CN113215494B - Preparation method of aviation invar alloy plate - Google Patents
Preparation method of aviation invar alloy plate Download PDFInfo
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- CN113215494B CN113215494B CN202110495828.9A CN202110495828A CN113215494B CN 113215494 B CN113215494 B CN 113215494B CN 202110495828 A CN202110495828 A CN 202110495828A CN 113215494 B CN113215494 B CN 113215494B
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- 239000000956 alloy Substances 0.000 title claims abstract description 47
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 47
- 229910001374 Invar Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000003723 Smelting Methods 0.000 claims abstract description 45
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000005242 forging Methods 0.000 claims abstract description 11
- 230000006698 induction Effects 0.000 claims abstract description 11
- 238000005098 hot rolling Methods 0.000 claims abstract description 9
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims description 34
- 230000008018 melting Effects 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 22
- 238000005096 rolling process Methods 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 14
- 238000003466 welding Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 229910000831 Steel Inorganic materials 0.000 claims description 9
- 239000010959 steel Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005422 blasting Methods 0.000 claims description 6
- 238000010309 melting process Methods 0.000 claims description 6
- 238000007670 refining Methods 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 230000001680 brushing effect Effects 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000010079 rubber tapping Methods 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 238000010583 slow cooling Methods 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000008199 coating composition Substances 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000203 mixture Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- 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
- C21C7/10—Handling in a vacuum
-
- 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
- C21D1/26—Methods of annealing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
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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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/16—Remelting metals
- C22B9/18—Electroslag remelting
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- 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
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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
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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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
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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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
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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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
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a preparation method of an aviation invar alloy plate, which adopts a double-vacuum combined smelting mode of vacuum induction smelting and protective atmosphere constant smelting speed electroslag smelting to produce an electroslag remelting ingot, and the electroslag remelting ingot is subjected to blank forming, finishing and high-temperature forging, and is subjected to hot rolling and heat treatment. When the temperature of the plate prepared by the method is within 20-100 ℃, the expansion coefficient of the prepared 4J36 alloy plate needs to meet the condition that alpha is less than or equal to 0.9 multiplied by 10 < -6 >/DEG C; when the thickness of the 4J36 alloy plate is less than 20.0mm, the tensile strength of the 4J36 alloy plate is required to be equal to or more than 450MPa, the yield strength of the 4J36 alloy plate is required to be equal to or more than 250MPa, when the thickness of the 4J36 alloy plate is between 20.0mm and 70.0mm, the tensile strength of the 4J 3578 alloy plate is required to be equal to or more than 470MPa, and the yield strength of the 4J36 alloy plate is required to be equal to or more than 270 MPa.
Description
Technical Field
The invention belongs to the technical field of special material metallurgy materials, and relates to a preparation method of an invar alloy plate for aviation.
Background
Invar (4J36 alloy) has a mass percentage of Ni around 36%, and is also called invar because its dimensions hardly change with temperature. Curie Point of 4J36 is 2About 30 ℃ and the expansion coefficient alpha is extremely low in a temperature range lower than the Curie point, and the expansion coefficient alpha of 4J36 is less than or equal to 1.5 multiplied by 10 according to the regulation of YB/T5241' Low expansion iron nickel, iron nickel cobalt alloy-6/deg.C (temperature range 20-100 deg.C). Due to the characteristic of extremely low expansion coefficient of 4J36, 4J36 is widely applied to the fields of precision instruments, aerospace, electronic industry, thermal bimetallic strips, liquid natural gas storage tanks, shadow mask materials and the like.
At present, 4J36 is applied more and more in the field of aerospace, and the main purpose is to be used as an aviation mould. When 4J36 is used as an aerospace mold, it is necessary to perform compounding with a composite material and then heat and pressure treatment in an autoclave, so that it is necessary to ensure that the lower the expansion coefficient of 4J36, the better. If the expansion coefficient is too high, the deformation of the 4J36 die in the autoclave is increased, so that the overall die is deformed, and the overall assembly of the tool is further influenced. Meanwhile, since the 4J36 needs to undergo frequent temperature cycling and handling when used as an aerospace mold, the 4J36 mold is required to have certain mechanical strength to ensure the structural stability. Therefore, the research on the 4J36 alloy sheet material for the aviation die is more and more focused by research institutions and related enterprises.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of an aviation invar alloy plate, which can ensure that the expansion coefficient is at a lower value on the premise of stabilizing the mechanical property by a double-vacuum combined smelting mode of vacuum induction smelting and protective atmosphere constant smelting speed electroslag smelting.
The invention is realized by the following technical scheme:
a preparation method of an invar alloy plate for aviation comprises the following operations:
1) burdening according to chemical components, then carrying out vacuum melting, and then pouring into an ingot;
the chemical components by mass percentage are as follows: c: less than or equal to 0.02 percent, Mn: 0.2-0.6%, Si: 0.05-0.3%, P is less than or equal to 0.002%, S is less than or equal to 0.002%, Ni: 35.5 to 36.5 percent of Fe, less than or equal to 0.0015 percent of O, less than or equal to 0.10 percent of Ti, less than or equal to 0.2 percent of Al, Mg, Zr and Ti, and the balance of Fe; meanwhile, the requirements that C + Mn + Si is less than or equal to 0.7 percent and C/Ti is less than or equal to 0.5 are met;
baking the proportioned raw materials, and then sending the roasted proportioned raw materials into a medium-frequency induction smelting furnace for vacuum smelting, wherein the vacuum degree is 0.1-0.2 Pa, the refining power is 350-400 Kw, the refining temperature is 1480-1540 ℃, and the tapping temperature is 1480-1540 ℃;
pouring by adopting an upper pouring method after discharging, and immediately adding a heating agent after pouring; then, carrying out mold cooling for more than or equal to 10 hours, and demolding to obtain an ingot;
2) carrying out electroslag remelting on the cast ingot;
welding an auxiliary electrode after baking the cast ingot, and smelting in an electroslag furnace under the protection of gas; the current of the smelting arcing stage is controlled to be 3000-5000A, and the current of the smelting stable melting stage is controlled to be 8000-10000A; controlling the melting speed in the whole melting process to be 6-8 Kg/min; after the crystallization is finished, hanging an electroslag ingot, placing the electroslag ingot in a sand pit for slow cooling, wherein the cooling time is more than or equal to 24 hours, and obtaining an electroslag remelting ingot;
3) forging the remelted ingot at high temperature to form a blank;
heating an electroslag remelting ingot by using a gas heating furnace, wherein the charging temperature of the electroslag ingot is less than or equal to 300 ℃, heating to 700-900 ℃ along with the furnace, preserving heat for 120-200 min, then heating to 1000-1100 ℃, preserving heat for 90-150 min, and then discharging from the furnace for forging, wherein the final forging temperature is more than or equal to 900 ℃; obtaining a blank after forging;
4) after the blank is polished, brushing high-temperature-resistant paint, then carrying out hot rolling, and carrying out annealing treatment on a hot-rolled plate;
the hot rolling adopts a gas furnace, and the charging temperature is less than or equal to 500 ℃; heating along with the furnace, keeping the temperature at 1000-1150 ℃, keeping the temperature for 20-30 min, then starting rolling, and rolling with one fire, wherein the total rolling deformation is more than or equal to 80%, and the rolling passes are more than or equal to 10; the initial rolling temperature is more than or equal to 1050 ℃, and the final rolling temperature is more than or equal to 900 ℃;
after the edge cutting treatment is carried out on the air-cooled hot rolled plate, annealing is carried out: annealing in a resistance furnace, wherein the charging temperature is less than or equal to 500 ℃, the temperature is increased to 800-900 ℃ along with the furnace, the temperature is kept for 4-6 h, and the furnace is cooled to below 200 ℃ and discharged;
5) and performing shot blasting treatment on the annealed finished hot rolled plate.
Raw materials and auxiliary materials adopted for smelting are required to be baked, wherein the raw materials are required to be baked for more than 6 hours at 700-800 ℃; the auxiliary materials are required to be baked for more than 5 hours at the temperature of 150-250 ℃; the baking of the ingot mold is carried out at 100-200 ℃.
When vacuum smelting is carried out in the medium-frequency induction smelting furnace, the power is controlled to be more than 500Kw in the material melting stage, and the material melting time is controlled to be 4.5-5.5 h.
The heating agent group is formed by mixing 60-70% of aluminum powder and 30-40% of sodium nitrate in percentage by mass; the dosage of the heating agent is 0.2-0.6% of the mass of the molten steel.
The electroslag furnace is a gas protection electroslag furnace with constant melting speed, and argon protection is adopted in the whole melting process.
The high-temperature-resistant coating comprises SiO2：5～20％，Al2O3：35～65％，Fe2O3：1～5％，TiO2：1～10％，H2O: 20-35%; and brushing after the suspension is prepared.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention adopts a double-vacuum combined smelting mode of vacuum induction smelting and protective atmosphere constant smelting speed electroslag smelting to produce an electroslag remelting ingot, and the electroslag remelting ingot is subjected to blank forming, finishing, high-temperature forging to form a blank, hot rolling and heat treatment; thus ensuring that the components of the plate meet the relevant requirements in YB/T5241, not only achieving the purpose of reducing the oxygen content, but also ensuring that the expansion coefficient is in a lower value (the lower the expansion coefficient is, the better) on the premise of stabilizing the mechanical property; compared with the currently common intermediate frequency furnace smelting or the intermediate frequency furnace and VD furnace smelting, the smelting mode adopted by the invention can produce the 4J36 alloy ingot with lower expansion coefficient and gas content. When the temperature of the 4J36 alloy plate prepared by the invention is in the range of 20-100 ℃, the expansion coefficient of the 4J36 alloy plate meets the condition that alpha is less than or equal to 0.9 multiplied by 10-6/° c; when the thickness of the 4J36 alloy plate is less than 20.0mm, the tensile strength of the alloy plate is more than or equal to 450MPa, the yield strength of the alloy plate is more than or equal to 250MPa, and when the thickness of the 4J36 alloy plate is between 20.0mm and 70.0mm, the tensile strength of the alloy plate is required to be more than or equal to 250MPa470MPa or more, and the yield strength is required to meet 270MPa or more.
Factors influencing the expansion coefficient of 4J36 are mainly alloy components, but the influence of different smelting modes on the expansion coefficient is also remarkable. If the intermediate frequency furnace is adopted for smelting 4J36, because the probability of contact between molten steel and air is high, the content of gas contained in the steel is about 0.0100%, when the content of the gas is high, the welding of a 4J36 die is not facilitated, and the expansion coefficient of 4J36 can be increased; and the carbon content is generally below 0.01 percent, and the carbon content is too low to be combined with Ti to form compounds such as TiC and the like so as to improve the mechanical property of the 4J36 mould.
If the intermediate frequency furnace and the VD furnace are adopted, compared with the intermediate frequency furnace, the oxygen content can be reduced to a great extent, the C/Ti ratio can be controlled, and the purpose of strengthening 4J36 is achieved, but the expansion coefficient is high due to the fact that the content of C + Mn + Si is too high to a great extent.
The invention can achieve the purpose of reducing the oxygen content by a double-vacuum combined smelting mode of vacuum induction smelting and combined with protective atmosphere constant smelting speed electroslag smelting, and can ensure that the expansion coefficient is at a lower value on the premise of stabilizing the mechanical property.
Detailed Description
The present invention will now be described in further detail with reference to the following examples, which are intended to be illustrative, but not limiting, of the invention.
A preparation method of an invar alloy plate (4J36 alloy plate) for aviation comprises the following steps:
1) vacuum smelting:
the purpose of vacuum melting is to obtain an ingot with both chemical composition and expansion coefficient meeting the standard.
Firstly, proportioning according to target chemical components, wherein 0.2-0.6% of metal Mn, 0.05-0.15% of crystal Si, 35.5-36.5% of electrolytic Ni plate, 0.1-0.2% of sponge Ti and the balance of pure iron are proportioned; after the material preparation is finished, vacuum intermediate frequency induction melting and pouring are carried out;
raw materials adopted for smelting are all required to be baked, wherein pure iron as a raw material is required to be subjected to shot blasting treatment, and a raw material electrolytic nickel plate is required to be baked for more than 6 hours at 700-800 ℃; baking auxiliary materials such as a heating agent, a refractory material and the like at 150-250 ℃ for more than 5 hours; the baking of the ingot mold needs to be carried out at 100-200 ℃;
during smelting, high-power melting materials are adopted in a medium-frequency induction smelting furnace (the power is controlled to be more than 500Kw, the melting time is controlled to be 4.5-5.5 h), the vacuum degree is 0.1-0.2 Pa, the refining power is 350-400 Kw, the refining temperature is 1480-1540 ℃, and the tapping temperature is 1480-1540 ℃;
the pouring adopts an upper pouring method, and after the pouring is finished, the heating agent is immediately added, and consists of the following components: 70% of aluminum powder and 30% of sodium nitrate; the using amount of the heating agent is 0.2-0.6% of the weight of the molten steel; the purpose of adding the heating agent is to ensure that the molten steel can smoothly complete feeding;
and (5) after casting, cooling the mold for more than or equal to 10 hours, and demolding to obtain the ingot with a good structure.
2) Electroslag remelting:
the electroslag remelting aims at obtaining an electroslag ingot with components and expansion coefficients meeting the requirements; sawing the cast ingot vertically, grinding the surface of the cast ingot, and then baking the cast ingot at 200-300 ℃ for more than or equal to 24 hours;
welding the auxiliary electrode with the baked auxiliary electrode, wherein the welding position adopts V-shaped groove welding, and the welding position adopts 4J36 welding wire of the same steel grade, particularly adopts
The coiled welding wire ensures that the components of the electroslag ingot cannot change greatly, thereby ensuring that the expansion coefficient cannot change greatly, and then carrying out electroslag remelting operation;
the electroslag remelting adopts a gas protection electroslag furnace with a constant melting speed, argon protection is adopted in the whole melting process, the current in the melting and arc starting stage is controlled to be 3000-5000A, the current in the melting and stable melting stage is controlled to be 8000-10000A, and the current is properly reduced when feeding is started (generally reduced by 1/10-1/20); the melting speed of the whole melting process is controlled to be 6-8 Kg/min.
After the crystallization is finished, hanging the electroslag ingot out and placing the electroslag ingot in a sand pit for slow cooling, wherein the cooling time is more than or equal to 24 hours, and the purpose is to obtain the electroslag ingot with uniform crystallization and facilitate the subsequent hot working.
3) High temperature:
after the two ends of an electroslag ingot are sawn, the electroslag ingot is heated by a gas heating furnace, the charging temperature of the electroslag ingot is less than or equal to 300 ℃, the temperature is increased to 700-900 ℃ along with the furnace, the temperature is kept for 120-200 min, the temperature is increased to 1000-1100 ℃, the temperature is kept for 90-150 min, and then the electroslag ingot is discharged from the furnace and forged, wherein the final forging temperature needs to be more than or equal to 900 ℃. The cross-sectional dimensions of the forged billet were thick (110-.
4) Hot rolling and annealing:
sawing the above blank at two ends, milling surface and grinding, and coating high-temperature-resistant coating (SiO)2：5～20％，Al2O3：35～65％，Fe2O3：1～5％，TiO2：1～10％，H2O: 20-35% to prepare a suspension and then uniformly brushing the suspension), and then carrying out hot rolling;
the hot rolling adopts a gas furnace, the charging temperature is less than or equal to 500 ℃, the temperature is raised along with the furnace, the heat preservation temperature is 1000-1150 ℃, the rolling is started after the heat preservation time is 20-30 min, and the rolling is carried out in one fire: the total rolling deformation is more than or equal to 80 percent, the rolling passes are more than or equal to 10, the initial rolling temperature is more than or equal to 1050 ℃, the final rolling temperature is more than or equal to 900 ℃, and the cooling mode is air cooling.
And after the edge cutting treatment is carried out on the air-cooled hot rolled plate, annealing is carried out. Annealing is carried out in a resistance furnace, the charging temperature is less than or equal to 500 ℃, the temperature is increased to 800-900 ℃ along with the furnace, the temperature is kept for 4-6 h, and the furnace is cooled to be below 200 ℃ and taken out of the furnace. The 4J36 alloy plate can be completely recrystallized by annealing, and a finished plate with uniform microstructure can be obtained.
5) Shot blasting treatment:
performing shot blasting treatment on the annealed plate; and when the thickness is less than or equal to 20mm, carrying out leveling treatment and then carrying out shot blasting treatment.
The thickness of the prepared alloy plate is within 6.0-70.0mm, the width of the alloy plate is less than or equal to 2000.0mm, and the length of the alloy plate is less than or equal to 6000.0 mm.
In accordance with the above method, a plurality of batches of sheet metal were smelted as an example. The chemical compositions of each of the examples and comparative examples of hot rolled sheets having a specific thickness of 10.0mm are shown in Table 1. In the table, example 1 represents a melting method using the present invention, comparative example 2 represents an intermediate frequency furnace melting method, and comparative example 3 represents an intermediate frequency furnace plus VD furnace melting method.
TABLE 110.0 mm Hot-rolled sheet chemical composition Table for each of the examples and comparative examples
As can be seen from Table 1, the examples No. 1# and No. 2# are the chemical compositions of the 4J36 alloy sheet material according to the present invention.
The chemical compositions of the comparative examples 3# to 6# do not accord with the chemical compositions of the 4J36 alloy sheet material, and specifically comprise the following steps: the O content in the comparative examples No. 3# and No. 4# is respectively 0.0116% and 0.0124% which is higher than 0.0015%, which does not meet the requirement of the 4J36 alloy sheet material of the invention for the O content; the comparative example No. 5# has O content of 0.0044% higher than 0.0015% and C/Ti content of 0.95% higher than 0.50, which does not meet the requirements of the 4J36 alloy sheet material of the invention on O content and C/Ti content; the comparative example No. 6# has a C + Mn + Si content of 0.836% or more than 0.70 and a C/Ti ratio of 1.0 or more than 0.50, and does not meet the requirements of the present invention for the C + Mn + Si content and C/Ti content.
The tensile strength, yield strength and expansion coefficient in the temperature range of 20 to 100 ℃ of the examples and comparative examples in Table 1 are shown in Table 2.
TABLE comparison of the Properties of the examples and comparative examples of 210.0 mm Hot-rolled sheet
As can be seen from Table 2, the 4J36 alloy sheets according to the invention have the tensile strength of 450MPa or more, the yield strength of 250MPa or more and the expansion coefficient of 0.9X 10 or less in the examples No. 1 and No. 2-6/℃。
While comparative example No. 3# has an expansion coefficient of 0.9X 10-6The tensile strength is only 433MPa and is less than 450MPa, and the yield strength is only 244MPa and is smallThe pressure is 250MPa which is required by the invention, so the pressure is not in line with the requirement of the invention.
Comparative example No. 4# has a tensile strength of 430MPa only less than 450MPa required by the present invention, a yield strength of 233MPa only less than 250MPa required by the present invention, and an expansion coefficient of 1.0X 10-6a/deg.C is greater than 0.9 × 10 required by the present invention-6/deg.C, so it does not meet the requirements of the present invention.
In comparative examples No. 5# and No. 6# each of tensile strengths 488MPa and 480MPa, respectively, is larger than 450MPa required in the present invention, and yield strengths 296MPa and 277MPa, respectively, are larger than 250MPa required in the present invention, but the expansion coefficients thereof are 1.1X 10-6/° C and 1.2 × 10-6a/deg.C is greater than 0.9 × 10 required by the present invention-6/deg.C, so it does not meet the requirements of the present invention.
The chemical compositions of each of the examples and comparative examples of the hot rolled sheet having a thickness of 20.0mm are shown in Table 3. In the table, melting mode 1 represents a melting method to which the present invention pertains, melting mode 2 represents an intermediate frequency furnace melting method, and melting mode 3 represents an intermediate frequency furnace and VD furnace melting method.
TABLE 320.0 chemical composition Table for each of the examples and comparative examples of hot-rolled sheet
As can be seen from Table 3, the examples No. 7 and No. 8 are the chemical compositions of the 4J36 alloy sheet material according to the present invention; the O contents of the comparative examples No. 9# and No. 10# are respectively 0.0128% and 0.0078% which are higher than 0.0015%, which do not meet the requirement of the invention for the O content, and the contents of the components of the comparative example No. 11# meet the requirement of the invention; the comparative example No. 12# in which the C + Mn + Si content is 0.794% to more than 0.70 and the C/Ti ratio is 0.88 to more than the requirement 0.50 of the present invention does not meet the requirements of the present invention for the C + Mn + Si content and C/Ti content.
The tensile strength, yield strength and expansion coefficient in the temperature range of 20 to 100 ℃ of the examples and comparative examples in Table 3 are shown in Table 4.
TABLE comparison of the Properties of the examples and comparative examples of 420.0 mm Hot-rolled sheet
As can be seen from table 4: the embodiment examples of No. 7 and No. 8 are that the tensile strength of the 4J36 alloy sheet material is not less than 470MPa, the yield strength is not less than 270MPa and the expansion coefficient is not more than 0.9 multiplied by 10-6/℃。
The tensile strengths of No. 9# and No. 10# are 461MPa and 455MPa respectively, which are less than 470MPa required by the present invention, the yield strengths of 263MPa and 265MPa respectively, which are less than 270MPa required by the present invention, and the expansion coefficients of 1.2X 10 respectively-6/° C and 1.1 × 10-6a/deg.C is greater than 0.9 × 10 required by the present invention-6/deg.C, so it does not meet the requirements of the present invention.
In comparative example No. 11#, although the tensile strength of 498MPa is larger than 470MPa required in the present invention and the yield strength of 280MPa is larger than 270MPa required in the present invention, the expansion coefficient is 1.2X 10-6a/deg.C is greater than 0.9 × 10 required by the present invention-6/deg.C, so it does not meet the requirements of the present invention.
Comparative example No. 12# has a tensile strength of 468MPa less than 470MPa required by the present invention and a yield strength of 275MPa greater than 270MPa required by the present invention, but has an expansion coefficient of 1.2X 10-6a/deg.C is greater than 0.9 × 10 required by the present invention-6/deg.C, so it does not meet the requirements of the present invention.
In conclusion, the factors influencing the expansion coefficient of 4J36 are mainly alloy components, but the influence of different smelting modes on the expansion coefficient is also remarkable. If the intermediate frequency furnace is adopted for smelting 4J36, because the probability of contact between molten steel and air is high, the content of gas contained in the steel is about 0.0100%, when the content of the gas is high, the welding of a 4J36 die is not facilitated, and the expansion coefficient of 4J36 can be increased; and the carbon content is generally below 0.01 percent, and the carbon content is too low to be combined with Ti to form compounds such as TiC and the like so as to improve the mechanical property of the 4J36 mould.
If the intermediate frequency furnace and the VD furnace are adopted, compared with the intermediate frequency furnace, the oxygen content can be reduced to a great extent, the C/Ti ratio can be controlled, and the purpose of strengthening 4J36 is achieved, but the expansion coefficient is high due to the fact that the content of C + Mn + Si is too high to a great extent.
The invention can achieve the purpose of reducing the oxygen content by a double-vacuum combined smelting mode of vacuum induction smelting and combined with protective atmosphere constant smelting speed electroslag smelting, and can ensure that the expansion coefficient is at a lower value on the premise of stabilizing the mechanical property.
The embodiments given above are preferable examples for implementing the present invention, and the present invention is not limited to the above-described embodiments. Any non-essential addition and replacement made by the technical characteristics of the technical scheme of the invention by a person skilled in the art belong to the protection scope of the invention.
Claims (9)
1. The preparation method of the aviation invar alloy plate is characterized by comprising the following operations:
1) burdening according to chemical components, then carrying out vacuum melting, and then pouring into an ingot;
the chemical components by mass percentage are as follows: c: less than or equal to 0.02 percent, Mn: 0.2-0.6%, Si: 0.05-0.3%, P is less than or equal to 0.002%, S is less than or equal to 0.002%, Ni: 35.5 to 36.5 percent of Fe, less than or equal to 0.0015 percent of O, less than or equal to 0.10 percent of Ti, less than or equal to 0.2 percent of Al, Mg, Zr and Ti, and the balance of Fe; meanwhile, the requirements that C + Mn + Si is less than or equal to 0.7 percent and C/Ti is less than or equal to 0.5 are met;
baking the proportioned raw materials, and then feeding the roasted proportioned raw materials into a medium-frequency induction smelting furnace for vacuum smelting, wherein the vacuum degree is 0.1-0.2 Pa, the refining power is 350-400 kW, the refining temperature is 1480-1540 ℃, and the tapping temperature is 1480-1540 ℃;
pouring by adopting an upper pouring method after discharging, and immediately adding a heating agent after pouring; then, carrying out mold cooling for more than or equal to 10 hours, and demolding to obtain an ingot;
2) carrying out protective atmosphere constant melting speed electroslag melting on the cast ingot;
welding an auxiliary electrode after baking the cast ingot, and smelting in an electroslag furnace under the protection of gas; the current of the smelting arcing stage is controlled to be 3000-5000A, and the current of the smelting stable melting stage is controlled to be 8000-10000A; controlling the melting speed in the whole melting process to be 6-8 kg/min; after the crystallization is finished, hanging an electroslag ingot, placing the electroslag ingot in a sand pit for slow cooling, wherein the cooling time is more than or equal to 24 hours, and obtaining an electroslag remelting ingot;
3) forging the remelted ingot at high temperature to form a blank;
heating an electroslag remelting ingot by using a gas heating furnace, wherein the charging temperature of the electroslag ingot is less than or equal to 300 ℃, heating to 700-900 ℃ along with the furnace, preserving heat for 120-200 min, then heating to 1000-1100 ℃, preserving heat for 90-150 min, and then discharging from the furnace for forging, wherein the final forging temperature is more than or equal to 900 ℃; obtaining a blank after forging;
4) after the blank is polished, brushing high-temperature-resistant paint, then carrying out hot rolling, and carrying out annealing treatment on a hot-rolled plate;
the hot rolling adopts a gas furnace, and the charging temperature is less than or equal to 500 ℃; heating along with a furnace, keeping the temperature at 1000-1150 ℃, keeping the temperature for 20-30 min, then starting rolling, and rolling with one fire, wherein the total rolling deformation is more than or equal to 80%, and the number of rolling passes is more than or equal to 10; the initial rolling temperature is more than or equal to 1050 ℃, and the final rolling temperature is more than or equal to 900 ℃;
after the edge cutting treatment is carried out on the air-cooled hot rolled plate, annealing is carried out: annealing in a resistance furnace, wherein the charging temperature is less than or equal to 500 ℃, the temperature is increased to 800-900 ℃ along with the furnace, the temperature is kept for 4-6 h, and the furnace is cooled to below 200 ℃ and discharged;
5) performing shot blasting treatment on the annealed finished hot rolled plate;
when the temperature of the prepared plate is within 20-100 ℃, the expansion coefficient of the prepared plate meets the condition that alpha is less than or equal to 0.9 multiplied by 10-6/℃；
When the thickness is less than 20.0mm, the tensile strength is more than or equal to 450MPa, and the yield strength is more than or equal to 250 MPa; when the thickness is between 20.0mm and 70.0mm, the tensile strength is more than or equal to 470MPa, and the yield strength is more than or equal to 270 MPa.
2. The preparation method of the aviation invar alloy plate as claimed in claim 1, wherein raw materials and auxiliary materials adopted in smelting are required to be baked, wherein the raw materials are required to be baked for more than 6 hours at 700-800 ℃; the auxiliary materials are required to be baked for more than 5 hours at the temperature of 150-250 ℃; the baking of the ingot mold is carried out at 100-200 ℃.
3. The method for preparing the invar alloy plate for the aviation according to claim 1, wherein when vacuum melting is performed in the medium-frequency induction melting furnace, the power is controlled to be more than 500kW in the material melting stage, and the material melting time is controlled to be 4.5-5.5 h.
4. The method for preparing an invar alloy plate for aviation according to claim 1, wherein the heat generating agent group is formed by mixing 60-70% of aluminum powder and 30-40% of sodium nitrate in terms of mass fraction; the dosage of the heating agent is 0.2-0.6% of the mass of the molten steel.
5. The method for preparing the invar alloy plate for the aviation according to claim 1, wherein when the ingot and the auxiliary electrode are welded, a 4J36 welding wire made of the same material is used for welding, and a V-shaped groove is used for welding at the welding position.
6. The method for preparing an invar alloy plate for aviation according to claim 1, wherein the electroslag furnace is a constant melting speed gas shielded electroslag furnace, and argon gas is adopted for protection in the whole melting process.
7. The method for preparing invar alloy plate for aviation according to claim 1, wherein the cross-sectional dimension of the forged blank is thickness (110-.
8. The method of manufacturing an invar alloy sheet for aerospace use according to claim 1, wherein the high temperature resistant coating composition comprises SiO in mass fraction2：5~20%，Al2O3：35~65%，Fe2O3：1~5%，TiO2：1~10%，H2O: 20-35%; and brushing after the suspension is prepared.
9. The method of manufacturing an invar alloy sheet for aviation according to claim 1, wherein the cooling means in the rolling is air cooling.
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