CN111304555B - In-situ endogenously precipitated ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel and preparation method and application thereof - Google Patents

In-situ endogenously precipitated ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel and preparation method and application thereof Download PDF

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CN111304555B
CN111304555B CN202010246828.0A CN202010246828A CN111304555B CN 111304555 B CN111304555 B CN 111304555B CN 202010246828 A CN202010246828 A CN 202010246828A CN 111304555 B CN111304555 B CN 111304555B
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resistant steel
austenitic heat
endogenously
heat
precipitated
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CN111304555A (en
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刘天龙
骆智超
郑志斌
郑开宏
龙骏
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Institute of New Materials of Guangdong Academy of Sciences
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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
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/06—Deoxidising, e.g. killing
    • 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
    • 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
    • C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
    • 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
    • C22C33/06—Making ferrous alloys by melting using master alloys
    • 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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22C38/18—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
    • 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
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron

Abstract

The invention relates to the technical field of alloy materials, and discloses in-situ endogenously precipitated ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel and a preparation method and application thereof. The Cr-Mn-Ni-C-N austenitic heat-resistant steel comprises the following components in percentage by mass: cr: 8.5% -18%, Mn: 10% -12%, Ni: 3.5% -4.5%, Si: 0.5% -0.8%, endogenously precipitated ceramic particles: 2% -13%, total amount of C and N: 0.3 to 1.2 percent of iron and impurities in balance. The preparation method of the austenitic heat-resistant steel comprises the following steps: smelting and forging the preparation raw materials containing the chemical components of the austenitic heat-resistant steel. The uniform dispersion distribution of the ceramic particles can ensure that the austenitic heat-resistant steel has excellent room temperature and high temperature strength, particularly Cr2B. The TiC ceramic particles can enable the austenitic heat-resistant steel to have excellent high-temperature oxidation resistance.

Description

In-situ endogenously precipitated ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel and preparation method and application thereof
Technical Field
The invention relates to the technical field of alloy materials, in particular to in-situ endogenously precipitated ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel and a preparation method and application thereof.
Background
The heat-resistant steel is widely applied to the industrial fields of metallurgy, mines, petrochemical industry, electric power and electricity and the like and is used for preparing heat-resistant structural components. The oxidation resistance is an important performance index, so the research on the oxidation resistance of the heat-resistant steel is an important subject of the service of engineering structural materials. Heat-resistant steels can be classified into pearlite type heat-resistant steels, ferrite type heat-resistant steels, martensite type heat-resistant steels, and austenite type heat-resistant steels according to their structures at room temperature and use temperature conditions. The total amount of alloy elements of the pearlite heat-resistant steel is not more than 5%, the pearlite heat-resistant steel is mainly applied to the industries of power industry and petrochemical industry, the using temperature is 350-420 ℃, and the domestic representative steel grades comprise 15CrMo, 12Cr1MoV, 20Cr3WMoV and the like. The martensite heat-resistant steel is mainly used for preparing turbine last-stage blades, gas turbine blades, connecting pieces and the like, the using temperature is 570-600 ℃, and domestic representative steel grades comprise 2Cr12NiWMoV, 2Cr12WMoVNbB and the like. The ferritic heat-resistant steel is mainly used for preparing bypass pipes of power plants, the application temperature is lower than 800 ℃, and the representative steel grades comprise X10CrMoVNb9-1(T/P91) and X11CrMo9-1 (T/P9). The austenitic heat-resistant steel mainly takes Cr-Ni as a main material, is mainly used for preparing industrial heating furnaces and heat-resistant components thereof, petroleum cracking furnace hanging, cement cooling grid plates, ultra-supercritical boiler reheaters, superheater furnace tubes and the like, has excellent creep property at the temperature of over 600 ℃, has the oxidation resistance temperature of 850-1250 ℃, and represents steel numbers of 1Cr25Ni20Si2, 3Cr18Ni25Si2, Sanicro25 (produced by Sandvik company in Sweden) and SS2215 (produced by Yongxing special stainless steel member Co., Ltd. and Wu Ching stainless steel member Co., Ltd. in Jiangsu province in China).
Because of the excellent high-temperature strength and high-temperature oxidation resistance of the Cr-Ni series austenitic heat-resistant steel, the Cr-Ni series austenitic heat-resistant steel has wide application range and huge requirements and consumption at home and abroad. However, the Cr-Ni austenitic heat-resistant steel is expensive due to the influence of the fluctuation in the price of nickel resources. Cr-Mn- (Ni) -N series austenitic heat-resistant steel which replaces or partially replaces Ni by austenite stable elements such as Mn, N and the like is an ideal substitute material of Cr-Ni series austenitic heat-resistant steel due to excellent mechanical property and lower cost. However, the adverse effect of Mn on the oxidation resistance of austenitic heat-resistant steels limits the use of Cr-Mn- (Ni) -N based austenitic heat-resistant steels. Therefore, it is urgently needed to deeply research the oxidation resistance of the endogenously precipitated ceramic particle reinforced Cr-Mn- (Ni) -N austenitic heat-resistant steel and prepare the endogenously precipitated ceramic particle reinforced austenitic heat-resistant steel with low cost and high performance.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide an endogenously precipitated ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel, a preparation method thereof and application thereof in the field of buildings or steel products.
The invention is realized by the following steps:
in a first aspect, embodiments provide an endogenously precipitated ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel, which comprises the following chemical components in percentage by mass:
cr: 8.5% -18%, Mn: 10% -12%, Ni: 3.5% -4.5%, Si: 0.5% -0.8%, endogenously precipitated ceramic particles: 2% -13%, and the total amount of C and N: 0.3 to 1.2 percent of iron and the balance of inevitable trace elements.
In an alternative embodiment, the endogenous precipitating ceramic particles are Cr2B and/or carbon titanium ceramic particles, wherein the carbon titanium ceramic particles comprise TiC;
in an alternative embodiment, the endogenous precipitating ceramic particles are Cr2B particles, wherein the mass fraction of the B particles in the austenitic heat-resistant steel is 2-8%; more preferably, the mass fraction of the austenite heat-resistant steel is 2-5%;
in an alternative embodiment, the endogenous precipitating ceramic particles are Cr2When B is particles, the mass fraction of C in the austenitic heat-resistant steel is 0.2-0.5%, and the mass fraction of N in the austenitic heat-resistant steel is 0.2-0.3%;
in an optional embodiment, the endogenously precipitated ceramic particles are carbon-titanium ceramic particles, and the mass fraction of the carbon-titanium ceramic particles in the austenitic heat-resistant steel is 2-8%; more preferably, the mass fraction of the austenite heat-resistant steel is 2-6%;
in an optional embodiment, when the endogenously precipitated ceramic particles are carbon-titanium ceramic particles, the mass fraction of C except the endogenously precipitated ceramic particles in the austenitic heat-resistant steel is 0.3% to 0.5%, and the mass fraction of N in the austenitic heat-resistant steel is 0.1% to 0.3%;
in an alternative embodiment, the endogenous precipitating ceramic particles are Cr2Composition of B and carbon-titanium ceramic particlesThe composite particles account for 4 to 13 mass percent of the austenitic heat-resistant steel; more preferably, the mass fraction of the austenite heat-resistant steel is 4-7%;
in an alternative embodiment, the endogenous precipitating ceramic particles are Cr2When B and carbon-titanium ceramic particles are compounded, the mass fraction of C except the ceramic particles precipitated in the interior accounts for 0.2-0.5% of the austenitic heat-resistant steel, and the mass fraction of N accounts for 0.1-0.6% of the austenitic heat-resistant steel.
In an alternative embodiment, the inevitable trace elements comprise S less than or equal to 0.02% and P less than or equal to 0.02%;
preferably, S is less than or equal to 0.002 percent and P is less than or equal to 0.002 percent.
In an optional embodiment, the grain sizes of the endogenously precipitated ceramic grains are all in the range of 1-18 microns; preferably in the range of 3 to 6 microns.
In an alternative embodiment, the austenitic heat-resistant steel is a steel plate, and the thickness of the austenitic heat-resistant steel is 5-20 mm.
In a second aspect, embodiments provide a method for preparing an internally precipitated ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel provided in any of the above embodiments, including:
smelting, forging and heat treating the preparation raw materials containing the chemical components.
In an alternative embodiment, the smelting of the raw materials for preparation containing the chemical components is carried out in the following manner:
preparing alloy molten steel: mixing and smelting preparation raw materials containing iron and chromium until molten steel is clear, and performing preliminary deoxidation treatment until the oxygen content in the molten steel is less than 50 ppm; then adding preparation raw materials containing manganese, silicon and nickel, carrying out deep deoxidation after the molten steel is melted down until the oxygen content in the molten steel is less than 20ppm, finally adding the preparation raw materials containing titanium, boron, carbon and nitrogen, and casting the molten steel into an ingot after the molten steel is melted down again;
in an alternative embodiment, the smelting process is carried out with constant stirring; more preferably, the stirring manner is electromagnetic stirring;
in an alternative embodiment, the raw materials for preparing the alloy containing iron, chromium, manganese, nickel, titanium, silicon, boron, carbon and nitrogen are as follows: pure iron, ferrochrome, ferromanganese, pure nickel, sponge titanium, ferrosilicon, ferroboron, pig iron and ferrochrome nitride;
in an optional embodiment, the molten steel obtained by mixing and smelting preparation raw materials containing iron, chromium, manganese, nickel, titanium, silicon, boron, carbon and nitrogen is prepared by: melting pure iron and ferrochrome, initially deoxidizing and deslagging after melting down, sequentially adding ferromanganese, ferrosilicon and pure nickel for melting, deeply deoxidizing and deslagging after melting down, adding sponge titanium, ferroboron, pig iron and ferrochrome after melting down the molten steel, preserving heat for 5-10 minutes for deslagging after re-melting down the molten steel, and casting into ingots;
in an optional embodiment, the melting temperature of pure iron and ferrochrome is 1460-1500 ℃, the melting temperature is 1560-1590 ℃ after ferromanganese, ferrosilicon and pure nickel are added, and the melting temperature is 1600-1650 ℃ after sponge titanium, ferroboron, pig iron and ferrochrome are added;
in an optional embodiment, the casting temperature is set to be 1550-1570 ℃;
in an alternative embodiment, the deoxidizer of the primary deoxidation treatment and the deep deoxidation treatment is an aluminum wire; preferably, the deoxidation time of the primary deoxidation treatment is 8-10 minutes, and the deoxidation time of the deep deoxidation treatment is 15-20 minutes.
In an alternative embodiment, the forging is performed by:
homogenizing the cast ingot, and then carrying out free forging and cogging;
preferably, an air hammer is adopted for free forging and cogging;
preferably, the steel plate is forged into a plate blank with the thickness of 5-20 mm through free forging cogging;
preferably, the temperature of the homogenization treatment is 1120-1180 ℃; more preferably, the heat preservation time of the homogenization treatment is 2-6 h;
preferably, the free forging temperature is 950-1150 ℃; more preferably, the free forging heat preservation time is 0.5-1.5 h.
In an alternative embodiment, the forging further comprises performing a heat treatment, wherein the heat treatment is performed by:
carrying out water quenching treatment after the solid solution treatment;
in an optional embodiment, the temperature of the solution treatment is 1050-1150 ℃; more preferably, the heat preservation time is 0.5-1.5 h.
In a third aspect, an embodiment of the present invention provides an application of the above endogenously precipitated ceramic particle-reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel or the above endogenously precipitated ceramic particle-reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel prepared by the above preparation method in the fields of metallurgy, mining, petrochemical industry, and power and electricity.
The invention has the following beneficial effects:
according to the endogenetic precipitation ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel obtained through the design, the low-Ni austenitic heat-resistant steel is adopted, Mn and N are utilized to replace part of nickel in the existing high-Cr high-Ni austenitic heat-resistant steel, the cost of raw materials is reduced, and the endogenetic precipitation ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel has excellent room temperature and high temperature strength and good toughness by adjusting the proportion of the content of each chemical component, and more importantly, the endogenetic precipitation ceramic particles are introduced into the heat-resistant steel, so that the austenitic heat-resistant steel also has excellent high-temperature oxidation resistance.
According to the preparation method of the endogenetic precipitation ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel, which is obtained through the design, the endogenetic precipitation ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel provided by the invention can be prepared.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic view of a manufacturing process of the present invention;
FIG. 2 is a metallographic structure photograph of an endogenously precipitated ceramic particle-reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel prepared in example 2 of the present invention;
FIG. 3 shows the oxidation resistance of the endogenously precipitated ceramic particle-reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel prepared in example 1, example 3 and a comparative example at 850 ℃;
FIG. 4 shows the oxidation resistance of the endogenously precipitated ceramic particle-reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel prepared in example 1, example 3 and comparative example at 950 ℃.
Icon: 1-a vacuum melting system; 2-alloy raw materials; 3-a crucible; 4, ingot casting; 5-a first heat treatment furnace; 6-air hammer; 7-ingot casting after homogenization treatment; 8-a plate blank; 9-a second heat treatment furnace; 10-plate blank after solution treatment; 11-a water tank; 12-water quenching liquid; 13-austenitic heat-resistant steel sheet; and 14-precipitating ceramic particles in the interior.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides an endogenetic precipitation ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel, and a preparation method and application thereof.
The invention provides an endogenetic precipitation ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel, which comprises the following chemical components in percentage by mass:
cr: 8.5% -18%, Mn: 10% -12%, Ni: 3.5% -4.5%, Si: 0.5% -0.8%, endogenously precipitated ceramic particles: 2% -13%, and the total amount of C and N: 0.3 to 1.2 percent of iron and the balance of inevitable trace elements.
It should be noted that, in the technical solutions provided in the present invention except for the following specific 31 examples, the ratios of the respective elements are all ratios in the austenitic heat-resistant steel, and are ratios in the austenitic heat-resistant steel in the form of non-endogenously precipitated ceramic particles.
The austenitic heat-resistant steel provided by the embodiment of the invention adopts low-Ni austenitic heat-resistant steel, Mn and N are used for replacing part of nickel in the existing high-Cr high-Ni austenitic heat-resistant steel, the cost of raw materials is reduced, the mixture ratio of the contents of all chemical components is adjusted to enable the endogenously precipitated ceramic particles to reinforce Cr-Mn-Ni-C-N austenitic heat-resistant steel to have excellent room-temperature and high-temperature strength and good toughness, and the reactivity of the endogenously precipitated ceramic particles introduced into the heat-resistant steel enables the austenitic heat-resistant steel to have excellent high-temperature oxidation resistance.
Preferably, in order to ensure better performance of the austenitic heat-resistant steel, the endogenously precipitated ceramic particles are Cr2B and carbon titanium ceramic particles, the carbon titanium ceramic particles including TiC. In most cases, when the target ceramic particles comprise TiC, there will also be a small amount of TiN in the preparation processxCy(x+y＝1，x>0，y>0) Ceramic particles are produced which have properties and properties similar to TiC. Thus, in particular embodiments, when the ceramic particles comprise TiC, a small amount of TiN is typically includedxCy。
Preferably, in order to further ensure the performance of the austenitic heat-resistant steel, the endogenous precipitation ceramic particles are Cr2B particles, wherein the mass fraction of the B particles in the austenitic heat-resistant steel is 2-8%; more preferably, the content thereof in the austenitic heat-resistant steel is 2 to 5% by mass.
Preferably, in order to further ensure the performance of the austenitic heat-resistant steel, when the endogenous precipitation ceramic particles are Cr2When B particles exist, the mass fraction of C in the austenitic heat-resistant steel is 0.2-0.5%, and the mass fraction of N in the austenitic heat-resistant steel is 0.2-0.3%;
preferably, in order to further ensure the performance of the austenitic heat-resistant steel, the ceramic particles are carbon titanium particles, and the mass fraction of the carbon titanium particles in the austenitic heat-resistant steel is 2-8%; more preferably, the mass fraction of the austenite heat-resistant steel is 2-6%;
preferably, in order to further ensure the performance of the austenitic heat-resistant steel, when the endogenously precipitated ceramic particles are carbon-titanium ceramic particles, the mass fraction of C except the endogenously precipitated ceramic particles in the austenitic heat-resistant steel is 0.3% to 0.5%, and the mass fraction of N in the austenitic heat-resistant steel is 0.1% to 0.3%;
preferably, in order to further ensure the performance of the austenitic heat-resistant steel, the endogenous precipitation ceramic particles are Cr2B and carbon-titanium ceramic particles, wherein the mass fraction of the composite particles in the austenitic heat-resistant steel is 4-13%; more preferably, the mass fraction of the austenite heat-resistant steel is 4-7%;
preferably, in order to further ensure the performance of the austenitic heat-resistant steel, when the endogenous precipitation ceramic particles are Cr2And B and carbon-titanium ceramic particles, wherein C except the endogenously precipitated ceramic particles accounts for 0.2-0.5% of the mass fraction of the austenitic heat-resistant steel, and N accounts for 0.1-0.6% of the mass fraction of the austenitic heat-resistant steel.
Preferably, the inevitable trace elements comprise less than or equal to 0.02 percent of S and less than or equal to 0.02 percent of P. Phosphorus and sulfur are impurities brought from preparation raw materials during preparation of the austenitic heat-resistant steel, and the content of phosphorus and sulfur is controlled within the range, so that the performance of the austenitic heat-resistant steel cannot be influenced. Preferably, in each of the preferred embodiments provided herein, S is about 0.002% and P is about 0.002%.
It should be noted that the content of inevitable trace elements is very small, and the total content is less than 0.02%, which can be almost ignored.
In a preferred embodiment of the present invention, the austenitic heat-resistant steel is a steel plate having a thickness of 10 mm. The yield strength of the steel plate at room temperature is 490-580 MPa, the yield strength at 850 ℃ is 210-240 MPa, and the yield strength at 950 ℃ is 160-190 MPa.
The embodiment of the invention provides a preparation method of the internally precipitated ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel, which comprises the following steps:
smelting, forging and carrying out heat treatment on the preparation raw materials containing the chemical components of the endogenously precipitated ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel. As shown in fig. 1, the steps in the figure are respectively numbered as: (1) adding alloy raw materials; (2) casting; (3) carrying out free forging and cogging after homogenization treatment; (4) a forging method; (5) forging into a plate blank; (6) carrying out water quenching after the solution treatment; (7) quenching; (8) and quenching to obtain the final endogenetic precipitation ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel plate.
The specific method comprises the following steps:
s1, preparing alloy molten steel: alloy raw materials 2 containing iron, chromium, manganese, nickel, titanium, silicon, boron, carbon and nitrogen are placed in a crucible 3 in a vacuum melting system 1 to be mixed and melted to obtain molten steel.
In each embodiment provided by the invention, the preparation raw materials containing iron, chromium, manganese, nickel, titanium, silicon, boron, carbon and nitrogen sequentially comprise: pure iron, ferrochrome, ferromanganese, pure nickel, sponge titanium, ferrosilicon, ferroboron, pig iron and ferrochrome nitride, and more specifically, the mass percent of carbon in the pure iron selected in each preferred embodiment provided by the invention is less than 0.02%; the ferrochrome also contains 60 percent of chromium by mass, 2 percent of carbon by mass and the balance of iron; the ferromanganese contains 80 mass percent of manganese and the balance of iron; the purity of the pure nickel is 99.98 percent; the purity of the titanium sponge is more than 99.9 percent; the ferrosilicon contains silicon with the mass percentage of 75 percent, and the balance is iron; the ferroboron contains 20 mass percent of boron and the balance of iron; the pig iron contains 4% of carbon by mass, and the balance of iron; the ferrochromium nitride contains 55 mass percent of chromium, 8 mass percent of nitrogen and the balance of iron.
The method comprises the specific steps of heating pure iron and ferrochrome in a vacuum induction furnace to 1460-1500 ℃ for melting, primarily deoxidizing and deslagging after melting down until the oxygen content in molten steel is less than 50ppm, then sequentially adding ferromanganese, ferrosilicon and pure nickel, heating to 1560-1590 ℃, deeply deoxidizing and deslagging after melting down the molten liquid again, deeply deoxidizing until the oxygen content in the molten steel is less than 20ppm, then sequentially adding sponge titanium, ferroboron, pig iron and ferrochrome, continuing heating to 1600-1650 ℃, preserving heat for 5-10 minutes after the molten steel is melted down again, deslagging, stopping heating, and casting the molten steel into a casting mold to obtain an ingot 4 when the temperature is reduced to 1550-1570 ℃.
Preferably, the deoxidizer of the primary deoxidation treatment and the deep deoxidation treatment is an aluminum wire; further preferably, the deoxidation time of the primary deoxidation treatment is 8 to 10 minutes, and the deoxidation time of the deep deoxidation treatment is 15 to 20 minutes.
S2, placing the cooled and solidified ingot 4 into a first heat treatment furnace 5, heating to 1120-1180 ℃, preserving heat for 2-6 hours, and carrying out homogenization treatment.
And S3, carrying out free forging and cogging on the homogenized cast ingot 7 by using an air hammer 6 at 950-1150 ℃, and forging the cast ingot into a plate blank 8 with the thickness of 5-20 mm.
S4, placing the plate blank into a second heat treatment furnace 9, heating to 1050-1150 ℃, preserving heat for 0.5-1.5 hours, and carrying out solid solution treatment.
S5, placing the plate blank 10 after the solution treatment in a water tank 11, and carrying out quenching treatment in a room-temperature water quenching solution 12 to obtain a final endogenously precipitated ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel plate 13, wherein endogenously precipitated ceramic particles 14 are distributed in the austenitic heat-resistant steel plate 13.
The austenitic heat-resistant steel sheet produced by the method of the present invention has a small amount of TiN in most cases when the target ceramic particles to be produced include TiCxCy(x+y＝1，x>0，y>0) Ceramic particles are generated, the crystal structure of the ceramic particles is the same as that of TiC, the mass of the ceramic particles is very close to that of TiC, and when the chemical components of the Cr-Mn-Ni-C-N austenitic heat-resistant steel are enhanced by the ceramic particles which are internally precipitated and provided by the application to prepare the austenitic heat-resistant steel, even a small amount of TiN is generatedxCyThe ceramic particles have no effect on the content of the whole ceramic particles, and have little effect on the total content of carbon and nitrogen in the base alloy (which means the alloy other than the ceramic particles in the austenitic heat-resistant steel).
The preparation method provided by the invention, (1) the endogenetic precipitated ceramic particles are introduced in an in-situ endogenetic mode, so that the problem of poor interface bonding between the endogenetic precipitated ceramic particles and the alloy matrix is avoided; (2) the consumption of noble elements Ni is reduced, and the cost of the material can be reduced; (3) more alloying elements are not needed to be added, and the high-temperature strength and the oxidation resistance can be effectively improved.
The endogenetic precipitation ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel provided by the embodiment of the invention or the endogenetic precipitation ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel prepared by the preparation method provided by the embodiment of the invention can be applied to the fields of metallurgy, mine, petrochemical industry and power and electricity, and particularly mainly refers to structural components in various power equipment, chemical equipment, metallurgical equipment and on-mine equipment.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides an endogenously precipitated ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel and a preparation method thereof.
The mass fraction of the alloy elements of the endogenously precipitated ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel is as follows: cr: 21.6%, Mn: 10%, Ni: 4%, Ti: 2%, Si: 0.8%, C: 0.6%, N: 0.6%, B: 0.4%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the components, Ti and B elements exist in the form of endogenously precipitated ceramic particles.
Firstly, preparing materials. The ingredients are mixed according to the chemical components.
And secondly, smelting. Heating pure iron and ferrochrome in a vacuum induction furnace to 1460 ℃ for melting, preliminarily deoxidizing and deslagging after a molten liquid is melted down, sequentially adding ferromanganese, ferrosilicon and pure nickel, heating to 1560 ℃, deeply deoxidizing and deslagging after the molten liquid is melted down again, sequentially adding sponge titanium, ferroboron, pig iron and ferrochrome, continuously heating to 1600 ℃, keeping the temperature for 10 minutes after melting down, deslagging again, stopping heating, and casting molten steel into a casting mold to obtain cast ingots when the temperature is reduced to 1550 ℃. The whole smelting process is continuously subjected to electromagnetic stirring.
And thirdly, forging. And putting the cooled and solidified ingot into a heat treatment furnace, heating to 1120 ℃, preserving the heat for 6 hours, and carrying out homogenization treatment.
The homogenized ingot was subjected to free forging with an air hammer at 950 ℃ to break the ingot into a slab having a thickness of 10 mm.
Fourthly, heat treatment. And putting the plate blank into a heat treatment furnace, heating to 1050 ℃, preserving the heat for 1.5 hours, and carrying out solid solution treatment. And then water quenching treatment is carried out to obtain the final endogenetic precipitation ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel plate.
Example 2
The embodiment provides an endogenously precipitated ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel and a preparation method thereof.
The mass fraction of the alloy elements of the endogenously precipitated ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel is as follows: cr: 25.2%, Mn: 10%, Ni: 4%, Ti: 3%, Si: 0.8%, C: 0.9%, N: 0.5%, B: 0.8%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the components, Ti and B elements exist in the form of endogenously precipitated ceramic particles.
Firstly, preparing materials. The ingredients are mixed according to the chemical components.
And secondly, smelting. Heating pure iron and ferrochrome in a vacuum induction furnace to 1500 ℃ for melting, preliminarily deoxidizing and deslagging after a molten liquid is melted down, sequentially adding ferromanganese, ferrosilicon and pure nickel, heating to 1590 ℃, deeply deoxidizing and deslagging after the molten liquid is melted down again, sequentially adding sponge titanium, ferroboron, pig iron and ferrochrome, continuously heating to 1650 ℃, keeping the temperature for 8 minutes after melting down, deslagging again, stopping heating, and casting molten steel into a casting mold to obtain cast ingots when the temperature is reduced to 1570 ℃. The whole smelting process is continuously subjected to electromagnetic stirring.
And thirdly, forging. And (4) putting the cooled and solidified ingot into a heat treatment furnace, heating to 1180 ℃, preserving heat for 2 hours, and carrying out homogenization treatment.
The homogenized ingot was subjected to free forging by an air hammer at 1150 ℃ to form a billet having a thickness of 10 mm.
Fourthly, heat treatment. And putting the plate blank into a heat treatment furnace, heating to 1150 ℃, and preserving heat for 0.5 hour to carry out solution treatment. And then water quenching treatment is carried out to obtain the final endogenetic precipitation ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel plate, and the metallographic structure photograph of the steel plate is shown in figure 2.
Example 3
The embodiment provides an endogenously precipitated ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel and a preparation method thereof.
The mass fraction of the alloy elements of the endogenously precipitated ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel is as follows: cr: 19.8%, Mn: 10%, Ni: 4%, Ti: 1%, Si: 0.8%, C: 0.5%, N: 0.5%, B: 0.2%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the components, Ti and B elements exist in the form of endogenously precipitated ceramic particles.
Firstly, preparing materials. The ingredients are mixed according to the chemical components.
And secondly, smelting. Heating pure iron and ferrochrome in a vacuum induction furnace to 1480 ℃ for melting, preliminarily deoxidizing and deslagging after a molten liquid is melted down, sequentially adding ferromanganese, ferrosilicon and pure nickel, heating to 1570 ℃, deeply deoxidizing and deslagging after the molten liquid is melted down again, sequentially adding sponge titanium, ferroboron, pig iron and ferrochrome, continuously heating to 1630 ℃, keeping the temperature for 5 minutes after melting down, deslagging again, stopping heating, and casting molten steel into a casting mold to obtain an ingot when the temperature is reduced to 1560 ℃. The whole smelting process is continuously subjected to electromagnetic stirring.
And thirdly, forging. And putting the cooled and solidified ingot into a heat treatment furnace, heating to 1150 ℃, preserving the heat for 4 hours, and carrying out homogenization treatment.
The homogenized ingot was subjected to free forging with an air hammer at 1050 ℃ to cogging, and the ingot was forged into a slab having a thickness of 10 mm.
Fourthly, heat treatment. And putting the plate blank into a heat treatment furnace, heating to 1100 ℃, and preserving the heat for 1 hour to carry out solution treatment. And then water quenching treatment is carried out to obtain the final endogenetic precipitation ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel plate.
Example 4
This example is substantially the same as example 3, except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 21.6%, Mn: 10%, Ni: 4%, Si: 0.8%, Ti: 2%, B: 0.4%, C: 0.3%, N: 0.3%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the components, Ti and B elements exist in the form of endogenously precipitated ceramic particles.
Example 5
This example is substantially the same as example 3, except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 19.8%, Mn: 10%, Ni: 4%, Ti: 2%, Si: 0.8%, C: 0.3%, N: 0.3%, B: 0.2%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the components, Ti and B elements exist in the form of endogenously precipitated ceramic particles.
Example 6
This example is substantially the same as example 3, except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 25.2%, Mn: 10%, Ni: 4%, Ti: 2%, Si: 0.8%, B: 0.8%, C: 0.3%, N: 0.3%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the components, Ti and B elements exist in the form of endogenously precipitated ceramic particles.
Example 7
This example is substantially the same as example 3, except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 18%, Mn: 10%, Ni: 4%, Ti: 1.6%, Si: 0.8%, C: 0.7%, N: 0.3%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the components, Ti element exists in the form of endogenous precipitated ceramic particles.
Example 8
This example is substantially the same as example 3, except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 18%, Mn: 10%, Ti: 6.4%, Ni: 4%, C: 1.9%, Si: 0.8%, N: 0.3%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the components, Ti element exists in the form of endogenous precipitated ceramic particles.
Example 9
This example is substantially the same as example 3, except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 18%, Mn: 10%, Ni: 4%, Ti: 3.2%, C: 1.1%, Si: 0.8%, N: 0.3%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the components, Ti element exists in the form of endogenous precipitated ceramic particles.
Example 10
This example is substantially the same as example 3, except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 19.8%, Mn: 10%, Ni: 4%, Si: 0.8%, C: 0.3%, N: 0.3%, B: 0.2%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the above components, the element B exists in the form of endogenous precipitated ceramic particles.
Example 11
This example is substantially the same as example 3, except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 21.6%, Mn: 10%, Ni: 4%, Si: 0.8%, B: 0.4%, C: 0.3%, N: 0.3%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the above components, the element B exists in the form of endogenous precipitated ceramic particles.
Example 12
This example is substantially the same as example 3, except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 25.2%, Mn: 10%, Ni: 4%, Si: 0.8%, B: 0.8%, C: 0.3%, N: 0.3%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the above components, the element B exists in the form of endogenous precipitated ceramic particles.
Example 13
This example is substantially the same as example 3, except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 19.8%, Mn: 10%, Ni: 4%, Si: 0.8%, C: 0.5%, N: 0.2%, B: 0.2%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the above components, the element B exists in the form of endogenous precipitated ceramic particles.
Example 14
This example is substantially the same as example 3, except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 21.6%, Mn: 10%, Ni: 4%, Si: 0.8%, C: 0.5%, B: 0.4%, N: 0.2%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the above components, the element B exists in the form of endogenous precipitated ceramic particles.
Example 15
This example is substantially the same as example 3, except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 25.2%, Mn: 10%, Ni: 4%, Si: 0.8%, B: 0.8%, C: 0.5%, N: 0.2%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the above components, the element B exists in the form of endogenous precipitated ceramic particles.
Example 16
This example is substantially the same as example 3, except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 19.8%, Mn: 10%, Ni: 4%, Ti: 2%, C: 1.0%, Si: 0.8%, B: 0.2%, N: 0.1%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the components, Ti and B elements exist in the form of endogenously precipitated ceramic particles.
Example 17
This example is substantially the same as example 3, except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 21.6%, Mn: 10%, Ni: 4%, Ti: 2%, C: 1.0%, Si: 0.8%, B: 0.4%, N: 0.1%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the components, Ti and B elements exist in the form of endogenously precipitated ceramic particles.
Example 18
This example is substantially the same as example 3, except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 25.2%, Mn: 10%, Ni: 4%, Ti: 2%, C: 1.0%, Si: 0.8%, B: 0.8%, N: 0.1%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the components, Ti and B elements exist in the form of endogenously precipitated ceramic particles.
Example 19
This example is substantially the same as example 3, except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 18%, Mn: 10%, Ni: 4%, Ti: 1.6%, C: 0.9%, Si: 0.8%, N: 0.1%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the components, Ti element exists in the form of endogenous precipitated ceramic particles.
Example 20
This example is substantially the same as example 3, except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 18%, Mn: 10%, Ni: 4%, Ti: 3.2%, C: 1.3%, Si: 0.8%, N: 0.1%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the components, Ti element exists in the form of endogenous precipitated ceramic particles.
Example 21
This example is substantially the same as example 3, except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 18%, Mn: 10%, Ni: 4%, Ti: 6.4%, C: 2.1%, Si: 0.8%, N: 0.1%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements, wherein in the components, Ti element exists in the form of endogenous precipitated ceramic particles.
Example 22
This example is substantially the same as example 1 except that the chemical composition of the austenitic heat-resistant steel differs only in the chromium content: cr: 16 percent.
Example 23
This example is substantially the same as example 1 except that the chemical composition of the austenitic heat-resistant steel differs only in the chromium content: cr: 17 percent.
Example 24
This example is substantially the same as example 1 except that the austenitic heat-resistant steel has a different manganese content in the chemical composition: mn: 11 percent.
Example 25
This example is substantially the same as example 1 except that the austenitic heat-resistant steel has a different manganese content in the chemical composition: mn: 12 percent.
Example 26
This example is substantially the same as example 1 except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 16%, Mn: 10%, Ni: 4%, Ti: 2%, Si: 0.8%, C: 0.6%, N: 0.6%, B: 0.2%, S: 0.002%, P: 0.002%. The balance of iron and some inevitable trace elements. In the above composition, Ti and B elements exist in the form of internally precipitated ceramic particles.
Example 27
This example is substantially the same as example 1 except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 17%, Mn: 10%, Ni: 4%, Ti: 2%, Si: 0.8%, C: 0.6%, N: 0.6%, B: 0.8%, S: 0.002%, P: 0.002%. The balance of iron and some inevitable trace elements. In the above composition, Ti and B elements exist in the form of internally precipitated ceramic particles.
Example 28
This example is substantially the same as example 1 except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 18%, Mn: 11%, Ni: 4%, Ti: 2%, Si: 0.8%, C: 0.6%, N: 0.6%, B: 0.4%, S: 0.002%, P: 0.002%. The balance of iron and some inevitable trace elements. In the above composition, Ti and B elements exist in the form of internally precipitated ceramic particles.
Example 29
This example is substantially the same as example 1 except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 18%, Mn: 12%, Ni: 4%, Ti: 2%, Si: 0.8%, C: 0.6%, N: 0.6%, B: 0.8%, S: 0.002%, P: 0.002%. The balance of iron and some inevitable trace elements. In the above composition, Ti and B elements exist in the form of internally precipitated ceramic particles.
In the above-mentioned austenitic heat-resistant steels of examples 1 to 29, in which the chemical composition included Ti, the titanium element was present mostly in the form of ceramic particles of titanium carbide and a small amount of TiNxCyThe ceramic particles are in the form of ceramic particles, so that the nitrogen element in the ceramic particles is low in quality, and the residual nitrogen element content in the matrix alloy does not influence the austenite stability of the matrix alloy.
Example 30
This example is substantially the same as example 1 except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 16%, Mn: 10%, Ni: 4%, Si: 0.8%, Ti: 3%, Si: 0.8%, C: 0.6%, N: 0.6%, B: 0.8%, S: 0.002%, P: 0.002%. The balance of iron and some inevitable trace elements. Wherein the ceramic particles are present in a proportion of about 12.2%.
Example 31
This example is substantially the same as example 1 except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 17%, Mn: 10%, Ni: 4%, Ti: 3%, Si: 0.8%, C: 0.6%, N: 0.6%, B: 0.4%, S: 0.002%, P: 0.002%. The balance of iron and some inevitable trace elements. Wherein the ceramic particles are present in a proportion of about 8%.
Comparative example 1
This example is substantially the same as example 1 except that the austenitic heat-resistant steel has a different chemical composition: the chemical components of the austenitic heat-resistant steel in the embodiment are as follows: cr: 18%, Mn: 10%, Ni: 4%, Si: 0.8%, C: 0.3%, N: 0.3%, S: 0.002%, P: 0.002%, and the balance of iron and some inevitable trace elements.
Comparative example 2
The comparative example provides a high-chromium high-nickel austenitic heat-resistant steel, which comprises the following components:
cr: 18%, Ni: 30%, Mn: 0.5%, Si: 0.5%, C: 0.2%, P: 0.016%, S: 0.004%, and the balance of iron.
Experimental example 1
The austenitic heat-resistant steel sheets provided in examples 1 to 31 and comparative examples 1 and 2 were respectively tested for oxidation resistance at 850 ℃ and 950 ℃, and the results are reported in tables 1 and 2.
TABLE 1 Oxidation resistance at 850 ℃ of various groups of austenitic heat-resistant steel plates
Figure BDA0002434184490000191
Figure BDA0002434184490000201
TABLE 2 Oxidation resistance at 950 ℃ of various groups of austenitic heat-resistant steel plates
Figure BDA0002434184490000202
Figure BDA0002434184490000211
Figure BDA0002434184490000221
As can be seen from tables 1 and 2, the oxidation weight gain speed of each example of the present invention is much lower than that of comparative example 1, and thus it can be seen that the addition of the internally precipitated ceramic particles to the austenitic heat-resistant steel can significantly improve the oxidation resistance thereof. Comparing example 1 with comparative example 2, the oxidation resistance of example 1 is obviously better than that of comparative example 2, which shows that the substitution of manganese and nitrogen for part of nickel in the existing high-Cr high-Ni austenitic heat-resistant steel not only reduces the cost, but also improves the oxidation resistance of the heat-resistant steel.
The oxidation weight gain over time during the oxidation resistance experiments of example 1, example 3 and comparative example 1 was recorded and figures 3 and 4 were prepared. The base alloy in the figure is referred to as comparative example 1. As can be seen from the figure, when the content of the endogenously precipitated ceramic particles is 4-13%, the oxidation resistance is better.
In conclusion, the endogenetic precipitation ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel provided by the invention adopts low-Ni austenitic heat-resistant steel, Mn and N are used for replacing part of nickel in the existing high-Cr high-Ni austenitic heat-resistant steel and replacing part of nickel in the existing high-Cr high-Ni austenitic heat-resistant steel, the cost of raw materials is reduced, and the mixture ratio of the contents of all chemical components is adjusted to ensure that the endogenetic precipitation ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel has excellent room temperature and high temperature strength and good toughness. Preferably, the inclusion of the precipitated Cr is introduced especially in heat-resistant steel2The reactivity of B and/or carbon titanium endogenously precipitated ceramic particles enables the austenitic heat-resistant steel to have excellent high-temperature oxidation resistance.
The preparation method of the endogenetic precipitation ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel can prepare the endogenetic precipitation ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel provided by the invention. In a preferred embodiment, the preparation process also has the following advantages: (1) the endogenetic precipitation ceramic particles are introduced in an in-situ endogenetic mode, so that the problem of poor interface bonding between the endogenetic precipitation ceramic particles and an alloy matrix is solved, (2) the consumption of noble component Ni is reduced, and the cost of the material can be reduced. (3) More alloying elements are not needed to be added, and the high-temperature strength and the oxidation resistance can be effectively improved. (4) The preparation method does not adopt a powder metallurgy preparation process, and can prepare large-scale heat-resistant structural parts.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (17)

1. The endogenetic precipitation ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel is characterized by comprising the following chemical components in percentage by mass:
cr: 8.5% -18%, Mn: 10% -12%, Ni: 3.5% -4.5%, Si: 0.5% -0.8%, endogenously precipitated ceramic particles: 2% -13%, and the total amount of C and N: 0.3% -1.2% of iron and inevitable trace elements as the rest; the endogenously precipitated ceramic particles are Cr2B particles, or Cr2B and carbon-titanium ceramic particles, the carbon-titanium ceramic particles comprising TiC.
2. The endogenously precipitated ceramic particle-reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel of claim 1, wherein the endogenously precipitated ceramic particles are Cr2And B particles account for 2-8% of the austenitic heat-resistant steel by mass fraction.
3. The endogenously precipitated ceramic particle-reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel according to claim 2, characterized in that the endogenously precipitated ceramic particles are Cr2B particles, the mass of which is in the austenitic heat-resistant steelThe fraction is 2% -5%.
4. The endogenously precipitated ceramic particle-reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel according to claim 2, characterized in that the endogenously precipitated ceramic particles are Cr2And in the case of B particles, the mass fraction of C in the austenitic heat-resistant steel is 0.2-0.5%, and the mass fraction of N in the austenitic heat-resistant steel is 0.2-0.3%.
5. The endogenously precipitated ceramic particle-reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel of claim 1, wherein the endogenously precipitated ceramic particles are Cr2And B and carbon-titanium ceramic particles, wherein the mass fraction of the composite particles in the austenitic heat-resistant steel is 4-13%.
6. The endogenously precipitated ceramic particle-reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel of claim 5, wherein the endogenously precipitated ceramic particles are Cr2And B and carbon-titanium ceramic particles, wherein the mass fraction of the composite particles in the austenitic heat-resistant steel is 4-7%.
7. The endogenously precipitated ceramic particle-reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel of claim 1, wherein the endogenously precipitated ceramic particles are Cr2And B and carbon-titanium ceramic particles, wherein C except the endogenously precipitated ceramic particles accounts for 0.2-0.5% of the mass fraction of the austenitic heat-resistant steel, and N accounts for 0.1-0.6% of the mass fraction of the austenitic heat-resistant steel.
8. The endogenously precipitated ceramic particle-reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel according to claim 1, characterized in that S is less than or equal to 0.02% and P is less than or equal to 0.02% among the inevitable trace elements.
9. The endogenously precipitated ceramic particle-reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel according to claim 8, characterized in that S is less than or equal to 0.002% and P is less than or equal to 0.002% of the inevitable trace elements.
10. The endogenously precipitated ceramic particle-reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel according to any one of claims 1-9, characterized in that the particle size of the endogenously precipitated ceramic particles is in the range of 1-18 microns.
11. The endogenously precipitated ceramic particle-reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel according to claim 10, characterized in that the particle size of the endogenously precipitated ceramic particles is within the range of 3-6 microns.
12. The endogenously precipitated ceramic particle-reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel according to any one of claims 1 to 9, characterized in that the austenitic heat-resistant steel is a steel plate with a thickness of 5 to 20 mm.
13. The method for preparing the internally precipitated ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel as claimed in any one of claims 1 to 12, comprising:
smelting, forging and carrying out heat treatment on the preparation raw materials containing the chemical components.
14. The production method according to claim 13, wherein the raw material for production containing the chemical component is smelted in such a manner that:
preparing alloy molten steel: mixing and smelting preparation raw materials containing iron and chromium until molten steel is clear, and performing preliminary deoxidation treatment until the oxygen content in the molten steel is less than 50 ppm; then adding preparation raw materials containing manganese, silicon and nickel, carrying out deep deoxidation after the molten steel is melted down until the oxygen content in the molten steel is less than 20ppm, finally adding the preparation raw materials containing titanium, boron, carbon and nitrogen, and casting the molten steel into an ingot after the molten steel is melted down again;
the smelting process is carried out in the process of continuous stirring; the stirring mode is electromagnetic stirring;
the preparation raw materials containing iron, chromium, manganese, nickel, titanium, silicon, boron, carbon and nitrogen are as follows in sequence: pure iron, ferrochrome, ferromanganese, pure nickel, sponge titanium, ferrosilicon, ferroboron, pig iron and ferrochrome nitride;
the molten steel is prepared by mixing and smelting preparation raw materials containing iron, chromium, manganese, nickel, titanium, silicon, boron, carbon and nitrogen: melting the pure iron and the ferrochrome, initially deoxidizing and deslagging after melting down, sequentially adding the ferromanganese, the ferrosilicon and the pure nickel for melting, deeply deoxidizing and deslagging after melting down, adding the sponge titanium, the ferroboron, the pig iron and the ferrochrome nitride after melting down the molten steel, preserving heat for 5-10 minutes after the molten steel is melted down again for deslagging, and casting into an ingot;
setting the melting temperature of pure iron and ferrochrome to 1460-1500 ℃, setting the melting temperature to 1560-1590 ℃ after adding the ferromanganese, the ferrosilicon and the pure nickel, and setting the melting temperature to 1600-1650 ℃ after adding the sponge titanium, the ferroboron, the pig iron and the ferrochrome nitride;
setting the casting temperature to 1550-1570 ℃;
the deoxidizer of the preliminary deoxidation treatment and the deep deoxidation treatment is an aluminum wire; the deoxidation time of the primary deoxidation treatment is 8-10 minutes, and the deoxidation time of the deep deoxidation treatment is 15-20 minutes.
15. The method of manufacturing according to claim 13, wherein forging is performed by:
homogenizing the cast ingot, and then carrying out free forging and cogging;
adopting an air hammer to carry out free forging and cogging;
forging the blank into a plate blank with the thickness of 5-20 mm through free forging cogging;
the temperature of homogenization treatment is 1120-1180 ℃; the heat preservation time of the homogenization treatment is 2-6 h;
the free forging temperature is 950-1150 ℃; the free forging heat preservation time is 0.5-1.5 h.
16. The method of claim 13, further comprising performing a heat treatment after forging, the heat treatment being:
carrying out water quenching treatment after the solid solution treatment;
preferably, the temperature of the solution treatment is 1050-1150 ℃; more preferably, the heat preservation time is 0.5-1.5 h.
17. The application of the endogenously precipitated ceramic particle-reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel according to any one of claims 1 to 9 or the endogenously precipitated ceramic particle-reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel prepared by the preparation method according to any one of claims 13 to 16 in the fields of metallurgy, mining, petrochemical industry and power and electricity.
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