises the following steps:
step 1, smelting: the smelting is carried out by adopting a vacuum induction smelting furnace under the protection of vacuum argon. Specifically, according to the component proportion of the martensitic stainless steel, before smelting, adding industrial pure iron, metal chromium, metal nickel, metal molybdenum, metal cobalt and metal copper into a smelting furnace, smelting at 1528 ℃ until furnace burden is fully melted, then adding graphite, vacuumizing until the vacuum degree reaches below 20Pa, preserving heat for 20min, and carrying out vacuum refining; then, the vacuum pump is closed, argon is filled until the total pressure is 40000Pa, then metal aluminum, metal niobium, metal vanadium, nickel-magnesium alloy and rare earth cerium are sequentially added through an external storage bin, smelting is continued at 1530 ℃ until furnace burden is fully melted, and finally, steel ingots with the diameter of 10cm and the length of 30cm are cast at 1528 ℃.
The microstructure of the ultra-high strength and toughness martensitic stainless steel prepared in this example in the peak aging state is shown in fig. 8. Through mechanical property test, the hardness of the martensitic stainless steel is 52.1HRC, the tensile strength is 1921MPa, the elongation is 12.2%, and the impact energy is 26J.
Example 4
The super-high strength and toughness martensitic stainless steel comprises the following chemical components in percentage by mass:
0.21C-13Cr-6.6Ni-1.8Mo-8.2Co-0.35V-0.02Nb-0.8Cu-0.53Al-0.005Mg-0.06Ce (wt.%), P: less than or equal to 0.02 percent, S: less than or equal to 0.02 percent and the balance of Fe. The microstructure of the martensitic stainless steel is mainly lath martensite, accounts for 88 percent, and simultaneously has a small amount of austenite of 6 percent.
The preparation method of the ultra-high strength and toughness martensitic stainless steel comprises the following steps:
step 1, smelting: the smelting is carried out by adopting a vacuum induction smelting furnace under the protection of vacuum argon. Specifically, according to the component proportion of the martensitic stainless steel, before smelting, adding industrial pure iron, metal chromium, metal nickel, metal molybdenum, metal cobalt and metal copper into a smelting furnace, smelting at 1528 ℃ until furnace burden is fully melted, then adding graphite, vacuumizing until the vacuum degree reaches below 20Pa, preserving heat for 20min, and carrying out vacuum refining; then, the vacuum pump is closed, argon is filled until the total pressure is 40000Pa, then metal aluminum, metal niobium, metal vanadium, nickel-magnesium alloy and rare earth cerium are sequentially added through an external storage bin, smelting is continued at 1530 ℃ until furnace burden is fully melted, and finally, steel ingots with the diameter of 10cm and the length of 30cm are cast at 1528 ℃.
The microstructure of the ultra-high strength and toughness martensitic stainless steel prepared in this example in the peak aging state is shown in fig. 9. Through mechanical property test, the hardness of the martensitic stainless steel is 52.25HRC, the tensile strength is 1930MPa, the elongation is 13.1 percent, and the notch impact energy is 26.5J.
Example 5
The super-high strength and toughness martensitic stainless steel comprises the following chemical components in percentage by mass:
0.1C-11Cr-8Ni-3.8Mo-8.5Co-0.2V-0.01Nb-0.5Cu-0.8Al-0.004Mg-0.07Ce (wt.%), P: less than or equal to 0.02 percent, S: less than or equal to 0.02 percent and the balance of Fe. The microstructure of the martensitic stainless steel is mainly lath martensite, accounts for 86%, and has a small amount of 7% of austenite.
The preparation method of the ultra-high strength and toughness martensitic stainless steel comprises the following steps:
step 1, smelting: the smelting is carried out by adopting a vacuum induction smelting furnace under the protection of vacuum argon. Specifically, according to the component proportion of the martensitic stainless steel, before smelting, adding industrial pure iron, metallic chromium, metallic nickel, metallic molybdenum, metallic cobalt and metallic copper into a smelting furnace, smelting at 1540 ℃ until furnace burden is fully melted, then adding graphite, vacuumizing until the vacuum degree reaches below 20Pa, preserving heat for 20min, and carrying out vacuum refining; then, the vacuum pump is closed, argon is filled until the total pressure is 40000Pa, then metal aluminum, metal niobium, metal vanadium, nickel-magnesium alloy and rare earth cerium are sequentially added through an external bin, smelting is continued at 1545 ℃ until furnace burden is fully melted, and finally, steel ingots with the diameter of 10cm and the length of 30cm are cast at 1540 ℃.
The mechanical property test shows that the ultra-high strength and toughness martensitic stainless steel prepared by the steel grade of the embodiment has the hardness of 52.5HRC, the tensile strength of 1943MPa, the elongation of 13.5% and the notch impact energy of 26J.
Example 6
The super-high strength and toughness martensitic stainless steel comprises the following chemical components in percentage by mass:
0.25C-11.5Cr-5.2Ni-1.5Mo-6.5Co-0.2V-0.02Nb-1.5Cu-0.35Al-0.005Mg-0.08Ce (wt.%), P: less than or equal to 0.02 percent, S: less than or equal to 0.02 percent and the balance of Fe.
The microstructure of the martensitic stainless steel is mainly lath martensite, and the proportion is 89%, and simultaneously, the microstructure has a small amount of austenite of 4%.
The preparation method of the ultra-high strength and toughness martensitic stainless steel comprises the following steps:
step 1, smelting: the smelting is carried out by adopting a vacuum induction smelting furnace under the protection of vacuum argon. Specifically, according to the component proportion of the martensitic stainless steel, before smelting, adding industrial pure iron, metallic chromium, metallic nickel, metallic molybdenum, metallic cobalt and metallic copper into a smelting furnace, smelting at 1545 ℃ until furnace burden is fully melted, then adding graphite, vacuumizing until the vacuum degree reaches below 20Pa, preserving heat for 20min, and carrying out vacuum refining; then, a vacuum pump is closed, argon is filled until the total pressure is 40000Pa, then, metallic aluminum, metallic niobium, metallic vanadium, nickel-magnesium alloy and rare earth cerium are sequentially added through an external storage bin, smelting is continued at 1545 ℃ until furnace burden is fully melted, and finally, casting is carried out at 1545 ℃ to form a steel ingot with the diameter of 10cm and the length of 30 cm.
The mechanical property test of the ultra-high strength and toughness martensitic stainless steel prepared by the embodiment shows that the hardness of the martensitic stainless steel is 53.1HRC, the tensile strength is 1981MPa, the elongation is 12.6 percent, and the impact energy is 25.1J.
Example 7
The super-high strength and toughness martensitic stainless steel comprises the following chemical components in percentage by mass:
0.25C-11.5Cr-5.2Ni-1.5Mo-6.5Co-0.2V-0.02Nb-1.5Cu-0.35Al-0.003Mg-0.06Ce (wt.%), P: less than or equal to 0.02 percent, S: less than or equal to 0.02 percent and the balance of Fe.
The microstructure of the martensitic stainless steel is mainly lath martensite, and the proportion is 89%, and simultaneously, the microstructure has a small amount of austenite of 4%.
The preparation method of the ultra-high strength and toughness martensitic stainless steel comprises the following steps:
step 1, smelting: the smelting is carried out by adopting a vacuum induction smelting furnace under the protection of vacuum argon. Specifically, according to the component proportion of the martensitic stainless steel, before smelting, adding industrial pure iron, metallic chromium, metallic nickel, metallic molybdenum, metallic cobalt and metallic copper into a smelting furnace, smelting at 1545 ℃ until furnace burden is fully melted, then adding graphite, vacuumizing until the vacuum degree reaches below 20Pa, preserving heat for 20min, and carrying out vacuum refining; then, a vacuum pump is closed, argon is filled until the total pressure is 40000Pa, then, metallic aluminum, metallic niobium, metallic vanadium, nickel-magnesium alloy and rare earth cerium are sequentially added through an external storage bin, smelting is continued at 1545 ℃ until furnace burden is fully melted, and finally, casting is carried out at 1545 ℃ to form a steel ingot with the diameter of 10cm and the length of 30 cm.
The mechanical property test of the ultra-high strength and toughness martensitic stainless steel prepared by the embodiment shows that the hardness of the martensitic stainless steel is 53.1HRC, the tensile strength is 1981MPa, the elongation is 12.6 percent, and the impact energy is 25.1J.
Example 8
The super-high strength and toughness martensitic stainless steel comprises the following chemical components in percentage by mass: 0.22C-12.5Cr-5.8Ni-2.5Mo-7.5Co-0.25V-0.03Nb-0.9Cu-0.45Al-0.005Mg-0.05Ce (wt.%), P: less than or equal to 0.02 percent, S: less than or equal to 0.02 percent and the balance of Fe.
The microstructure of the martensitic stainless steel is mainly lath martensite, and the proportion is 89%, and simultaneously, the microstructure has a small amount of austenite of 5%.
The preparation method of the ultra-high strength and toughness martensitic stainless steel comprises the following steps:
step 1, smelting: the smelting is carried out by adopting a vacuum induction smelting furnace under the protection of vacuum argon. Specifically, according to the component proportion of the martensitic stainless steel, before smelting, adding industrial pure iron, metallic chromium, metallic nickel, metallic molybdenum, metallic cobalt and metallic copper into a smelting furnace, smelting at 1545 ℃ until furnace burden is fully melted, then adding graphite, vacuumizing until the vacuum degree reaches below 20Pa, preserving heat for 30min, and carrying out vacuum refining; then, the vacuum pump is closed, argon is filled until the total pressure is 35000Pa, then, metallic aluminum, metallic niobium, metallic vanadium, nickel-magnesium alloy and rare earth cerium are sequentially added through an external storage bin, smelting is continued at 1545 ℃ until furnace burden is fully melted, and finally, casting is carried out at 1545 ℃ to form a steel ingot with the diameter of 10cm and the length of 30 cm.
According to the mechanical property test, the hardness of the martensitic stainless steel prepared by the embodiment is 52.8HRC, the tensile strength is 1926MPa, the elongation is 13.6%, and the impact energy is 26.5J.
The present invention discloses a detailed preparation method and process flow of an ultra-high toughness martensitic stainless steel, and the above examples only express the embodiments of the present invention, but do not represent the limitation of the scope of the present invention, and it must be pointed out that all the changes or modifications made on the premise of the inventive concept are within the protection scope of the present invention.
Claims (10)
1. The composite reinforced type ultrahigh-strength and high-toughness martensitic stainless steel is characterized by comprising the following components: according to the mass percentage: c: 0.1-0.25%, Cr: 11-13%, Ni: 5.0-8.0%, Mo: 1.5-4.0%, Co: 6.5-8.5%, V: 0.2 to 0.4%, Nb: 0.01 to 0.04%, Cu: 0.5-1.5%, Al: 0.3-0.8%, Mg: 0.002-0.006%, Ce: 0.01-0.08%, P: less than or equal to 0.02 percent, S: less than or equal to 0.02 percent and the balance of Fe.
2. The composite reinforced type ultra-high strength and toughness martensitic stainless steel as claimed in claim 1, wherein the microstructure of the martensitic stainless steel comprises lath martensite and austenite, the ratio of lath martensite is 85% -95%, and the ratio of austenite is 4% -8%.
3. The composite reinforced type ultrahigh-strength martensitic stainless steel as claimed in claim 1, wherein the tensile strength of the martensitic stainless steel is not less than 1900MPa, the hardness is not less than 52HRC, the elongation is not less than 12%, and the notch impact energy is not less than 25J.
4. The preparation method of the composite reinforced type ultrahigh-strength martensitic stainless steel as claimed in claim 1, characterized by comprising the following steps:
step 1, smelting: according to the component proportion of the martensitic stainless steel, before smelting, adding industrial pure iron, metal chromium, metal nickel, metal molybdenum, metal cobalt and metal copper into a smelting furnace, smelting until furnace burden is fully melted, then adding graphite, and vacuumizing for vacuum refining; then the vacuum pump is closed, argon is filled, then metal aluminum, metal niobium, metal vanadium, nickel-magnesium alloy and rare earth cerium are sequentially added, the smelting is continued until furnace burden is fully melted, and finally steel ingots are cast;
step 2, casting post-treatment: cutting off a head shrinkage cavity and a tail of the steel ingot, smearing a refractory decarburization-resistant coating, heating the steel ingot along with a furnace, performing high-temperature homogenization treatment, and then cooling to room temperature;
step 3, forging: heating the steel ingot along with a furnace, forging into a plate blank after three piers and three pulls, and cooling to room temperature to obtain a forged plate;
step 4, heat treatment after forging: heating the forged plate for solution treatment; then quenching to room temperature; then the temperature is raised to the room temperature after the deep cooling treatment; then, the temperature is continuously increased to the aging temperature for aging treatment, and finally the temperature is cooled to the room temperature.
5. The production method according to claim 4, wherein in the step 1:
adding industrial pure iron, chromium metal, nickel metal, molybdenum metal, cobalt metal and copper metal into a smelting furnace, and smelting until furnace burden is fully melted, wherein the smelting temperature is 1530 +/-30 ℃;
sequentially adding metal aluminum, metal niobium, metal vanadium, nickel magnesium or nickel, and continuously smelting until furnace burden is fully melted, wherein the smelting temperature is 1530 +/-30 ℃;
the casting temperature of the cast steel ingot is 1530 +/-30 ℃.
6. The preparation method according to claim 4, wherein in the step 1, the smelting is performed by using a vacuum induction smelting furnace; the vacuum refining conditions are as follows: keeping the vacuum degree below 20Pa, and keeping the temperature for 20-30 min;
the total pressure in the furnace after argon filling is 30000-40000 Pa.
7. The production method according to claim 4, wherein in the step 2:
the method for carrying out high-temperature homogenization treatment on the steel ingot by furnace heating comprises the following steps: heating with the furnace at a rate of 4-6 ℃/min to 1200-1250 ℃, preserving heat for 8-10 h, and performing high-temperature homogenization treatment;
the method for cooling to room temperature comprises the following steps: cooling to 1100-1150 ℃ with the furnace, taking out, and air cooling to room temperature.
8. The method according to claim 4, wherein in the step 3, the furnace heating is furnace heating to 1150-1250 ℃, the forging finish forging temperature is 1150-1250 ℃, and the cooling to room temperature is cooling to room temperature on asbestos.
9. The method according to claim 4, wherein in step 4:
the method for heating and carrying out solution treatment comprises the following steps: instantaneously heating the steel to 1070-1100 ℃, and then preserving heat for 0.5-1 h;
the quenching mode is water cooling;
the subzero treatment is cooling in liquid nitrogen for 4-8 hours;
the method for carrying out aging treatment by raising the temperature to the aging temperature comprises the following steps: raising the temperature to 480 ℃ and 500 ℃ at the heating rate of 450-480 ℃/h, and continuing the aging treatment for 20-25 h;
the cooling mode to the room temperature is air cooling.
10. The preparation method according to claim 9, wherein before the aging treatment, the temperature is raised to 530-550 ℃ at a temperature raising rate of 450-480 ℃/h, the pre-aging treatment is carried out for 30-40 min, then the temperature is cooled to room temperature, and the temperature is raised to the aging temperature again at 450-480 ℃/h for the aging treatment.
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Application publication date: 20220913 |