CN117385214A - Nickel-based superalloy deoxidizing and desulfurizing method based on non-calcareous refractory crucible - Google Patents
Nickel-based superalloy deoxidizing and desulfurizing method based on non-calcareous refractory crucible Download PDFInfo
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- CN117385214A CN117385214A CN202311687001.3A CN202311687001A CN117385214A CN 117385214 A CN117385214 A CN 117385214A CN 202311687001 A CN202311687001 A CN 202311687001A CN 117385214 A CN117385214 A CN 117385214A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 232
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 159
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 93
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 60
- 239000002184 metal Substances 0.000 claims abstract description 60
- 239000000126 substance Substances 0.000 claims abstract description 48
- 230000008569 process Effects 0.000 claims abstract description 44
- 239000011819 refractory material Substances 0.000 claims abstract description 44
- 238000007670 refining Methods 0.000 claims abstract description 37
- 238000003723 Smelting Methods 0.000 claims abstract description 34
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 30
- 230000023556 desulfurization Effects 0.000 claims abstract description 30
- 238000002844 melting Methods 0.000 claims abstract description 29
- 230000008018 melting Effects 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- HXQQNYSFSLBXQJ-UHFFFAOYSA-N COC1=C(NC(CO)C(O)=O)CC(O)(CO)CC1=NCC(O)=O Chemical compound COC1=C(NC(CO)C(O)=O)CC(O)(CO)CC1=NCC(O)=O HXQQNYSFSLBXQJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000006698 induction Effects 0.000 claims abstract description 18
- 238000003837 high-temperature calcination Methods 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 26
- 238000005245 sintering Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 15
- 230000001681 protective effect Effects 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 12
- 238000009694 cold isostatic pressing Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000013461 design Methods 0.000 claims description 8
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001308 synthesis method Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 241001062472 Stokellia anisodon Species 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000000956 alloy Substances 0.000 description 32
- 229910045601 alloy Inorganic materials 0.000 description 30
- 239000011575 calcium Substances 0.000 description 18
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 18
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 238000009826 distribution Methods 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 239000000292 calcium oxide Substances 0.000 description 12
- 235000012255 calcium oxide Nutrition 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 8
- 238000005266 casting Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 230000036571 hydration Effects 0.000 description 7
- 238000006703 hydration reaction Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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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
- C22C1/023—Alloys based on nickel
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
-
- 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
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B14/00—Crucible or pot furnaces
- F27B14/04—Crucible or pot furnaces adapted for treating the charge in vacuum or special atmosphere
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B14/00—Crucible or pot furnaces
- F27B14/08—Details peculiar to crucible or pot furnaces
- F27B14/10—Crucibles
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3213—Strontium oxides or oxide-forming salts thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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- C04B2235/6567—Treatment time
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B14/00—Crucible or pot furnaces
- F27B14/04—Crucible or pot furnaces adapted for treating the charge in vacuum or special atmosphere
- F27B2014/045—Vacuum
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B14/00—Crucible or pot furnaces
- F27B14/08—Details peculiar to crucible or pot furnaces
- F27B14/10—Crucibles
- F27B2014/102—Form of the crucibles
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- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a deoxidizing and desulfurizing method for nickel-based superalloy based on a non-calcareous refractory material crucible, which adopts the non-calcareous refractory material crucible to smelt the nickel-based superalloy through a vacuum induction smelting furnace, and simultaneously adds metal simple substances to realize deoxidizing and desulfurizing, and comprises the following steps: placing a non-calcareous refractory crucible into a vacuum induction melting furnace, and placing a nickel-based superalloy into the non-calcareous refractory crucible; vacuumizing the furnace chamber to a certain vacuum degree, heating the furnace chamber to a smelting temperature, and then smelting and refining; adding a metal simple substance Y into the nickel-based superalloy in the vacuumizing, smelting or refining process; in the refining process, adding metal simple substances Ba and Ca into the nickel-based superalloy; and (5) finishing deoxidation and desulfurization of the nickel-based superalloy after refining. Based on the non-calcareous refractory material crucible and the addition of the metal simple substance, the deoxidization and desulfurization of the nickel-based superalloy can be realized, the service life of the crucible is prolonged, and the production cost of the nickel-based superalloy is reduced.
Description
Technical Field
The invention belongs to the technical field of nickel-based superalloy preparation, and particularly relates to a nickel-based superalloy deoxidization desulfurization method based on a non-calcareous refractory crucible.
Background
The application of the nickel-based superalloy has great importance and significance, which provides a key material foundation for the modern engineering technology, while the nickel-based superalloy applied to hot end components such as turbine blades, combustors, turbine discs and the like in China mainly depends on import. The quality of the nickel-base superalloy plays a decisive role in the performance of the component. The purity level of the nickel-base superalloy is one of important parameters for evaluating the excellent performance of the nickel-base superalloy at present, is also one of important indexes for measuring the manufacturing level of the nickel-base superalloy, and is a problem to be solved in the urgent need of developing the nickel-base superalloy by strictly controlling the content of impurity elements and improving the purity of the alloy.
The content of oxygen element and sulfur element in the nickel-based superalloy is high and difficult to remove, inclusions such as oxides, sulfides and the like are easy to form with alloy elements, and large-size inclusions can damage the continuity of a matrix and cause uneven structure, so that the strength, toughness, plasticity, creep property and the like of the alloy are greatly influenced, strict requirements are provided for controlling the content of the oxygen element and the sulfur element in the nickel-based superalloy, and the nickel-based superalloy has important significance for improving the stability and the service performance of the alloy in view of the research of deoxidization and desulfurization technology in the nickel-based superalloy.
The deoxidization and desulfurization of the nickel-based superalloy are realized in the smelting stage, and for the nickel-based superalloy, crucible vacuum induction smelting is the first step for realizing smelting preparation of the nickel-based superalloy and is also a key step for improving the purity of the nickel-based superalloy. In the vacuum induction smelting process, the nickel-based superalloy melt is directly contacted with a refractory crucible, so that the selection of the refractory crucible is important for the deoxidizing and desulfurizing effects of the alloy.
Refractory crucibles are generally made of materials such as alumina, magnesia, and calcia. However, alumina is very likely to enter the alloy melt due to its own lamellar structure and brittle nature, forming inclusions which contaminate the alloy melt; magnesium oxide is easy to generate decomposition reaction under vacuum condition, so that oxygen is supplied to alloy melt, the alloy melt is further polluted, the deoxidization and desulfurization effects of the alloy melt are affected, meanwhile, the magnesium element in the magnesium oxide crucible volatilizes to cause that the melt at the interface is stirred severely, oxygen and sulfur element in the alloy cannot be attached to the crucible wall, and in addition, the oxygen and sulfur element cannot form stable compounds with the constituent elements of the magnesium oxide crucible, so that the deoxidization and desulfurization effects cannot be achieved.
In-situ deoxidization and desulfurization of nickel-based superalloy can only be realized by a calcium oxide crucible, because Ca element melted into alloy melt by calcium oxide can react with S element in the melt to form CaS compound, and the compound can be attached to the inner wall of the crucible, thereby realizing desulfurization of the alloy melt. However, calcium oxide (density of about 3.35 g/cm) is very easy to absorb water in the air to generate calcium hydroxide (density of about 2.24 g/mL), so that the volume of the crucible is expanded, and the crucible is damaged due to hydration; meanwhile, although calcium oxide can reduce grain boundaries to inhibit hydration by coarsening grains before being used, after smelting nickel-based superalloy, large grain boundaries can be eroded away by alloy due to the fact that the inner wall of a calcium oxide crucible is impacted by alloy melt at high temperature, a plurality of small grain boundaries and small grains appear, and then the grain boundaries are increased in large area, hydration can be caused and aggravated, and great difficulty exists in industrial scale application.
In the actual smelting process, the nickel-base superalloy is required to be subjected to deoxidization and desulfurization treatment in an additional mode, and C is usually adopted to remove O in the alloy, but the deoxidization limit exists in the mode, and the deoxidization limit concentration of CO is 10 multiplied by 10 -6 About wt%, thus, it is also necessary to conduct deep deoxidation by other methods, but it is now common to conduct deep deoxidation by adding Al element although the oxygen content can be controlled to 5 to 6X 10 -6 About wt%, but with more advanced deoxidation, control is difficult.
The invention patent with the application publication number of CN116003108A discloses a preparation method of a forming crucible with desulfurization and rare earth element addition, which comprises the following steps: adding binder and sintering aid into main raw materials of alkaline earth metal oxide, rare earth oxide and auxiliary raw materials of acidic and neutral oxide, uniformly mixing according to proportion and granularity, wherein the alkaline earth metal oxide is one or more of CaO, srO, baO and MgO, caO is necessary raw material, and the rare earth oxide is Y 2 O 3 、CeO 2 And La (La) 2 O 3 Any one or more of them, the content of which is not less than 50wt%; and (3) adopting a cold isostatic press for compression molding, and sintering to obtain a molded crucible product. By adopting the technical scheme for preparing the crucible, the raw materials must contain calcium oxide, and although the calcium oxide crucible can realize high-temperature alloy desulfurization, calcium oxide is extremely easy to absorb water in the air to generate calcium hydroxide, so that the crucible is hydrated and damaged. The invention patent with application publication number CN105777162A discloses a doped Y 2 O 3 BaZrO of (A) 3 Refractory material for preparing crucible for smelting titanium and titanium alloy, the material composition is as follows in mole percent: 40-58% of barium carbonate or barium oxide or barium hydroxide or barium chloride, 40-58% of zirconia and 0.1-15% of yttriaThe powder is made into a crucible through the procedures of molding, sintering and the like. The crucible prepared by the technical scheme does not react with the titanium alloy at high temperature, and the oxygen content in the prepared alloy ingot is basically unchanged compared with that of the master alloy, namely, the crucible prepared by the refractory material does not have deoxidization effect on the titanium alloy.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a nickel-based superalloy deoxidizing and desulfurizing method based on a non-calcareous refractory material crucible, which adopts the non-calcareous refractory material crucible, simultaneously adds a metal simple substance additive, and melts the nickel-based superalloy through a vacuum induction melting furnace, so as to deoxidize and desulfurize the nickel-based superalloy, and the deoxidizing and desulfurizing process comprises the following steps:
step one: preparing a non-calcareous refractory crucible for later use according to design requirements;
step two: placing a non-calcareous refractory crucible into a vacuum induction melting furnace, and simultaneously placing a nickel-based superalloy into the non-calcareous refractory crucible;
step three: closing the vacuum induction smelting furnace, vacuumizing the furnace chamber to a certain vacuum degree, heating the furnace chamber to a smelting temperature in a state of maintaining the certain vacuum degree, and then smelting and refining the nickel-based superalloy;
step four: adding a metal simple substance Y into the nickel-base superalloy in the process of vacuumizing the furnace chamber or in the process of smelting the nickel-base superalloy or in the process of refining the nickel-base superalloy; in the refining process of the nickel-based superalloy, adding a metal simple substance Ba and a metal simple substance Ca into the nickel-based superalloy simultaneously;
step five: and after the refining of the nickel-base superalloy is finished, the deoxidization and desulfurization of the nickel-base superalloy can be completed.
Preferably, in the first step, the non-calcareous refractory crucible is made of a non-calcareous refractory material consisting of SrO and ZrO 2 Is reacted at high temperature to generate Sr as the compound 4 Zr 3 O 10 The method comprises the steps of carrying out a first treatment on the surface of the The non-calcareous refractory material comprises the non-calcareous refractory materialIs composed of SrO 45-53wt% and ZrO 2 Accounting for 47 to 55 weight percent.
In the invention, the zirconium element is derived from any one or more substances of zirconium oxide, zirconium hydroxide and zirconium oxychloride; the strontium element is selected from one or more of strontium oxide, strontium carbonate and strontium hydroxide. The intermediate products of the substances after high-temperature calcination are oxides of the corresponding substances, and the mass range of the oxides is required to meet the design requirements of the invention.
In any of the above schemes, preferably, in the first step, the preparation method of the non-calcareous refractory crucible comprises the following steps in sequence:
step A: respectively weighing SrO and ZrO according to design requirements 2 Standby;
and (B) step (B): srO and ZrO 2 Putting the mixture into a mixer for uniform mixing to form a mixture;
step C: calcining the mixture at high temperature by a high-temperature solid-phase synthesis or high-temperature electrofusion synthesis method, and after the high-temperature calcination is finished, preparing the non-calcareous refractory material;
step D: the prepared non-calcareous refractory material is adopted, a crucible is molded by a manual ramming molding or cold isostatic pressing molding method, and then the molded crucible is put into a sintering furnace for high-temperature calcination, and after the high-temperature calcination is finished, the non-calcareous refractory material crucible can be prepared.
In any of the above embodiments, it is preferable that in step B, srO and ZrO 2 The mixing temperature is room temperature, the mixing speed is 5-20r/min, and the mixing time is 0.5-12h.
In any of the above schemes, preferably, in the step C, the mixture is calcined at high temperature by a high-temperature solid phase synthesis method, wherein the technological parameters of the high-temperature calcination are that the mixture is firstly put into a sintering furnace, then is heated from room temperature to 800 ℃ at a heating rate of 100-300 ℃/h, and is kept for 2-4h; continuously raising the temperature from 800 ℃ to 1200-1600 ℃ at the heating rate of 300-500 ℃/h, and preserving the temperature for 2-8h; continuously cooling from 1200-1600 ℃ to room temperature at a cooling rate of 100-200 ℃/h; the whole high-temperature calcination process is carried out under normal pressure without introducing protective gas.
In any of the above schemes, preferably, in the step C, the mixture is calcined at a high temperature by a high temperature electric melting synthesis method, wherein the technological parameters of the high temperature calcination are that the mixture is put into an electric melting furnace and the electric melting furnace is started, the electric melting temperature is 2900-3200 ℃, the electric melting time is 2-12h, and the whole high temperature calcination process is carried out under normal pressure without introducing protective gas.
In any of the above schemes, preferably, in the step D, the crucible is molded by a manual ramming molding method, wherein the ramming molding temperature is room temperature, the non-calcareous refractory material is added for 5-10 times, and the ramming time is 5-20min each time; the crucible is formed by a cold isostatic pressing method, wherein the cold isostatic pressing temperature is room temperature, the pressure is 100-180MPa, and the dwell time is 2-60min.
In any one of the above schemes, preferably, in the step D, the formed crucible is put into a sintering furnace for high-temperature calcination, wherein the technological parameters of the high-temperature calcination are that firstly, the formed crucible is put into the sintering furnace, and then the temperature is raised from room temperature to 1200 ℃ at a heating rate of 100-300 ℃/h, and the temperature is kept for 2-4 hours; continuously raising the temperature from 1200 ℃ to 1600-1800 ℃ at the heating rate of 300-500 ℃/h, and preserving the temperature for 2-8h; continuously cooling from 1600-1800 ℃ to 1200 ℃ at a cooling rate of 100-200 ℃/h, and preserving heat for 0.5-2h; continuously reducing the temperature from 1200 ℃ to 400 ℃ at the cooling rate of 100-200 ℃/h, and preserving the temperature for 0.1-0.5h; continuously cooling from 400 ℃ to room temperature at a cooling rate of 300-500 ℃/h; the whole high-temperature calcination process is carried out under normal pressure without introducing protective gas.
In any of the above-mentioned embodiments, it is preferable that in the third step, the vacuum degree in the cavity is maintained at 1×10 during the deoxidation and desulfurization -3 -10Pa; the smelting temperature of the nickel-based superalloy is 1400-1600 ℃; the refining temperature of the nickel-based superalloy is 1400-1600 ℃ and the refining time is 40min.
In any of the above schemes, preferably, in the fourth step, in the 10 th to 20 th min of refining the nickel-base superalloy, adding a metal simple substance Y into the nickel-base superalloy; simultaneously adding a metal simple substance Ba and a metal simple substance Ca into the nickel-based superalloy within 20-40min of refining the nickel-based superalloy; the total addition amount of the metal simple substance Y, the metal simple substance Ba and the metal simple substance Ca is not more than 5 weight percent of the mass of the nickel-based superalloy, wherein the addition amount of the metal simple substance Y is not more than 2 weight percent of the mass of the nickel-based superalloy.
In the invention, the used blendors, sintering furnaces, electric melting furnaces, manual ramming forming equipment, cold isostatic pressing forming equipment, vacuum induction melting furnaces and the like are selected according to actual use conditions, and the special requirements on equipment types are not required. The nickel-based superalloy is a master alloy material or an alloy raw material bulk material; after the nickel-based superalloy is deoxidized and desulfurized, taking out alloy liquid from the vacuum induction melting furnace for casting to obtain castings, wherein the casting equipment, the casting process and the like are adopted by the prior art. The metal simple substance Y, the metal simple substance Ba and the metal simple substance Ca are added in the form of bulk or powder raw materials.
According to the invention, the nickel-based superalloy is used as a raw material, a metal simple substance additive is added, a non-calcareous refractory crucible is used, and the nickel-based superalloy is smelted in vacuum through a vacuum induction smelting furnace, so that deoxidization and desulfurization of the nickel-based superalloy are realized. Sr is prepared by the invention 4 Zr 3 O 10 The thermodynamic stability of the refractory material is obviously superior to that of the existing Al mainly considering that at the smelting refining temperature (1400-1600 ℃) of the nickel-based superalloy 2 O 3 、ZrO 2 And MgO refractory, which is excellent in hydration resistance, although it is inferior in stability to CaO refractory, and which has a perovskite structure without the presence of an obvious hydration phase, and thus is remarkably superior to CaO in service life. Comprehensively consider, compared with the existing refractory material, sr 4 Zr 3 O 10 Refractory materials have the advantage of being better.
Considering that the high-performance nickel-base superalloy has very strict control on the O content and the S content, in the actual smelting process, the nickel-base superalloy needs to be subjected to O removal and S removal treatment in an additional mode, and C is generally adopted to remove O element in the nickel-base superalloy, so that the limit exists, and the deoxidization limit concentration of CO is 10 multiplied by 10 -6 About wt%, it is necessary to perform deep deoxidization by other methods, and it is common to perform deep deoxidization by adding Al element. Although the oxygen content can be controlled to be 5-6×10 -6 About wt%, but with more advanced deoxidation, control is difficult.
The invention adopts Y element with better affinity to O element for deep deoxidation, and considers that the S removal process and O removal process are synchronously carried out, because Sr 4 Zr 3 O 10 The refractory material is partially decomposed into SrO in the nickel-based superalloy melt, and SrS is combined with S element at the side of the refractory material and the nickel-based superalloy melt, so that the SrO is further combined with a deoiling product Al 2 O 3 And (3) reacting to generate a desulfurization slag phase. In consideration of realizing the extreme desulfurization, the Ba element with stronger binding capacity with the S element is also required to be introduced to form a BaS phase which is more stable than SrS, so that the preparation of the high-purity nickel-based superalloy is realized. This is mainly because Al is present in synchronization during the formation of BaS and SrS during desulfurization 2 O 3 The Al element is derived from the nickel-based superalloy component, and then Al 2 O 3 And generating composite oxide slag with BaS and SrS, and attaching the composite oxide slag on the inner wall of a crucible so as to realize desulfurization. However due to Al 2 O 3 And Y 2 O 3 The impurities are easy to enter the alloy melt in the electromagnetic stirring process, and the impurities can be separated from the alloy melt by synchronously adding Ca element, because the vapor pressure of Ca is lower, and the volatilization of Ca in the melt can cause the violent stirring of the melt, so the impurities are separated from the alloy melt, the effect of purifying the alloy melt is achieved, and the preparation of the high-purity nickel-based superalloy is further realized.
The nickel-based superalloy deoxidizing and desulfurizing method based on the non-calcareous refractory crucible has the following beneficial effects:
(1) By SrO/ZrO 2 As a matrix, the high-stability non-calcareous refractory material Sr is realized by controlling the chemical proportion and the technological parameters 4 Zr 3 O 10 Meanwhile, the preparation of the high-purity nickel-base superalloy can avoid hydration phase, further solve the problem that the refractory material is hydrated in the actual use process, improve the use stability of the refractory material, reduce the generation rate of oxygen supply and inclusion of the refractory material into the nickel-base superalloy, thereby reducing the preparation difficulty of the high-purity nickel-base superalloy and productionCost.
(2) Through adding the Ba/Ca/Y metal simple substance, the effects of simultaneously deoxidizing, desulfurizing and purifying the nickel-based superalloy melt are achieved, and the impurity and inclusion content in the nickel-based superalloy is effectively reduced.
(3) The purifying and smelting process of the nickel-based superalloy is simple and efficient, the alloy processing mode is reduced in actual production, and industrial production and popularization can be realized.
(4) The non-calcareous refractory material with high stability is adopted, so that the pollution of the refractory material to alloy melt is reduced, the removal of O element and S element in the alloy is realized through one-time smelting, the content of the O element and the S element is reduced to below 3ppm, and meanwhile, the influence of harmful elements and impurities on the alloy can be effectively controlled.
Drawings
FIG. 1 is a process flow diagram of a preferred embodiment of a method for deoxidizing and desulphurizing a nickel-based superalloy based on a non-calcareous refractory crucible in accordance with the present invention.
FIG. 2 is a secondary electron topography of the inner wall of the crucible after deoxidizing and desulphurizing the nickel-base superalloy in the embodiment shown in FIG. 1;
FIG. 3 is a view of a surface sweep of an element of the inner wall of the crucible after deoxidizing and desulfurizing the nickel-base superalloy in the embodiment shown in FIG. 1;
FIG. 4 is a diagram showing the main element distribution of the inner wall of the crucible after deoxidizing and desulfurizing the nickel-base superalloy in the embodiment shown in FIG. 1, wherein: (a) is an oxygen element distribution chart, (b) is an yttrium element distribution chart, (c) is a zirconium element distribution chart, (d) is a sulfur element distribution chart, (e) is a calcium element distribution chart, and (f) is a strontium element distribution chart.
Detailed Description
For a further understanding of the present invention, the present invention will be described in detail with reference to the following examples.
Embodiment one:
according to a preferred embodiment of the deoxidizing and desulfurizing method for the nickel-based superalloy based on a non-calcareous refractory crucible, the non-calcareous refractory crucible is adopted, a metal simple substance additive is added at the same time, the nickel-based superalloy is smelted by a vacuum induction smelting furnace, and then deoxidizing and desulfurizing are carried out on the nickel-based superalloy, and the deoxidizing and desulfurizing process comprises the following steps:
step one: preparing a non-calcareous refractory crucible for later use according to design requirements;
step two: placing a non-calcareous refractory crucible into a vacuum induction melting furnace, and simultaneously placing a nickel-based superalloy into the non-calcareous refractory crucible;
step three: closing the vacuum induction smelting furnace, vacuumizing the furnace chamber to a certain vacuum degree, heating the furnace chamber to a smelting temperature in a state of maintaining the certain vacuum degree, and then smelting and refining the nickel-based superalloy;
step four: adding a metal simple substance Y into the nickel-base superalloy in the process of vacuumizing the furnace chamber or in the process of smelting the nickel-base superalloy or in the process of refining the nickel-base superalloy; in the refining process of the nickel-based superalloy, adding a metal simple substance Ba and a metal simple substance Ca into the nickel-based superalloy simultaneously;
step five: and after the refining of the nickel-base superalloy is finished, the deoxidization and desulfurization of the nickel-base superalloy can be completed.
In the first step, the non-calcareous refractory crucible is made of a non-calcareous refractory material consisting of SrO and ZrO 2 Is reacted at high temperature to generate Sr as the compound 4 Zr 3 O 10 The method comprises the steps of carrying out a first treatment on the surface of the The non-calcareous refractory material comprises 49wt% of SrO and 49wt% of ZrO 2 Accounting for 51 weight percent. In this embodiment, the zirconium element is derived from any one or more substances selected from zirconia, zirconium hydroxide and zirconium oxychloride, the strontium element is derived from any one or more substances selected from strontium oxide, strontium carbonate and strontium hydroxide, and an intermediate product obtained by calcining each substance at a high temperature is an oxide of the corresponding substance, and the mass of the oxide meets the design requirements of this embodiment.
In the first step, the preparation method of the non-calcareous refractory crucible comprises the following steps in sequence:
step A: respectively weighing SrO and ZrO according to design requirements 2 Standby;
and (B) step (B): srO and ZrO 2 Putting the mixture into a mixer for uniform mixing to form a mixture;
step C: calcining the mixture at high temperature by a high-temperature solid-phase synthesis method, and after the high-temperature calcination is finished, preparing the non-calcareous refractory material;
step D: the prepared non-calcareous refractory material is adopted, a crucible is molded by a manual ramming molding method, the molded crucible is placed into a sintering furnace for high-temperature calcination, and the non-calcareous refractory material crucible can be prepared after the high-temperature calcination is finished.
In step B, srO and ZrO 2 The mixing temperature is room temperature, the mixing speed is 12r/min, and the mixing time is 6h.
In the step C, the mixture is calcined at high temperature by a high-temperature solid phase synthesis method, wherein the technological parameters of the high-temperature calcination are that the mixture is firstly put into a sintering furnace, then the temperature is increased from room temperature to 800 ℃ at a heating rate of 200 ℃/h, and the temperature is kept for 3 hours; continuously raising the temperature from 800 ℃ to 1400 ℃ at a heating rate of 400 ℃/h, and preserving the temperature for 5h; continuing to cool from 1400 ℃ to room temperature at a cooling rate of 150 ℃/h; the whole high-temperature calcination process is carried out under normal pressure without introducing protective gas.
In the step D, the crucible is molded by a manual ramming molding method, wherein the ramming molding temperature is room temperature, the non-calcareous refractory material is added for 8 times, and the ramming time is 12 minutes each time. The molded crucible is put into a sintering furnace for high-temperature calcination, wherein the technological parameters of the high-temperature calcination are that firstly, the molded crucible is put into the sintering furnace, and then the temperature is raised from room temperature to 1200 ℃ at a heating rate of 200 ℃/h, and the temperature is kept for 3 hours; continuously raising the temperature from 1200 ℃ to 1700 ℃ at a heating rate of 400 ℃/h, and preserving the temperature for 5h; continuously reducing the temperature from 1700 ℃ to 1200 ℃ at the cooling rate of 150 ℃/h, and preserving the heat for 1h; continuously reducing the temperature from 1200 ℃ to 400 ℃ at the cooling rate of 150 ℃/h, and preserving the temperature for 0.3h; continuing to cool from 400 ℃ to room temperature at a cooling rate of 400 ℃/h; the whole high-temperature calcination process is carried out under normal pressure without introducing protective gas.
In the deoxidation and desulfurization process, the vacuum degree in the furnace chamber is kept at 5Pa, the smelting temperature of the nickel-based superalloy is 1500 ℃, the refining temperature of the nickel-based superalloy is 1500 ℃, and the refining time is 40min.
In the fourth step, adding a metal simple substance Y into the nickel-based superalloy at 15min of refining the nickel-based superalloy; at the 30 th minute of refining the nickel-based superalloy, adding a metal simple substance Ba and a metal simple substance Ca into the nickel-based superalloy at the same time; the total addition amount of the metal simple substance Y, the metal simple substance Ba and the metal simple substance Ca is 5 weight percent of the mass of the nickel-based superalloy, wherein the addition amount of the metal simple substance Y is 2 weight percent of the mass of the nickel-based superalloy.
In the embodiment, the sulfur content in the nickel-based superalloy before smelting is 8ppm and the sulfur content in the nickel-based superalloy after desulfurization is 3ppm, which are measured by a sulfur-carbon analyzer; the oxygen content in the nickel-base superalloy before smelting was 10ppm and the oxygen content in the nickel-base superalloy after deoxidization was 3ppm, as measured by an oxygen-nitrogen analyzer. Scanning electron microscope testing is carried out on the inner wall of the crucible after the nickel-based superalloy deoxidization and desulfurization, the secondary electron morphology of the inner wall of the crucible is shown in fig. 2, the element surface scanning diagram of the inner wall of the crucible is shown in fig. 3, the main element distribution of the inner wall of the crucible is shown in fig. 4, and fig. 4 is as follows: (a) is an oxygen element distribution chart, (b) is an yttrium element distribution chart, (c) is a zirconium element distribution chart, (d) is a sulfur element distribution chart, (e) is a calcium element distribution chart, and (f) is a strontium element distribution chart.
The nickel-based superalloy deoxidizing and desulfurizing method based on the non-calcareous refractory crucible has the following beneficial effects: by SrO/ZrO 2 As a matrix, the high-stability non-calcareous refractory material Sr is realized by controlling the chemical proportion and the technological parameters 4 Zr 3 O 10 Meanwhile, the hydration phase is avoided, the problem that the refractory material is hydrated in the actual use process is solved, the use stability of the refractory material is improved, the oxygen supply and inclusion generation rate of the refractory material to the nickel-based superalloy is reduced, and the preparation difficulty of the high-purity nickel-based superalloy is reduced; through adding the Ba/Ca/Y metal simple substance, the effects of simultaneously deoxidizing, desulfurizing and purifying the nickel-based superalloy melt are achieved, and the impurity and inclusion content in the nickel-based superalloy is effectively reduced; the content of O element and S element in the nickel-based superalloy is reduced to3ppm or less.
Embodiment two:
according to another preferred embodiment of the deoxidizing and desulfurizing method for the nickel-based superalloy based on the non-calcareous refractory crucible of the present invention, the composition, the preparation steps, the deoxidizing and desulfurizing method for the nickel-based superalloy, the technical principle and the beneficial effects and the like of the non-calcareous refractory crucible are the same as those of the first embodiment, except that:
in the first step, the non-calcareous refractory crucible is made of a non-calcareous refractory material consisting of SrO and ZrO 2 Is reacted at high temperature to generate Sr as the compound 4 Zr 3 O 10 The method comprises the steps of carrying out a first treatment on the surface of the The non-calcareous refractory comprises, by mass, 53% SrO and 53% ZrO 2 Accounting for 47 weight percent.
The preparation method of the non-calcareous refractory crucible comprises the following steps: in step B, srO and ZrO 2 The mixing temperature is room temperature, the mixing speed is 20r/min, and the mixing time is 0.5h.
In the step C, the mixture is calcined at high temperature by a high-temperature solid-phase synthesis method, wherein the technological parameters of the high-temperature calcination are that the mixture is firstly put into a sintering furnace, then the temperature is increased from room temperature to 800 ℃ at a heating rate of 300 ℃/h, and the temperature is kept for 2h; continuously raising the temperature from 800 ℃ to 1600 ℃ at the heating rate of 500 ℃/h, and preserving the heat for 2h; continuing to cool from 1600 ℃ to room temperature at a cooling rate of 200 ℃/h; the whole high-temperature calcination process is carried out under normal pressure without introducing protective gas.
In the step D, the crucible is molded by a manual tamping molding method, wherein the tamping molding temperature is room temperature, the non-calcareous refractory material is added for 10 times, and the tamping time is 5min each time. The molded crucible is put into a sintering furnace for high-temperature calcination, wherein the technological parameters of the high-temperature calcination are that firstly, the molded crucible is put into the sintering furnace, and then the temperature is raised from room temperature to 1200 ℃ at the heating rate of 300 ℃/h, and the temperature is kept for 2 hours; continuously raising the temperature from 1200 ℃ to 1800 ℃ at the heating rate of 500 ℃/h, and preserving the heat for 2h; continuously reducing the temperature from 1800 ℃ to 1200 ℃ at the cooling rate of 200 ℃/h, and preserving the temperature for 0.5h; continuously reducing the temperature from 1200 ℃ to 400 ℃ at the cooling rate of 200 ℃/h, and preserving the temperature for 0.1h; continuing to cool from 400 ℃ to room temperature at a cooling rate of 500 ℃/h; the whole high-temperature calcination process is carried out under normal pressure without introducing protective gas.
In the deoxidation and desulfurization process, the vacuum degree in the furnace chamber is kept at 10Pa, the smelting temperature of the nickel-based superalloy is 1600 ℃, the refining temperature of the nickel-based superalloy is 1600 ℃, and the refining time is 40min.
In the fourth step, adding a metal simple substance Y into the nickel-based superalloy at the 20 th min of refining the nickel-based superalloy; at 40min of refining the nickel-based superalloy, adding a metal simple substance Ba and a metal simple substance Ca into the nickel-based superalloy at the same time; the total addition amount of the metal simple substance Y, the metal simple substance Ba and the metal simple substance Ca is 4 weight percent of the mass of the nickel-based superalloy, wherein the addition amount of the metal simple substance Y is 1 weight percent of the mass of the nickel-based superalloy.
Embodiment III:
according to another preferred embodiment of the deoxidizing and desulfurizing method for the nickel-based superalloy based on the non-calcareous refractory crucible of the present invention, the composition, the preparation steps, the deoxidizing and desulfurizing method for the nickel-based superalloy, the technical principle and the beneficial effects and the like of the non-calcareous refractory crucible are the same as those of the first embodiment, except that:
in the first step, the non-calcareous refractory crucible is made of a non-calcareous refractory material consisting of SrO and ZrO 2 Is reacted at high temperature to generate Sr as the compound 4 Zr 3 O 10 The method comprises the steps of carrying out a first treatment on the surface of the The non-calcareous refractory comprises, by mass, 45% of SrO and 45% of ZrO 2 55wt%.
The preparation method of the non-calcareous refractory crucible comprises the following steps: in step B, srO and ZrO 2 The mixing temperature is room temperature, the mixing speed is 5r/min, and the mixing time is 12h.
In the step C, the mixture is calcined at high temperature by a high-temperature solid phase synthesis method, wherein the technological parameters of the high-temperature calcination are that the mixture is firstly put into a sintering furnace, then the temperature is increased from room temperature to 800 ℃ at a heating rate of 100 ℃ per hour, and the temperature is kept for 4 hours; continuously raising the temperature from 800 ℃ to 1200 ℃ at the heating rate of 300 ℃/h, and preserving the heat for 8h; continuing to cool from 1200 ℃ to room temperature at a cooling rate of 100 ℃/h; the whole high-temperature calcination process is carried out under normal pressure without introducing protective gas.
In the step D, the crucible is formed by a manual tamping forming method, wherein the tamping forming temperature is room temperature, the non-calcareous refractory material is added for 5 times, and the tamping time is 20 minutes each time. The molded crucible is put into a sintering furnace for high-temperature calcination, wherein the technological parameters of the high-temperature calcination are that firstly, the molded crucible is put into the sintering furnace, and then the temperature is raised from room temperature to 1200 ℃ at a heating rate of 100 ℃/h, and the temperature is kept for 4 hours; continuously raising the temperature from 1200 ℃ to 1600 ℃ at the heating rate of 300 ℃/h, and preserving the heat for 8h; continuously reducing the temperature from 1600 ℃ to 1200 ℃ at the cooling rate of 100 ℃/h, and preserving the heat for 2h; continuously reducing the temperature from 1200 ℃ to 400 ℃ at the cooling rate of 100 ℃/h, and preserving the temperature for 0.5h; continuing to cool from 400 ℃ to room temperature at a cooling rate of 300 ℃/h; the whole high-temperature calcination process is carried out under normal pressure without introducing protective gas.
In the third step, the vacuum degree in the furnace chamber is kept to be 1 multiplied by 10 in the deoxidation and desulfurization process -3 Pa, the smelting temperature of the nickel-based superalloy is 1400 ℃, the refining temperature of the nickel-based superalloy is 1400 ℃, and the refining time is 40min.
In the fourth step, adding a metal simple substance Y into the nickel-based superalloy at the 10 th min of refining the nickel-based superalloy; at 20min of refining the nickel-based superalloy, adding a metal simple substance Ba and a metal simple substance Ca into the nickel-based superalloy at the same time; the total addition amount of the metal simple substance Y, the metal simple substance Ba and the metal simple substance Ca is 4.5 weight percent of the mass of the nickel-based superalloy, wherein the addition amount of the metal simple substance Y is 1.5 weight percent of the mass of the nickel-based superalloy.
For the three embodiments, the step C can be performed by high-temperature electric melting synthesis, wherein the high-temperature calcination process comprises the steps of placing the mixture into an electric melting furnace and starting the electric melting furnace, and the electric melting synthesis temperature is 2900-3200 ℃ and the electric melting synthesis time is 2-12h, and the whole high-temperature calcination process is performed under normal pressure without introducing protective gas. And D, forming the crucible by a cold isostatic pressing method, wherein the cold isostatic pressing temperature is room temperature, the pressure is 100-180MPa, and the pressure maintaining time is 2-60min.
The blendor, the sintering furnace, the electric melting furnace, the manual ramming forming equipment, the cold isostatic pressing forming equipment, the vacuum induction melting furnace and the like used in the three embodiments are selected according to actual use conditions, and special requirements are not made on equipment types. The nickel-based superalloy is a master alloy material; after the nickel-based superalloy is deoxidized and desulfurized, taking out alloy liquid from the vacuum induction melting furnace for casting to obtain castings, wherein the casting equipment, the casting process and the like are adopted by the prior art. The metal simple substance Y, the metal simple substance Ba and the metal simple substance Ca are added in the form of bulk or powder raw materials.
The specific description is as follows: the technical scheme of the invention relates to a plurality of parameters, and the beneficial effects and remarkable progress of the invention can be obtained by comprehensively considering the synergistic effect among the parameters. In addition, the value ranges of all the parameters in the technical scheme are obtained through a large number of tests, and aiming at each parameter and the mutual combination of all the parameters, the inventor records a large number of test data, and the specific test data are not disclosed herein for a long period of time.
It will be appreciated by those skilled in the art that the non-calcareous refractory crucible-based nickel-based superalloy deoxidizing desulfurization method of the present invention includes any combination of the above summary of the invention and detailed description of the invention and the various parts shown in the drawings, which are limited in length and are not described in detail in order to simplify the description. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A nickel-based superalloy deoxidization desulfurization method based on a non-calcareous refractory crucible is characterized by comprising the following steps of: a non-calcareous refractory crucible is adopted, a metal simple substance additive is added at the same time, a nickel-based superalloy is smelted by a vacuum induction smelting furnace, and then deoxidization and desulfurization are carried out on the nickel-based superalloy, the deoxidization and desulfurization process comprises the following steps,
step one: preparing a non-calcareous refractory crucible for later use according to design requirements;
step two: placing a non-calcareous refractory crucible into a vacuum induction melting furnace, and simultaneously placing a nickel-based superalloy into the non-calcareous refractory crucible;
step three: closing the vacuum induction melting furnace, and vacuumizing the furnace chamber to 1X 10 -3 -a vacuum degree of 10Pa, heating the furnace chamber to a melting temperature in a state of maintaining the vacuum degree, and then melting and refining the nickel-based superalloy;
step four: adding a metal simple substance Y into the nickel-base superalloy in the process of vacuumizing the furnace chamber or in the process of smelting the nickel-base superalloy or in the process of refining the nickel-base superalloy; in the refining process of the nickel-based superalloy, adding a metal simple substance Ba and a metal simple substance Ca into the nickel-based superalloy simultaneously;
step five: and after the refining of the nickel-base superalloy is finished, the deoxidization and desulfurization of the nickel-base superalloy can be completed.
2. The method for deoxidizing and desulfurizing nickel-base superalloy based on a non-calcareous refractory crucible according to claim 1, wherein: in the first step, the non-calcareous refractory crucible is made of a non-calcareous refractory material consisting of SrO and ZrO 2 Is reacted at high temperature to generate Sr as the compound 4 Zr 3 O 10 The method comprises the steps of carrying out a first treatment on the surface of the The non-calcareous refractory material comprises, by mass, 45-53% of SrO and 45-53% of ZrO 2 Accounting for 47 to 55 weight percent.
3. The method for deoxidizing and desulfurizing nickel-base superalloy based on a non-calcareous refractory crucible according to claim 2, wherein: in the first step, the preparation method of the non-calcareous refractory crucible comprises the following steps in sequence,
step A: respectively weighing SrO and ZrO according to design requirements 2 Standby;
and (B) step (B): srO and ZrO 2 Putting the mixture into a mixer for uniform mixing to form a mixture;
step C: calcining the mixture at high temperature by a high-temperature solid-phase synthesis or high-temperature electrofusion synthesis method, and after the high-temperature calcination is finished, preparing the non-calcareous refractory material;
step D: the prepared non-calcareous refractory material is adopted, a crucible is molded by a manual ramming molding or cold isostatic pressing molding method, and then the molded crucible is put into a sintering furnace for high-temperature calcination, and after the high-temperature calcination is finished, the non-calcareous refractory material crucible can be prepared.
4. A method for deoxidizing and desulfurizing a nickel-base superalloy based on a non-calcareous refractory crucible according to claim 3, wherein: in step B, srO and ZrO 2 The mixing temperature is room temperature, the mixing speed is 5-20r/min, and the mixing time is 0.5-12h.
5. The method for deoxidizing and desulfurizing nickel-base superalloy based on a non-calcareous refractory crucible according to claim 4, wherein: in the step C, the mixture is calcined at high temperature by a high-temperature solid phase synthesis method, wherein the technological parameters of the high-temperature calcination are that the mixture is firstly put into a sintering furnace, and then the temperature is raised from room temperature to 800 ℃ at a heating rate of 100-300 ℃/h, and the temperature is kept for 2-4h; continuously raising the temperature from 800 ℃ to 1200-1600 ℃ at the heating rate of 300-500 ℃/h, and preserving the temperature for 2-8h; continuously cooling from 1200-1600 ℃ to room temperature at a cooling rate of 100-200 ℃/h; the whole high-temperature calcination process is carried out under normal pressure without introducing protective gas.
6. The method for deoxidizing and desulfurizing nickel-base superalloy based on a non-calcareous refractory crucible according to claim 5, wherein: in the step C, the mixture is calcined at high temperature by a high-temperature electric melting synthesis method, wherein the technological parameters of the high-temperature calcination are that the mixture is put into an electric melting furnace and the electric melting furnace is started, the electric melting synthesis temperature is 2900-3200 ℃, the electric melting synthesis time is 2-12h, and the whole high-temperature calcination process is carried out under normal pressure without introducing protective gas.
7. The method for deoxidizing and desulfurizing nickel-base superalloy based on a non-calcareous refractory crucible according to claim 6, wherein: in the step D, forming the crucible by a manual tamping forming method, wherein the tamping forming temperature is room temperature, the non-calcareous refractory material is added for 5-10 times, and the tamping time is 5-20min each time; the crucible is formed by a cold isostatic pressing method, wherein the cold isostatic pressing temperature is room temperature, the pressure is 100-180MPa, and the dwell time is 2-60min.
8. The method for deoxidizing and desulfurizing nickel-base superalloy based on a non-calcareous refractory crucible according to claim 7, wherein: in the step D, the formed crucible is put into a sintering furnace for high-temperature calcination, wherein the technological parameters of the high-temperature calcination are that firstly, the formed crucible is put into the sintering furnace, and then the temperature is raised from room temperature to 1200 ℃ at a heating rate of 100-300 ℃/h, and the temperature is kept for 2-4h; continuously raising the temperature from 1200 ℃ to 1600-1800 ℃ at the heating rate of 300-500 ℃/h, and preserving the temperature for 2-8h; continuously cooling from 1600-1800 ℃ to 1200 ℃ at a cooling rate of 100-200 ℃/h, and preserving heat for 0.5-2h; continuously reducing the temperature from 1200 ℃ to 400 ℃ at the cooling rate of 100-200 ℃/h, and preserving the temperature for 0.1-0.5h; continuously cooling from 400 ℃ to room temperature at a cooling rate of 300-500 ℃/h; the whole high-temperature calcination process is carried out under normal pressure without introducing protective gas.
9. The method for deoxidizing and desulfurizing nickel-base superalloy based on a non-calcareous refractory crucible according to claim 8, wherein: in the third step, the smelting temperature of the nickel-based superalloy is 1400-1600 ℃; the refining temperature of the nickel-based superalloy is 1400-1600 ℃ and the refining time is 40min.
10. The method for deoxidizing and desulfurizing nickel-base superalloy based on a non-calcareous refractory crucible according to claim 9, wherein: in the fourth step, adding a metal simple substance Y into the nickel-based superalloy within 10-20min of refining the nickel-based superalloy; simultaneously adding a metal simple substance Ba and a metal simple substance Ca into the nickel-based superalloy within 20-40min of refining the nickel-based superalloy; the total addition amount of the metal simple substance Y, the metal simple substance Ba and the metal simple substance Ca is not more than 5 weight percent of the mass of the nickel-based superalloy, wherein the addition amount of the metal simple substance Y is not more than 2 weight percent of the mass of the nickel-based superalloy.
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