CN116855812A - NbMoCrTaTi refractory high-entropy alloy and smelting method thereof - Google Patents
NbMoCrTaTi refractory high-entropy alloy and smelting method thereof Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 72
- 239000000956 alloy Substances 0.000 title claims abstract description 72
- 238000003723 Smelting Methods 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000006698 induction Effects 0.000 claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 38
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 32
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 24
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 17
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 15
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 56
- 239000011651 chromium Substances 0.000 claims description 31
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 29
- 229910052786 argon Inorganic materials 0.000 claims description 28
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 26
- 238000002844 melting Methods 0.000 claims description 23
- 230000008018 melting Effects 0.000 claims description 23
- 239000010955 niobium Substances 0.000 claims description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 22
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 14
- 239000011733 molybdenum Substances 0.000 claims description 14
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000002893 slag Substances 0.000 claims description 12
- 238000005266 casting Methods 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 9
- 229910000599 Cr alloy Inorganic materials 0.000 claims description 8
- GKLVJDKEMZBILE-UHFFFAOYSA-N [Nb].[Mo].[Cr] Chemical compound [Nb].[Mo].[Cr] GKLVJDKEMZBILE-UHFFFAOYSA-N 0.000 claims description 8
- 239000000788 chromium alloy Substances 0.000 claims description 8
- 238000007872 degassing Methods 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 6
- 239000007769 metal material Substances 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 238000003466 welding Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 150000001485 argon Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- 238000009849 vacuum degassing Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000005474 detonation Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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Abstract
A NbMoCrTaTi refractory high-entropy alloy and a smelting method thereof belong to the technical field of metallurgy. The chemical components and the mass contents thereof are as follows: 18 to 22 percent of Nb, 19.5 to 21.5 percent of Mo, 10 to 12 percent of Cr, 38 to 42 percent of Ta, 8.5 to 10.5 percent of Ti and the balance of unavoidable impurity elements. The smelting process is divided into 3 stages by adopting vacuum induction smelting, plasma induction smelting and vacuum consumable smelting, wherein the main task of the first stage is vacuum degassing, and gases such as N, O, H are effectively removed; in the second stage, the metal tantalum is rapidly melted by utilizing the centralized advantage of plasma energy to prepare an alloy ingot which is preliminarily and uniformly mixed; the third stage is to remove the inclusions and gas by utilizing the advantage of vacuum consumption, and mix the alloy again after remelting and solidification. The obtained FeCrCoNiAl high-entropy alloy cast ingot has good uniformity and good macrosegregation index of five elements.
Description
Technical Field
The invention belongs to the technical field of metallurgy, and relates to a NbMoCrTaTi refractory high-entropy alloy and a smelting method thereof.
Background
The high-entropy alloy is a metal alloy which is formed by mixing 5 or more metal elements according to an equal atomic ratio or a near equal atomic ratio and has high mixing entropy, has good thermal stability, lower stacking fault energy, good radiation resistance, corrosion resistance and other performances, and is widely applied to aerospace, nuclear power, chemical industry, food and other industries. Among a plurality of high-entropy alloys, the refractory high-entropy alloy has a more stable tissue structure, has good mechanical, oxidation, damp-heat and corrosion resistance in high-temperature, damp-heat, damp, acid, alkali and other environments, is hopeful to replace the traditional nickel-based high-temperature alloy, and has wide application prospect.
Refractory high-entropy alloy is divided into 3 kinds according to the structure, the first is single-phase alloy of single bcc phase or B2 phase, and the second is single-phase alloy comprising bcc+Laves and bcc+M 5 Si 3 、fcc+Ll 2 Bcc+hcp, B2+bcc and B2+Al 3 Zr 5 Isophase alloys, and the third is 3bcc, 2bcc+Laves, bcc+Laves+M 5 Si 3 、bcc+Laves+Ll 2 、bcc+B2+Al 3 Zr 5 、B2+Laves+Al 3 Zr 5 Isophasic alloys. As can be seen, most of the high-entropy alloys use bcc phase as matrix structure, so elements with bcc structure such as Nb, mo, ta, W are often used as main elements in component system design.
However, as Nb, mo, ta, W and other elements belong to the 4d and 5d regions, the atomic size and valence electron arrangement difference are large, so that the atomic diffusion capacity and Cheng Jianneng force difference of each element are large, the difficulty of uniform preparation in a liquid phase form is increased, and the preparation is usually carried out in a powder metallurgy method for inhibiting segregation. However, the powder metallurgy has high cost, long process flow and low production efficiency, and is difficult to be applied in large scale, which severely restricts the rapid development of high-entropy alloy.
In order to solve the problem of large-scale production of high-entropy alloy, a great deal of research work is done by metallurgical workers.
Publication No. CN115198158A discloses an antioxidation refractory high-entropy alloy and a preparation method thereof, wherein the antioxidation refractory high-entropy alloy is obtained by adopting a vacuum arc furnace for coarse-step smelting, and then through turnover casting, homogenizing annealing and densification treatment, the method is quite novel, but has extremely high requirements on equipment, for example, the vacuum degree is required to reach 5 multiplied by 10 during homogenizing annealing -3 Pa or below, but the current industrial vacuum pump cannot be realized, so that the method is difficult to popularize on a large scale.
Publication number CN115213406a discloses a method for preparing refractory high-entropy alloy by explosion loading, which adopts the procedures of vacuum ball milling, sealing, explosive filling, detonation and the like to prepare refractory high-entropy alloy, and is very advanced, but residues after detonation end tend to influence the cleanliness of the high-entropy alloy, and detonation devices and 8701 explosive belong to controlled articles, so that the method is not preferable.
Publication No. CN115109981A discloses an oxide dispersion strengthening TaNbVTi refractory high-entropy alloy, a preparation method and application thereof, wherein the method adopts ball milling, spray granulation and spheroidization to pelletize, and then electron beam smelting is carried out to obtain the refractory high-entropy alloy, the method is very unique, but the requirements on the raw materials are too strict, the requirements on powders such as Ta, nb, V, ti and the like are 10-80 mu m, and Y is the same 2 O 3 The powder is more required to be 20-50 nm and is on the marketIt is difficult to supply a large amount of the materials, so that the materials cannot be applied on a large scale.
In addition, publication number CN115044870A, CN114855049A, CN114855050a, etc. all disclose relatively novel and advanced refractory high-entropy alloy preparation methods, but the large-scale processes are complex, the cost is too high, and the large-scale prospect is dim.
In summary, there is no industrial technology method with low comprehensive cost, simple process and stable quality in the currently disclosed technology.
Disclosure of Invention
In order to solve the technical problems, the invention provides an NbMoCrTaTi refractory high-entropy alloy and a smelting method thereof. The invention adopts the following technical scheme:
the NbMoCrTaTi refractory high-entropy alloy comprises the following chemical components in percentage by mass: 18 to 22 percent of Nb, 19.5 to 21.5 percent of Mo, 10 to 12 percent of Cr, 38 to 42 percent of Ta, 8.5 to 10.5 percent of Ti and the balance of unavoidable impurity elements.
The smelting method of the NbMoCrTaTi refractory high-entropy alloy comprises the following steps of:
(1) Vacuum induction melting
A. Putting 50+/-5% of metallic chromium, all niobium strips and molybdenum strips into a zirconia prefabricated crucible of a vacuum induction furnace, and electrifying and melting under vacuum;
B. after furnace burden is melted, adding residual metal chromium in batches, after all the furnace burden is melted, heating, regulating to high vacuum for degassing until [ O ] < 10ppm, [ N ] < 10ppm, [ H ] < 1ppm;
C. stopping vacuum, filling argon, adjusting the temperature to 1520-1550 ℃, and carrying out charged casting;
D. cooling the cast ingot to room temperature, demolding, and cutting into thin strips to obtain niobium-molybdenum-chromium alloy strips;
(2) Plasma induction melting
E. Loading slag accounting for 3-5% of the total amount of the niobium-molybdenum-chromium alloy strip, the metal tantalum and the metal material into a zirconia prefabricated crucible of a plasma induction furnace, and introducing a plasma power supply and an induction power supply to quickly melt;
F. stopping the plasma power supply after furnace burden is melted down, keeping the spray gun to blow argon, skimming slag, adding titanium sponge in a separated mode, and increasing the induction power supply to fully stir molten metal after the titanium sponge is completely melted down;
G. adjusting the temperature to 1450-1480 ℃, and performing charged casting to obtain an alloy ingot serving as a consumable electrode;
(3) Vacuum consumable remelting
H. Annealing and polishing the consumable electrode, and then welding the consumable electrode to the dummy electrode;
I. vacuum consumable remelting is carried out, and the melting speed is kept at 90-150 kg/h;
J. demoulding after smelting, and slowly cooling the cast ingot in an argon protection furnace.
Further, in the step A, the vacuum degree is less than or equal to 0.67Pa during melting; in the step B, the temperature is raised to 1660-1700 ℃ of the molten metal, and the vacuum degree is less than or equal to 0.06Pa during degassing.
Further, in the step C, the argon filling amount is 35000-70000 Pa, and the purity is more than or equal to 99.99% after drying; in the step D, the cast ingot is cut into 30X 30-50X 50mm 2 Thin strips of the specification.
In the step E, the purity of the plasma medium gas is more than or equal to 99.99 percent, and the flow rate of the dehydrated argon gas is 120-200L/min.
Further, in the step F, the addition amount of the titanium sponge is based on the covering of the metal liquid level; in the step G, the length-diameter ratio of the casting ingot mould is more than or equal to 6.
Further, in the step H, the annealing temperature of the consumable electrode is 1200-1250 ℃ and the time is 16-20H.
Further, in the step I, the vacuum degree is kept to be less than or equal to 0.1Pa during vacuum consumable remelting.
Further, in the step J, the surface temperature of the cast ingot is more than or equal to 650 ℃ during demoulding, and the cast ingot is slowly cooled to less than or equal to 200 ℃ and is discharged from the furnace.
The beneficial effects of adopting above-mentioned technical scheme to produce lie in:
(1) The smelting process is divided into three stages of vacuum induction smelting, plasma induction smelting and vacuum consumable smelting, wherein the main task of the first stage is vacuum degassing, and gases such as N, O, H in alloy, particularly metal chromium, are effectively removed; in the second stage, the metal tantalum is quickly melted by utilizing the centralized advantage of plasma energy, so that the scouring of electromagnetic stirring to crucible refractory materials is reduced, and an alloy ingot which is preliminarily and uniformly mixed is prepared for the first time; the third stage is to remove the inclusions and gas by utilizing the advantage of vacuum consumption, and mix the alloy again after remelting and solidification.
(2) The zirconia prefabricated crucible with better chemical stability is used in vacuum induction smelting and plasma induction smelting, so that the chemical reaction between a metal molten pool and the crucible can be greatly reduced, the oxygen supply of the crucible and the inclusion carry-in are effectively reduced, and the stability and cleanliness of the chemical components of the alloy are ensured.
(3) In order to ensure the stability of chemical components, the high vacuum degree melting less than or equal to 0.1Pa is adopted for vacuum self-consuming time, so that the precise control of the element Ti easy to oxidize is ensured.
(4) The smelting method is relatively simple, the used equipment is conventional special smelting equipment, the process feasibility is high, and the smelting raw materials have no special requirements. The high temperature of the plasma induction furnace is utilized to rapidly melt the metal tantalum, so that the efficiency is improved, and the production cost can be further reduced; the produced cast ingot has uniform components and high quality stability; the macrosegregation index of Nb, mo, cr, ta, ti element is good, and the use requirement of the alloy is met; has better industrial application prospect and is worth popularizing.
Description of the embodiments
The present invention will be described in further detail with reference to examples.
Example 1
The NbMoCrTaTi refractory high-entropy alloy is smelted by adopting a vacuum induction furnace with rated capacity of 50kg, and the raw materials used are niobium strips (content of 99.99%), molybdenum strips (content of 99.99%), metallic chromium (content of 99.6%), metallic tantalum (content of 99.9%), titanium sponge (content of 99.6%), and the chemical compositions and target contents of the NbMoCrTaTi refractory high-entropy alloy are shown in Table 1. The production steps comprise:
(1) Vacuum induction melting:
(1) 3kg of metallic chromium, 9kg of niobium strips and 9.75kg of molybdenum strips are put into a zirconia prefabricated crucible of a vacuum induction furnace, and 3.02kg of metallic chromium is put into a secondary bin;
(2) vacuumizing to below 0.67Pa, starting to melt by power transmission, and melting metal chromium, niobium and molybdenum strips in the crucible after 2 hours;
(3) adding residual metal chromium from a storage bin in an partitioned manner, after the metal chromium is completely melted, raising the temperature to maintain the temperature of the metal solution to 1680 ℃, adjusting the temperature to be within 0.05Pa of high vacuum, and degassing for 20min to less than or equal to 10ppm of [ O ], [ N ] < 10ppm, and [ H ] < 1ppm;
(4) stopping vacuum, filling the dried argon with purity more than or equal to 99.99% at 35000Pa, adjusting the temperature to 1520 ℃, and carrying out charged uniform casting;
(5) cooling the cast ingot to room temperature, demolding, and cutting into thin strips; specification is 30X 30mm 2 。
(2) Plasma induction melting:
(1) putting the cut niobium molybdenum chromium alloy strip, 21.085kg of metallic tantalum and slag accounting for 3.6% of the total weight of the metallic material into a zirconia crucible of a plasma induction furnace, combining a plasma power supply, wherein the plasma medium gas is dried argon with the purity of more than or equal to 99.99%, the argon flow is 120L/min, and then starting the induction power supply to melt rapidly;
(2) stopping the plasma power supply after furnace burden is melted down, keeping the spray gun to blow argon, skimming slag, adding 4.27kg of titanium sponge in batches, wherein the adding amount of the titanium sponge is based on the condition that the metal liquid surface is covered each time, and increasing the induction power supply to fully stir the metal liquid after the titanium sponge is completely melted down;
(3) the temperature was adjusted to 1450 ℃, and an alloy ingot having a specification of phi 90m×680mm was cast with electricity to be used as a consumable electrode.
(3) Vacuum consumable remelting:
(1) annealing the consumable electrode at 1200 ℃ for 16 hours;
(2) after cooling to room temperature and polishing the surface, welding the surface to the false electrode;
(3) vacuum consumable remelting is carried out, the vacuum degree is kept to be less than or equal to 0.1Pa in the smelting process, and the smelting speed is kept to be 90kg/h;
(4) after smelting, demoulding, and putting the ingot into an argon protection furnace to slowly cool to 200 ℃ when the surface temperature of the ingot is 650 ℃, and discharging.
And after smelting, sampling the center, R/4, R/2, 3R/4 and the edges of the bottom of the ingot, and detecting components (R: the radius of the high-entropy alloy ingot). The results were as follows:
table 1: example 1 high entropy alloy ingot chemical composition and content (wt%)
Table 1 shows that FeCrCoNiAl high-entropy alloy cast ingots have good uniformity after being smelted by a vacuum induction furnace, plasma induction smelting and vacuum consumable smelting, and the macrosegregation index of Nb, mo, cr, ta, ti element is between 0.97 and 1.02, thereby meeting the use requirement of the alloy.
Example 2
The high-entropy alloy refractory to NbMoCrTaTi is smelted by adopting a vacuum induction furnace with rated capacity of 100kg, and the raw materials used are niobium strips (content of 99.99%), molybdenum strips (content of 99.99%), metallic chromium (content of 99.6%), metallic tantalum (content of 99.9%), titanium sponge (content of 99.6%), and the chemical compositions and target contents of the high-entropy alloy refractory to NbMoCrTaTi are shown in Table 2. The production steps comprise:
(1) Vacuum induction melting:
(1) 5kg of metallic chromium, 22kg of niobium strips and 21.5kg of molybdenum strips are put into a zirconia prefabricated crucible of a vacuum induction furnace, and 5.04kg of metallic chromium is put into a secondary bin;
(2) vacuumizing to below 0.67Pa, starting to melt by power transmission, and melting metallic chromium, niobium strips and molybdenum strips in the crucible after 2.5 hours;
(3) adding metal chromium from a stock bin in an internal mode, after the metal chromium is completely melted, heating to maintain the temperature of the metal liquid to 1660 ℃, adjusting the temperature to be within 0.06Pa of high vacuum, and degassing for 30min to less than or equal to 10ppm of [ O ], [ N ] < 10ppm, [ H ] < 1ppm;
(4) stopping vacuum, filling dried argon gas with purity more than or equal to 99.99% and 60000Pa, adjusting the temperature to 1550 ℃, and carrying out charged uniform-speed casting;
(5) cooling the cast ingot to room temperature, demolding, and cutting into thin strips; specification is 50X 50mm 2 。
(2) Plasma induction melting:
(1) putting the cut niobium molybdenum chromium alloy strip, 38.2kg of metallic tantalum and slag accounting for 5.0% of the total weight of the metallic material into a zirconia crucible of a plasma induction furnace, switching on a plasma power supply, wherein plasma medium gas is dried argon with the purity of more than or equal to 99.99%, the flow rate of the argon is 200L/min, and switching on the induction power supply to melt rapidly;
(2) stopping the plasma power supply after furnace burden is melted down, keeping the spray gun to blow argon, skimming slag, adding 8.53kg of titanium sponge in batches, wherein each time the titanium sponge is added in an amount which is based on the coverage of the metal liquid level, and increasing the induction power supply to fully stir the metal liquid after the titanium sponge is completely melted down;
(3) the temperature was adjusted to 1480℃and an alloy ingot having a specification of phi 100mm by 900mm was cast with electricity and used as a consumable electrode.
(3) Vacuum consumable remelting:
(1) annealing the consumable electrode at 1230 ℃ for 20 hours;
(2) after cooling to room temperature and polishing the surface, welding the surface to the false electrode;
(3) vacuum consumable remelting is carried out, the vacuum degree is kept to be less than or equal to 0.1Pa in the smelting process, and the smelting speed is kept to be 105kg/h;
(4) after smelting, demoulding, and putting the ingot into an argon protection furnace to slowly cool to 190 ℃ when the surface temperature of the ingot is 670 ℃, and discharging.
And after smelting, sampling the center, R/4, R/2, 3R/4 and the edges of the bottom of the ingot, and detecting components (R: the radius of the high-entropy alloy ingot). The results were as follows:
table 2: example 2 high entropy alloy ingot chemical composition and content (wt%)
Table 2 shows that after vacuum induction furnace smelting, plasma induction smelting and vacuum consumable smelting, feCrCoNiAl high-entropy alloy cast ingots have good uniformity, and the macrosegregation index of Nb, mo, cr, ta, ti element is between 0.98 and 1.03, so that the use requirement of the alloy is met.
Example 3
The NbMoCrTaTi refractory high-entropy alloy is smelted by adopting a vacuum induction furnace with rated capacity of 50kg, and the raw materials used are niobium strips (content of 99.99%), molybdenum strips (content of 99.99%), metallic chromium (content of 99.6%), metallic tantalum (content of 99.9%), titanium sponge (content of 99.6%), and the chemical compositions and target contents of the NbMoCrTaTi refractory high-entropy alloy are shown in Table 3. The production steps comprise:
(1) Vacuum induction melting:
(1) 3kg of metallic chromium, 9.5kg of niobium strips and 10kg of molybdenum strips are put into a zirconia prefabricated crucible of a vacuum induction furnace, and 2.52kg of metallic chromium is put into a secondary bin;
(2) vacuumizing to below 0.67Pa, starting to melt by power transmission, and melting metal chromium, niobium and molybdenum strips in the crucible after 2 hours;
(3) adding residual metal chromium from a storage bin in an partitioned manner, after the metal chromium is completely melted, raising the temperature to maintain the temperature of the metal liquid at 1670 ℃, adjusting the temperature to be within 0.05Pa of high vacuum, and degassing for 25 minutes until the concentration of [ O ] < 10ppm, [ N ] < 10ppm, [ H ] < 1ppm;
(4) stopping vacuum, filling dried argon with purity more than or equal to 99.99% at 50000Pa, adjusting temperature to 1530 ℃, and carrying out charged uniform casting;
(5) cooling the cast ingot to room temperature, demolding, and cutting into thin strips; specification is 40X 40mm 2 。
(2) Plasma induction melting:
(1) putting the cut niobium molybdenum chromium alloy strip, 19.85kg of metallic tantalum and slag accounting for 3.0% of the total weight of the metallic material into a zirconia crucible of a plasma induction furnace, switching on a plasma power supply, wherein plasma medium gas is dried argon with purity of more than or equal to 99.99%, the flow rate of the argon is 160L/min, and switching on the induction power supply to melt rapidly;
(2) stopping the plasma power supply after furnace burden is melted down, keeping the spray gun to blow argon, skimming slag, adding 5.27kg of titanium sponge in batches, wherein the adding amount of the titanium sponge is based on the condition that the metal liquid surface is covered each time, and increasing the induction power supply to fully stir the metal liquid after the titanium sponge is completely melted down;
(3) the temperature was adjusted to 1465℃and an alloy ingot having a specification of phi 90 m.times.650 mm was cast with electricity to serve as a consumable electrode.
(3) Vacuum consumable remelting:
(1) annealing the consumable electrode at 1220 ℃ for 18h;
(2) after cooling to room temperature and polishing the surface, welding the surface to the false electrode;
(3) vacuum consumable remelting is carried out, the vacuum degree is kept to be less than or equal to 0.1Pa in the smelting process, and the smelting speed is kept to be 95kg/h;
(4) after smelting, demoulding, and putting the ingot into an argon protection furnace to slowly cool to 180 ℃ when the surface temperature of the ingot is 680 ℃, and discharging.
And after smelting, sampling the center, R/4, R/2, 3R/4 and the edges of the bottom of the ingot, and detecting components (R: the radius of the high-entropy alloy ingot). The results were as follows:
table 3: example 3 high entropy alloy ingot chemical composition and content (wt%)
Table 3 shows that after vacuum induction furnace smelting, plasma induction smelting and vacuum consumable smelting, feCrCoNiAl high-entropy alloy cast ingots have good uniformity, and the macrosegregation index of Nb, mo, cr, ta, ti element is between 0.96 and 1.03, so that the use requirement of the alloy is met.
Example 4
The high-entropy alloy refractory to NbMoCrTaTi is smelted by adopting a vacuum induction furnace with rated capacity of 250kg, and the raw materials used are niobium strips (content of 99.99%), molybdenum strips (content of 99.99%), metallic chromium (content of 99.6%), metallic tantalum (content of 99.9%), titanium sponge (content of 99.6%), and the chemical compositions and target contents of the high-entropy alloy refractory to NbMoCrTaTi are shown in Table 4. The production steps comprise:
(1) Vacuum induction melting:
(1) 15kg of metallic chromium, 52.5kg of niobium strips and 51.25kg of molybdenum strips are put into a zirconia prefabricated crucible of a vacuum induction furnace, and 12.35kg of metallic chromium is put into a secondary bin;
(2) vacuumizing to below 0.67Pa, starting to melt by power transmission, and melting metal chromium, niobium and molybdenum strips in the crucible after 3 hours;
(3) adding metal chromium from a stock bin in an internal mode, after the metal chromium is completely melted, raising the temperature to keep the temperature of the metal liquid at 1700 ℃, adjusting the temperature to be within 0.05Pa of high vacuum, and degassing for 25 minutes to less than or equal to 10ppm of [ O ], [ N ] < 10ppm, [ H ] < 1ppm;
(4) stopping vacuum, filling dried argon with purity more than or equal to 99.99% under 70000Pa, adjusting the temperature to 1550 ℃, and carrying out charged uniform casting;
(5) cooling the cast ingot to room temperature, demolding, and cutting into thin strips; specification of 45X 45mm 2 。
(2) Plasma induction melting:
(1) putting the cut niobium molybdenum chromium alloy strip, 96.7kg of metallic tantalum and slag accounting for 4.4% of the total weight of the metallic material into a zirconia crucible of a plasma induction furnace, switching on a plasma power supply, wherein plasma medium gas is dried argon with purity of more than or equal to 99.99%, the flow rate of the argon is 180L/min, and switching on the induction power supply to melt rapidly;
(2) stopping the plasma power supply after furnace burden is melted down, keeping the spray gun to blow argon, skimming slag, adding 23.84kg of titanium sponge in batches, wherein each time the titanium sponge is added in an amount which is based on the coverage of the metal liquid level, and increasing the induction power supply to fully stir the metal liquid after the titanium sponge is completely melted down;
(3) the temperature was adjusted to 1465℃and an alloy ingot having a specification of phi 145 mm. Times.1800 mm was cast with electricity to serve as a consumable electrode.
(3) Vacuum consumable remelting:
(1) annealing the consumable electrode at 1250 ℃ for 19 hours;
(2) after cooling to room temperature and polishing the surface, welding the surface to the false electrode;
(3) vacuum consumable remelting is carried out, the vacuum degree is kept to be less than or equal to 0.1Pa in the smelting process, and the smelting speed is kept to be 150kg/h;
(4) after smelting, demoulding, and putting the ingot into an argon protection furnace to slowly cool to 190 ℃ when the surface temperature of the ingot is 660 ℃, and discharging.
And after smelting, sampling the center, R/4, R/2, 3R/4 and the edges of the bottom of the ingot, and detecting components (R: the radius of the high-entropy alloy ingot). The results were as follows:
table 4: example 4 high entropy alloy ingot chemical composition and content (wt%)
Table 4 shows that after vacuum induction furnace smelting, plasma induction smelting and vacuum consumable smelting, feCrCoNiAl high-entropy alloy cast ingots have good uniformity, and the macrosegregation index of Nb, mo, cr, ta, ti element is between 0.95 and 1.03, so that the use requirement of the alloy is met.
Claims (9)
1. An NbMoCrTaTi refractory high-entropy alloy, which is characterized in that: the chemical components and mass percent are as follows: 18 to 22 percent of Nb, 19.5 to 21.5 percent of Mo, 10 to 12 percent of Cr, 38 to 42 percent of Ta, 8.5 to 10.5 percent of Ti and the balance of unavoidable impurity elements.
2. Smelting method based on the NbMoCrTaTi refractory high-entropy alloy according to claim 1, characterized in that it comprises the following steps:
(1) Vacuum induction melting
A. Putting 50+/-5% of metallic chromium, all niobium strips and molybdenum strips into a zirconia prefabricated crucible of a vacuum induction furnace, and electrifying and melting under vacuum;
B. after furnace burden is melted, adding residual metal chromium in batches, after all the furnace burden is melted, heating, regulating to high vacuum for degassing until [ O ] < 10ppm, [ N ] < 10ppm, [ H ] < 1ppm;
C. stopping vacuum, filling argon, adjusting the temperature to 1520-1550 ℃, and carrying out charged casting;
D. cooling the cast ingot to room temperature, demolding, and cutting into thin strips to obtain niobium-molybdenum-chromium alloy strips;
(2) Plasma induction melting
E. Loading slag accounting for 3-5% of the total weight of the niobium molybdenum chromium alloy strip, the metal tantalum and the metal material into a zirconia prefabricated crucible of a plasma induction furnace, and introducing a plasma power supply and an induction power supply to quickly melt;
F. stopping the plasma power supply after furnace burden is melted down, keeping the spray gun to blow argon, skimming slag, adding titanium sponge in a separated mode, and increasing the induction power supply to fully stir molten metal after the titanium sponge is completely melted down;
G. adjusting the temperature to 1450-1480 ℃, and performing charged casting to obtain an alloy ingot serving as a consumable electrode;
(3) Vacuum consumable remelting
H. Annealing and polishing the consumable electrode, and then welding the consumable electrode to the dummy electrode;
I. vacuum consumable remelting is carried out, and the melting speed is kept at 90-150 kg/h;
J. demoulding after smelting, and slowly cooling the cast ingot in an argon protection furnace.
3. The method for smelting a refractory high-entropy alloy of NbMoCrTaTi according to claim 2, characterized in that: in the step A, the vacuum degree is less than or equal to 0.67Pa during melting; in the step B, the temperature is raised to 1660-1700 ℃ of the molten metal, and the vacuum degree is less than or equal to 0.06Pa during degassing.
4. A method of smelting a refractory high-entropy alloy of NbMoCrTaTi according to claim 3, characterized in that: in the step C, the argon filling amount is 35000Pa to 70000Pa, and the purity is more than or equal to 99.99 percent after drying; in the step D, the cast ingot is cut into 30X 30-50X 50mm 2 Thin strips of the specification.
5. The method for smelting a refractory high-entropy alloy of NbMoCrTaTi according to claim 4, wherein: in the step E, the purity of the plasma medium gas is more than or equal to 99.99 percent, and the flow of dehydrated argon is 120-200L/min.
6. The method for smelting a refractory high-entropy alloy of NbMoCrTaTi according to claim 5, wherein the steps of: in the step F, the addition of the titanium sponge is based on the covering of the metal liquid level; in the step G, the length-diameter ratio of the casting ingot mould is more than or equal to 6.
7. The method for smelting a refractory high-entropy alloy of NbMoCrTaTi according to claim 6, wherein: in the step H, the annealing temperature of the consumable electrode is 1200-1250 ℃ and the time is 16-20H.
8. The method for smelting a refractory high-entropy alloy of NbMoCrTaTi according to claim 7, wherein: in the step I, when vacuum consumable remelting is carried out, the vacuum degree is kept to be less than or equal to 0.1Pa.
9. The method for smelting a refractory high-entropy alloy of NbMoCrTaTi according to any one of claims 2-8, characterized in that: in the step J, the surface temperature of the cast ingot is more than or equal to 650 ℃ during demoulding, and the cast ingot is slowly cooled to less than or equal to 200 ℃ and is discharged from the furnace.
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