CN108866453A - A kind of martensite heat-resistant steel and preparation method thereof - Google Patents

A kind of martensite heat-resistant steel and preparation method thereof Download PDF

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CN108866453A
CN108866453A CN201810794256.2A CN201810794256A CN108866453A CN 108866453 A CN108866453 A CN 108866453A CN 201810794256 A CN201810794256 A CN 201810794256A CN 108866453 A CN108866453 A CN 108866453A
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resistant steel
martensite
type
temperature
martensite heat
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CN108866453B (en
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乔勋
王琳淋
李京泽
赵巧绒
孙琳琳
党波
白旭峰
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Taizhou Shunda Electric Furnace Co.,Ltd.
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Xijing University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18Hardening; Quenching with or without subsequent tempering
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/004Heat treatment of ferrous alloys containing Cr and Ni
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/005Heat treatment of ferrous alloys containing Mn
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/008Heat treatment of ferrous alloys containing Si
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/001Ferrous alloys, e.g. steel alloys containing N
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/008Martensite

Abstract

The invention discloses a kind of martensite heat-resistant steel and preparation method thereof, each element mass percent contained is:C:0.1~0.2%;Cr:9~14%;Ni:2.5~3.5%;Mo:1.0~2.0%;W:0.5~1.0%;Mn:0.5~1.0%;Si:0.10~0.5%;V:0.10~0.5%;Nb:0.1~0.5%;N:0.02~0.05%;Surplus is Fe;The carboritride being wherein precipitated is in Dispersed precipitate state, and the carboritride includes M2X type, M7C3 type, MX type and M6C type carbide.The Alloying Design of martensite heat-resistant steel is accurately controlled with tempering process and is combined by the present invention, by adjusting the content and type of alloying element, it is tempered using lower temperature, it is remarkably improved the high temperature toughness and tenacity of martensite heat-resistant steel, higher-strength and hardness are kept while obtaining high tenacity, avoids temper brittleness.

Description

A kind of martensite heat-resistant steel and preparation method thereof
Technical field
The invention belongs to technical field of heat-resistant steel, it is related to a kind of martensite heat-resistant steel and preparation method thereof.
Background technique
Martensite heat-resistant steel creep strength usually with higher, corrosion resistance, higher heat resistance and thermal conductivity, it is lower Thermal expansion coefficient is widely used in hot operation component, such as turbine blade, valve, steam boiler, exhaust valve for internal combustion engine, boat The equipment such as empty space flight and petrochemical industry.These components long services bear various load and (stretch, bending, turn round in hot environment Turn, impact, fatigue etc.) act on, while with high-temperature steam, air or contacts fuel gas, working environment is very harsh.With combustion gas wheel The development of machine and other high-temperature and high-pressure techniques, the performance to high temperature resistant component of machine is it is also proposed that increasingly higher demands.Due to In the high temperature environment, alloying element occurs to spread and cause structural transformation in steel, generates unfavorable shadow to the performance of high temperature components It rings.
For the high temperature obdurability for improving martensite heat-resistant steel, Alloying Treatment usually is carried out to martensite heat-resistant steel.Pass through The alloying elements such as Cr, Ni, Mn, Si, Mo are added, generate the reinforcing item of infusibility, and by tempering process, promote to strengthen item disperse analysis Out, tiny carbonitride or intermetallic compound are precipitated on martensitic matrix, such as MX, M2X, M7C3, M23C6 and The types such as M6C (M is metallic element, and X is nonmetalloid C, N etc.), to further increase the high temperature toughness and tenacity of heat resisting steel.Add The type and content of additional element is different, can significantly affect the performance of martensite heat-resistant steel, such as causes brittleness, processing difficulties, Cost increase etc..Tempering process is different, can also significantly affect the mechanical property of martensite heat-resistant steel.Lonneal causes material tough Property it is insufficient, easily cause temper brittleness;And tempering temperature is high, energy consumption increases, and the process time extends, and also results in the strength of materials It is insufficient, it is also possible to cause temper brittleness.
Summary of the invention
Present invention solves the problem in that a kind of martensite heat-resistant steel and preparation method thereof is provided, by martensite heat-resistant steel Alloying is combined with tempering process, is maintained higher intensity and hardness while obtaining high tenacity, is avoided temper brittleness.
The present invention is to be achieved through the following technical solutions:
A kind of martensite heat-resistant steel, each element mass percent contained are:
C:0.1~0.2%;Cr:9~14%;Ni:2.5~3.5%;Mo:1.0~2.0%;W:0.5~1.0%;Mn: 0.5~1.0%;Si:0.10~0.5%;V:0.10~0.5%;Nb:0.1~0.5%;N:0.02~0.05%;Surplus is Fe;
The carboritride being wherein precipitated be in Dispersed precipitate state, the carboritride include M2X type, M7C3 type, MX type and M6C type carbide.
Further, also contain B:0.10~0.5%, Co:0.10~0.5% element.
MX, M7C3 the type carbonitride being precipitated, are uniformly distributed in martensite lath.
, when carrying out tempering, tempering temperature is 560~610 DEG C for it, keeps the temperature 1.5~4 hours.
A kind of preparation method of martensite heat-resistant steel, including following operation:
1) the element ratio melting of following mass percent is become into steel ingot:
C:0.1~0.2%;Cr:9~14%;Ni:2.5~3.5%;Mo:1.0~2.0%;W:0.5~1.0%;Mn: 0.5~1.0%;Si:0.10~0.5%;V:0.10~0.5%;Nb:0.1~0.5%;N:0.02~0.05%;Surplus is Fe;
2) by the steel ingot of melting in 1150 DEG C~1050 DEG C progress higher temperature solid solutions, and 10~30 minutes are kept the temperature, makes to close Gold element is dissolved completely in austenite;High temperature forging is carried out later, and forging temperature is 1050~900 DEG C, to refine original Austria Family name's body tissue;
3) steel ingot is quenched after forging, the quenching oil that hardening media is 60 DEG C obtains the group based on martensite It knits;Finally carry out tempering:Tempering temperature is 560~610 DEG C, keeps the temperature 1.5~4h;
By tempering, the second-phase strength particle for being distributed small and dispersed is precipitated from martensitic matrix, obtains more Strengthening effect is dissipated, the martensite heat-resistant steel of obdurability is obtained.
Microelement B is also added into melting steel ingot:0.10~0.5%, Co:0.10~0.5% element.
MX, M7C3 type carbonitride of tiny distribution are precipitated in prepared martensite heat-resistant steel, is uniformly distributed in geneva In body lath.
Compared with prior art, the invention has the following beneficial technical effects:
Martensite heat-resistant steel provided by the invention and preparation method thereof, by the Alloying Design and tempering of martensite heat-resistant steel Technique is accurately controlled and is combined, and by adjusting the content and type of alloying element, is tempered using lower temperature, is remarkably improved horse The high temperature toughness and tenacity of family name's body heat resisting steel keeps higher-strength and hardness while obtaining high tenacity, avoids temper brittleness.
Martensite heat-resistant steel provided by the invention and preparation method thereof, in added alloying element, trace V, Nb, N can Significantly improve the creep rupture strength of material;The elements such as W, B, Co are added, it is appropriate to reduce Mo content, it can be mentioned by optimizing heat treatment High creep resistance energy;Cr can enhance creep rupture strength and creep strength;Si can improve inoxidizability;In melting, steel ingot is first Higher temperature solid solution is carried out, is dissolved completely in alloying element in austenite, carries out high temperature forging later with thinning microstructure;Forging After be quenched, obtain martensite based on tissue;Tempering is finally carried out, keeps the second of small and dispersed distribution mutually strong Change particle (such as V/Nb carboritride MX, M2X, M7C3 and M6C) to be precipitated from martensitic matrix, obtains dispersion-strengtherning effect Fruit.Carboritride of disperse educt etc. can play the role of pinning dislocation at high temperature, hinder dislocation motion, significantly improve horse The obdurability of family name's body heat resisting steel.
Martensite heat-resistant steel provided by the invention passes through metallographic, scanning electron microscope and transmission electron microscope observation Analysis, carboritride precipitation quantity is more, is in Dispersed precipitate state, predominantly M2X and M7C3 type carbide, while with few MX the and M6C type carboritride of amount;Martensite lath obtains replys to a certain extent, is distributed in fine uniform.Mechanical property into Row test shows that ballistic work is 132J, hardness 371HBW, tensile strength 1087MPa.
Detailed description of the invention
Fig. 1 is martensite heat-resistant steel metallographic microscope;
Fig. 2 is martensite heat-resistant steel scanning electron microscopy (SEM);
Fig. 3 martensite heat-resistant steel transmission electron microscopy figure (TEM).
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and It is not to limit.
To overcome the problems, such as conventional martensitic heat resisting steel obdurability deficiency and temper brittleness, a kind of novel martensitic of the present invention Heat resisting steel and preparation method thereof.The solution of the present invention main feature is shown as:
(1) based on martensite heat-resistant steel, by alloying adjust the elements such as C, Cr, Mo (reduce C content to 0.2%, It mentions high-Cr and is up to 14%, reduce Mo content most down to 0.5%), and the elements such as appropriate W, Nb, Co, N are added, formed new Type martensite heat-resistant steel;
(2) by tempering process control carboritride be precipitated type, pattern and distribution, diffusion-precipitation strengthen MC and The tiny carbide of M7C3 obtains dispersion-strengthened effect, avoids temper brittleness, reach high tenacity, while keeping higher-strength and hard Degree;
(3) it is tempered using lower temperature, simple process, high production efficiency, save the cost.
Martensite heat-resistant steel of the invention, the trade mark are represented by 15Cr12Ni2Mo2WMnSiVNbN, wherein each element content Percentage is C:0.1~0.2;Cr:9~14;Ni:2.5~3.5;Mo:0.5~1.5;W:0.5~1.0;Mn:0.5~1.0; Si:0.10~0.5;V:0.10~0.5;Nb:0.1~0.5;N:0.02~0.05, remaining is Fe;The carbon nitrification being wherein precipitated Object is in Dispersed precipitate state, and the carboritride includes M2X type, M7C3 type, MX type and M6C type carbide.
Further, while the elements (B such as micro B, Co may be contained:0.10~0.5%, Co:0.10~0.5%)
Alloying element added by the present invention, wherein trace V, Nb, N are remarkably improved the creep rupture strength of material;Add Enter the elements such as W, B, Co, it is appropriate to reduce Mo content, creep-resistant property can be improved by optimizing heat treatment;Cr can enhance high-temperature and durable Intensity and creep strength;Si can improve inoxidizability.
MX, M7C3 the type carbonitride being precipitated, are uniformly distributed in martensite lath.
Preparation method of the invention:
First to meeting the steel ingot of 15Cr12Ni2Mo2WMnSiVNbN alloying element in 1150 DEG C~1050 DEG C temperature ranges Higher temperature solid solution is carried out, alloying element is dissolved completely in austenite, carries out high temperature forging, forging temperature 1050 later ~900 DEG C, to reach thinning microstructure;It is quenched after forging, the quenching oil that hardening media is 60 DEG C, obtaining martensite is Main tissue;Finally carry out tempering:Tempering temperature is 560~610 DEG C, keeps the temperature 1.5~4 hours.
Further, including following operation:
1) the element ratio melting of following mass percent is become into steel ingot:
C:0.1~0.2%;Cr:9~14%;Ni:2.5~3.5%;Mo:1.0~2.0%;W:0.5~1.0%;Mn: 0.5~1.0%;Si:0.10~0.5%;V:0.10~0.5%;Nb:0.1~0.5%;N:0.02~0.05%;Surplus is Fe;
2) by the steel ingot of melting in 1150 DEG C~1050 DEG C progress higher temperature solid solutions, and 10~30 minutes are kept the temperature, makes to close Gold element is dissolved completely in austenite;High temperature forging is carried out later, and forging temperature is 1050~900 DEG C, to refine original Austria Family name's body tissue;
3) steel ingot is quenched after forging, the quenching oil that hardening media is 60 DEG C obtains the group based on martensite It knits;Finally carry out tempering:Tempering temperature is 560~610 DEG C, keeps the temperature 1.5~4h;
By tempering, the second-phase strength particle for being distributed small and dispersed is precipitated from martensitic matrix, obtains more Strengthening effect is dissipated, the martensite heat-resistant steel of obdurability is obtained.
MX, M7C3 type carbonitride of tiny distribution are precipitated in prepared martensite heat-resistant steel, is uniformly distributed in geneva In body lath.
The present invention is by tempering process, the second-phase strength particle for being distributed small and dispersed, as V/Nb carboritride MX, M2X, M7C3 and M6C etc. are precipitated from martensitic matrix, obtain dispersion-strengthened effect.Carboritride of disperse educt etc. is in height Temperature is lower can be played the role of pinning dislocation, hinder dislocation motion, and the obdurability of martensite heat-resistant steel is significantly improved.
Specific embodiment is given below.
Embodiment 1
Novel martensitic heat resisting steel and its preparation process
Smelting steel ingot alloying element percentage is:C:0.17;Cr:14;Ni:2.8;Mo:0.7;W:0.6;Mn:0.7;Si: 0.2;V:0.15;Nb:0.17;N:0.046;Co:0.12.Steel ingot weight 12Kg.After high temperature solid solution, high temperature forging and quenching, Tempering is carried out to blank.Tempering temperature is 575 DEG C, and tempering insulation time is 1.5 hours.
Separately sampled 3 in blank different parts, pass through metallographic, scanning electron microscope and transmission electron microscope observation Analyze (result is as shown in Figure 1, Figure 2, Figure 3 shows), carboritride be precipitated quantity it is more, be in Dispersed precipitate state, predominantly M2X and M7C3 type carbide, while with a small amount of MX and M6C type carboritride;Martensite lath obtain to a certain extent reply (see Fig. 2), it is distributed in fine uniform.M2X type in the carboritride, M7C3 type carbide, MX type, in M6C type carbide, M Indicate that the metallic elements such as Fe, V, Mo, X indicate the nonmetalloids such as C, N).
The mechanical property of 1 workpiece of embodiment is tested, ballistic work 132J, hardness 371HBW, tensile strength 1087MPa。
Embodiment 2
Novel martensitic heat resisting steel and its preparation process
Smelting steel ingot alloying element percentage is:C:0.11;Cr:11.3;Ni:3.2;Mo:1.3;W:0.8;Mn:0.55; Si:0.12;B:0.11;Nb:0.4;N:0.034.Steel ingot weight 15Kg.After high temperature solid solution, high temperature forging and quenching, to blank Carry out tempering.Tempering temperature is 595 DEG C, and tempering insulation time is 4 hours.
Separately sampled 3 in blank different parts, pass through metallographic, scanning electron microscope and transmission electron microscope observation Analysis, carboritride precipitation quantity is more, is in Dispersed precipitate state, predominantly M2X and M7C3 type carbide, while with few MX the and M6C type carboritride of amount;Martensite lath obtains replys to a certain extent, is distributed in fine uniform.
The mechanical property of 2 workpiece of embodiment is tested, ballistic work 137J, hardness 351HBW, tensile strength 973MPa。
Example given above is to realize the present invention preferably example, and the present invention is not limited to the above embodiments.This field Technical staff's technical solution according to the present invention technical characteristic any nonessential addition, the replacement made, belong to this The protection scope of invention.

Claims (7)

1. a kind of martensite heat-resistant steel, which is characterized in that its each element mass percent contained is:
C:0.1~0.2%;Cr:9~14%;Ni:2.5~3.5%;Mo:1.0~2.0%;W:0.5~1.0%;Mn:0.5~ 1.0%;Si:0.10~0.5%;V:0.10~0.5%;Nb:0.1~0.5%;N:0.02~0.05%;Surplus is Fe;
The carboritride being wherein precipitated is in Dispersed precipitate state, and the carboritride includes M2X type, M7C3 type, MX type With M6C type carbide.
2. martensite heat-resistant steel as described in claim 1, which is characterized in that also contain B:0.10~0.5%, Co:0.10~ 0.5% element.
3. martensite heat-resistant steel as described in claim 1, which is characterized in that MX, M7C3 the type carbonitride being precipitated, uniformly It is distributed in martensite lath.
4. martensite heat-resistant steel as described in claim 1, which is characterized in that, when carrying out tempering, tempering temperature is for it 560~610 DEG C, keep the temperature 1.5~4 hours.
5. a kind of preparation method of martensite heat-resistant steel, which is characterized in that including following operation:
1) the element ratio melting of following mass percent is become into steel ingot:
C:0.1~0.2%;Cr:9~14%;Ni:2.5~3.5%;Mo:1.0~2.0%;W:0.5~1.0%;Mn:0.5~ 1.0%;Si:0.10~0.5%;V:0.10~0.5%;Nb:0.1~0.5%;N:0.02~0.05%;Surplus is Fe;
2) by the steel ingot of melting in 1150 DEG C~1050 DEG C progress higher temperature solid solutions, and 10~30 minutes are kept the temperature, keeps alloy first Element is dissolved completely in austenite;High temperature forging is carried out later, and forging temperature is 1050~900 DEG C, to refine original austenite Tissue;
3) steel ingot is quenched after forging, the quenching oil that hardening media is 60 DEG C obtains the tissue based on martensite;Most After carry out tempering:Tempering temperature is 560~610 DEG C, keeps the temperature 1.5~4h;
By tempering, the second-phase strength particle for being distributed small and dispersed is precipitated from martensitic matrix, and it is strong to obtain disperse Change effect, obtains the martensite heat-resistant steel of obdurability.
6. the preparation method of martensite heat-resistant steel as claimed in claim 5, which is characterized in that be also added into melting steel ingot Microelement B:0.10~0.5%, Co:0.10~0.5% element.
7. the preparation method of martensite heat-resistant steel as claimed in claim 5, which is characterized in that prepared martensite heat-resistant steel Middle MX, M7C3 type carbonitride that tiny distribution is precipitated, is uniformly distributed in martensite lath.
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US11220733B1 (en) 2020-08-31 2022-01-11 University Of Science And Technology Beijing Low carbon martensitic high temperature strength steel and preparation method thereof
CN114032472A (en) * 2021-11-02 2022-02-11 西京学院 Novel cobalt-free maraging steel and strengthening and toughening treatment process thereof

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CN104694832A (en) * 2015-02-28 2015-06-10 钢铁研究总院 Martensitic stainless steel for nuclear reactor and preparation method of stainless steel

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US11220733B1 (en) 2020-08-31 2022-01-11 University Of Science And Technology Beijing Low carbon martensitic high temperature strength steel and preparation method thereof
WO2022041207A1 (en) * 2020-08-31 2022-03-03 北京科技大学 High-temperature high-strength low-carbon martensitic heat-resistant steel and preparation method therefor
CN114032472A (en) * 2021-11-02 2022-02-11 西京学院 Novel cobalt-free maraging steel and strengthening and toughening treatment process thereof
CN114032472B (en) * 2021-11-02 2023-02-07 西京学院 Cobalt-free maraging steel and strengthening and toughening treatment process thereof

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