CN116121595A - High-resistance electrothermal alloy Cr20Ni80Zr and preparation method thereof - Google Patents
High-resistance electrothermal alloy Cr20Ni80Zr and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 77
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 29
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 21
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 11
- 238000005242 forging Methods 0.000 claims abstract description 11
- 229910000449 hafnium oxide Inorganic materials 0.000 claims abstract description 11
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000000638 solvent extraction Methods 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 13
- 230000005855 radiation Effects 0.000 claims description 12
- 238000005096 rolling process Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000007670 refining Methods 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910026551 ZrC Inorganic materials 0.000 claims description 6
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 238000005098 hot rolling Methods 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052845 zircon Inorganic materials 0.000 claims description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 abstract description 19
- 230000007797 corrosion Effects 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 10
- 150000007513 acids Chemical class 0.000 abstract description 5
- 238000005336 cracking Methods 0.000 abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000011572 manganese Substances 0.000 description 13
- 239000011651 chromium Substances 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical group [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- VAPILSUCBNPFBS-UHFFFAOYSA-L disodium 2-oxido-5-[[4-[(4-sulfophenyl)diazenyl]phenyl]diazenyl]benzoate Chemical compound [Na+].[Na+].Oc1ccc(cc1C([O-])=O)N=Nc1ccc(cc1)N=Nc1ccc(cc1)S([O-])(=O)=O VAPILSUCBNPFBS-UHFFFAOYSA-L 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/16—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling wire rods, bars, merchant bars, rounds wire or material of like small cross-section
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J5/00—Methods for forging, hammering, or pressing; Special equipment or accessories therefor
- B21J5/002—Hybrid process, e.g. forging following casting
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/14—Obtaining zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Materials Engineering (AREA)
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- Crystallography & Structural Chemistry (AREA)
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- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a high-resistance electrothermal alloy Cr20Ni80Zr, which comprises the following elements in percentage by weight: c is less than or equal to 0.075; mn is less than or equal to 0.55%; p is less than or equal to 0.018 percent; s is less than or equal to 0.013 percent; si:0.85-1.50%; cr:20.0-23.0%; fe is less than or equal to 1.0 percent; al is less than or equal to 0.5%; zr:0.3-0.55%; ni: the balance. Compared with the prior high-resistance electrothermal alloy Cr20Ni80, the high-resistance electrothermal alloy Cr20Ni80Zr has the advantages of long service life, good processing performance and excellent corrosion resistance; zirconium has excellent corrosion resistance to various acids, alkalis and salts, can improve the corrosion resistance of the alloy, has good plasticity, and can avoid the phenomena of fracture, cracking and the like of the electrothermal alloy in the forging process; in the process of preparing zirconium, zirconium tetrachloride is produced during chlorination, zirconium tetrachloride can be dissolved in water before purification, then hafnium is separated from the aqueous solution, hafnium oxide can be produced by a solvent extraction separation method by using isohexide as a solvent, then the hafnium oxide is heated to 900 ℃ in the presence of carbon, and then the zirconium tetrachloride is produced by chlorination.
Description
Technical Field
The invention relates to the technical field of electrothermal alloy, in particular to a high-resistance electrothermal alloy material Cr20Ni80Zr and a preparation method thereof.
Background
The alloy is macroscopically homogeneous, contains multiple chemical substances of metal elements and generally has metal characteristics, any element can be used as an alloy element, but a large amount of the element is added into the alloy, so-called components of the alloy are the most basic and independent substances, or simply called components, of the alloy; depending on the atomic radius, electronegativity, electron concentration, and the like of the constituent elements, phases that may occur in the crystalline alloy are solid solutions that maintain the same structure as the pure elements of the substrate and intermediate phases that do not have the same structure as any constituent element, including normal valence compounds, electron compounds, levels, sigma phases, interstitial phases, and interstitial compounds of complex structure, and the like.
The chromium alloy has high strength and corrosion resistance, is commonly called stainless steel with an alloy composed of iron and nickel, is commonly used for cutting tools, forms an anti-corrosion alloy layer on the surface of the steel or the iron by methods such as spraying, deposition, high-temperature diffusion and the like, is a strong oxidant in organic synthesis and petroleum industry, chrome yellow, chrome orange, chrome green and the like can be used as inorganic pigments, the color-developing substance in alcohol detection used by traffic police is dichromate, the alcohol can react with the alcohol to develop the color, the nickel-chrome alloy can also be used for preparing laboratory resistors, high-resistance electrothermal alloys (high nickel, iron-chrome aluminum), high-temperature alloys, precise alloys, heat-resistant alloys, special alloys, stainless steel and the like are common and commonly used nickel-chrome alloys, and the lower the temperature is, the larger the resistance of the nickel-chrome alloy is in length, the cross-sectional area is at a certain time, and is contrary to the general rule.
Cr20Ni80 is a resistance electrothermal alloy, and the alloy has stable structure, stable electrical and physical properties, good high-temperature mechanical properties, good cold deformation plasticity and good weldability, can not generate brittle fracture after long-term use, is mainly used for manufacturing household appliances and heating elements with working temperature below 1000 ℃, has long service life, and can possibly generate phenomena of fracture, cracking and the like in the forging process when the existing Cr20Ni80 is required to be forged in the processing process, and meanwhile, the corrosion resistance of the existing Cr20Ni80 to various acids, alkalis and salts is poor.
In order to overcome the defects of the Cr20Ni80 electrothermal alloy, the applicant has developed a high-resistance electrothermal alloy material Cr20Ni80Zr.
Disclosure of Invention
Aiming at the defects of the existing Cr20Ni80 alloy wire, the invention provides the high-resistance electrothermal alloy Cr20Ni80Zr with various service performances superior to those of the Cr20Ni80 alloy material, and the electrothermal alloy has the advantages of long service life, good processing performance and excellent corrosion resistance, so as to improve the corrosion resistance of the electrothermal alloy material and improve the strength of the alloy.
In order to achieve the above purpose, the improved high-resistance electrothermal alloy Cr20Ni80Zr comprises the following elements in percentage by weight: c is less than or equal to 0.075; mn is less than or equal to 0.55%; p is less than or equal to 0.018 percent; s is less than or equal to 0.013 percent; si:0.85-1.50%; cr:20.0-23.0%; fe is less than or equal to 1.0 percent; al is less than or equal to 0.5%; zr:0.3-0.55%; ni: the balance.
Preferably, the electrothermal alloy Cr20Ni80Zr comprises the following elements in percentage by weight: 0.055% of C, 1.25% of Si, 0.30% of Mn, 0.009% of P, 0.010% of S, 21.7% of Cr, 0.30% of AL and Fe:0.8 percent of Zr, 0.45 percent of Zr and the balance of Ni.
Preferably, the electrothermal alloy Cr20Ni80Zr comprises the following elements in percentage by weight: 0.065% of C, 1.30% of Si, 0.35% of Mn, 0.015% of P, 0.009% of S and 20.3% of Cr; AL 0.29%, fe:0.7%, ti 0.10%, zr 0.50%, and the balance Ni.
The invention also provides a high-resistance electrothermal alloy Cr20Ni80Zr and a preparation method thereof, wherein the preparation method comprises the following steps:
smelting: adding Ni, cr, mn, fe, si, AL, P, S, C and other raw materials, and the temperature is as follows: 1400-1600 ℃ for a period of time: not less than 1h;
refining: adding raw material Zr for refining, wherein the temperature is 1852-1900 ℃ and the duration is as follows: not less than 1h;
forging: the hot forging is adopted, the radiation heat transfer is mainly adopted, the heat energy is converted into radiation energy through high-temperature gas and a hearth, and after the radiation energy transmitted in an electric microwave mode is absorbed by metal, the radiation energy is converted into heat energy to heat the metal;
and (3) hot rolling: the rolling process comprises a biting stage, a dragging stage, a stable rolling stage and a rolling finishing stage, wherein the starting rolling temperature is as follows: 1150 ℃, finishing temperature: 930 ℃;
annealing: completely annealing at 1050 ℃;
acid washing: and (3) removing surface oxide skin and adhesion salts by using a sulfuric acid aqueous solution with the concentration of 5% -20%.
Preferably, in one refining step, the Zr is prepared as follows before adding Zr as a raw material:
heating: heating zircon and carbon together by an electric furnace to generate zirconium carbide;
chlorination: introducing chlorine into zirconium carbide, and the temperature is as follows: zirconium tetrachloride can be produced at 500 ℃;
purifying: zirconium is reduced with magnesium at about 850 ℃, and magnesium chloride byproduct can be removed by vacuum distillation at about 900 ℃ to finally obtain spongy zirconium.
It is further preferable that hafnium is contained in zirconium tetrachloride produced during chlorination, zirconium tetrachloride is dissolved in water before purification, and then hafnium is separated from the aqueous solution, and hafnium oxide can be produced by a solvent extraction separation method using isohexide as a solvent, and then hafnium oxide is heated to 900 ℃ in the presence of carbon, and then chlorinated to zirconium tetrachloride, and then purification is performed.
Compared with the prior high-resistance electrothermal alloy Cr20Ni80, the high-resistance electrothermal alloy Cr20Ni80Zr has the advantages of long service life, good processing performance and excellent corrosion resistance; zirconium has excellent corrosion resistance to various acids, alkalis and salts, can improve the corrosion resistance of the alloy, has good plasticity, and can avoid the phenomena of fracture, cracking and the like of the electrothermal alloy in the forging process; in the process of preparing zirconium, zirconium tetrachloride is produced during chlorination, zirconium tetrachloride can be dissolved in water before purification, then hafnium is separated from the aqueous solution, hafnium oxide can be produced by a solvent extraction separation method by using isohexide as a solvent, then hafnium oxide is heated to 900 ℃ in the presence of carbon, then zirconium tetrachloride is produced by chlorination, and then purification is carried out.
Detailed Description
The features and advantages of the present invention are described in detail below in connection with the particular embodiments.
The invention relates to a high-resistance electrothermal alloy Cr20Ni80Zr, which comprises the following elements in percentage by weight: c is less than or equal to 0.075; mn is less than or equal to 0.55%; p is less than or equal to 0.018 percent; s is less than or equal to 0.013 percent; si:0.85-1.50%; cr:20.0-23.0%; fe is less than or equal to 1.0 percent; al is less than or equal to 0.5%; zr:0.3-0.55%; ni: the balance.
The electrothermal alloy Cr20Ni80Zr comprises the following elements in percentage by weight: 0.055% of C, 1.25% of Si, 0.30% of Mn, 0.009% of P, 0.010% of S, 21.7% of Cr, 0.30% of AL and Fe:0.8 percent of Zr, 0.45 percent of Zr and the balance of Ni.
The electrothermal alloy Cr20Ni80Zr comprises the following elements in percentage by weight: 0.065% of C, 1.30% of Si, 0.35% of Mn, 0.015% of P, 0.009% of S and 20.3% of Cr; AL 0.29%, fe:0.7 percent of Ti, 0.10 percent of Zr, 0.50 percent of Ni and the balance
The principle and the function of the designed components of the high-resistance electrothermal alloy Cr20Ni80Zr are further described:
(1) Action of nickel: the nickel is similar to silver white, hard, ductile and ferromagnetic metal element, can be highly polished and corrosion-resistant, is green after being dissolved in nitric acid, is mainly used for alloy and used as a catalyst, is insoluble in water, forms a compact oxide film on the surface of moist air at normal temperature, can prevent the body metal from being continuously oxidized, and has good stability; the invention can form solid solution with chromium at high temperature, and has high-temperature strength.
(2) Chromium action: chromium is a silvery and glossy metal, has ductility and very high corrosion resistance, can be used as an additive for aluminum alloy, cobalt alloy, titanium alloy, high-temperature alloy, resistance heating alloy and the like, is slowly oxidized even in the red-hot state in air, is insoluble in water and can play a role in protecting the metal by being plated on the metal.
(3) Silicon action: silicon action: the SiO2 produced by oxidizing the silicon at high temperature has stable chemical property, does not react with water, is distributed at the interface of the oxide film and the matrix metal, can prevent oxygen from penetrating, and reduces the oxidation speed of the alloy.
(4) Manganese action: the manganese is mainly used for desulfurizing and deoxidizing steel in the steel industry, is also used as an additive of alloy to improve the strength, hardness, elastic limit, wear resistance, corrosion resistance and the like of the steel, is also used as an austenite compound element in high alloy steel to refine stainless steel, special alloy steel, stainless steel welding rods and the like, but manganese can reduce the oxidation resistance of the alloy, and the content is generally controlled to be less than 1.0 percent.
(5) Iron function: the alloy has good ductility, electric conductivity and heat conductivity, is easy to rust in humid air, and can rust more quickly in humid air in the presence of acid, alkali or salt solution, iron and manganese can reduce the oxidation resistance of the alloy, increase the oxidation speed, and the content of the alloy is controlled strictly, generally below 0.55%.
(6) Zirconium function: zirconium can be used as a vitamin in the metallurgical industry, plays a powerful role in deoxidizing, removing nitrogen and desulfurizing, and the hardness and strength of the steel can be surprisingly improved by only adding one thousandth of zirconium; zirconium is doped into copper and pumped into copper wires, the conductivity is not weakened, the melting point is greatly improved, the zirconium-containing zinc-magnesium alloy is very suitable for being used as a high-voltage wire, the zirconium-containing zinc-magnesium alloy is light and resistant to high temperature, the strength is twice that of a common magnesium alloy, and the zirconium has excellent corrosion resistance to various acids, alkalis and salts and has good plasticity; according to the invention, the blocky zirconium is added into the alloy, so that the corrosion resistance of the electrothermal alloy can be improved, the service life of the electrothermal alloy is prolonged, the plasticity is good, and the phenomena of fracture, cracking and the like of the electrothermal alloy in the forging process can be avoided.
The invention is further illustrated by the following non-limiting examples.
The alloy materials of examples 1-5 contained the following components and amounts by weight percent: the high-resistance electrothermal alloy Cr20Ni80Zr is characterized in that the electrothermal alloy Cr20Ni80Zr comprises the following elements in percentage by weight:
a first group: 0.055% of C, 1.25% of Si, 0.30% of Mn, 0.009% of P, 0.010% of S, 21.7% of Cr, 0.30% of AL and Fe:0.8 percent of Zr, 0.45 percent of Zr and the balance of Ni.
Second group: 0.065% of C, 1.30% of Si, 0.35% of Mn, 0.015% of P, 0.009% of S and 20.3% of Cr; AL 0.29%, fe:0.7%, ti 0.10%, zr 0.50%, and the balance Ni.
Third group: 0.50% of C, 1.35% of Si, 0.50% of Mn, 0.007% of P, 0.0012% of S, 21.3% of Cr, 0.41% of AL and Fe:0.5%, ti 0.10%, zr 0.37%, and the balance Ni.
Fourth group: 0.070% of C, 0.40% of Si, 0.45% of Mn, 0.013% of P, 0.007% of S, 20.9% of Cr, 0.39% of AL and Fe:0.9%, ti 0.20%, zr 0.41%, and the balance Ni.
Fifth group: 0.063% of C, 1.45% of Si, 0.25% of Mn, 0.011% of P, 0.005% of S, 22.6% of Cr, 0.28% of AL and 0.011% of Fe:0.8 percent, 0.20 percent of Ti, 0.26 percent of Zr and the balance of Ni.
The preparation process of the five groups of embodiments comprises the following steps:
the ingredients were designed according to five sets of embodiments of the invention and then processed according to the following steps;
smelting: adding Ni, cr, mn, fe, si, AL, P, S, C and other raw materials, controlling the temperature to be 1400-1600 ℃ and the duration to be not less than 1h;
refining: adding raw material Zr for refining, wherein the temperature is controlled between 1852 ℃ and 1900 ℃ and the duration is not less than 1h;
forging: the hot forging is adopted, the radiation heat transfer is mainly adopted, the heat energy is converted into radiation energy through high-temperature gas and a hearth, and after the radiation energy transmitted in an electric microwave mode is absorbed by metal, the radiation energy is converted into heat energy to heat the metal;
and (3) hot rolling: the rolling process comprises a biting stage, a dragging stage, a stable rolling stage and a rolling finishing stage, wherein the initial rolling temperature is 1150 ℃, and the finishing temperature is 930 ℃;
annealing: completely annealing at 1050 ℃;
acid washing: and (3) removing surface oxide skin and adhesion salts by using a sulfuric acid aqueous solution with the concentration of 5% -20%.
In one refining step, before adding raw material Zr, the Zr is prepared as follows:
heating: heating zircon and carbon together by an electric furnace to generate zirconium carbide;
chlorination: introducing chlorine into zirconium carbide, and the temperature is as follows: zirconium tetrachloride can be produced at 500 ℃;
purifying: zirconium is reduced with magnesium at about 850 ℃, and magnesium chloride byproduct can be removed by vacuum distillation at about 900 ℃ to finally obtain spongy zirconium.
Zirconium tetrachloride is produced in the chlorination, which is dissolved in water before purification, and then separated from the aqueous solution, hafnium oxide is produced by solvent extraction separation using isohexide as a solvent, and then heated to 900 ℃ in the presence of carbon, and then chlorinated to zirconium tetrachloride, followed by purification.
The invention can replace the traditional electrothermal alloy Cr20Ni80, and has the advantages of long service life, good processing performance and excellent corrosion resistance compared with the traditional electrothermal alloy Cr20Ni 80; compared with the prior electrothermal alloy Cr20Ni80, the electrothermal alloy of the invention is added with zirconium metal during refining, and the temperature is controlled between 1852 ℃ and 1900 ℃; because zirconium has excellent corrosion resistance to various acids, alkalis and salts, the corrosion resistance of the alloy can be improved, the zirconium alloy has good plasticity, and the phenomena of fracture, cracking and the like of the heating wire in the forging process can be avoided; in the process of preparing zirconium, zirconium tetrachloride is produced during chlorination, zirconium tetrachloride can be dissolved in water before purification, then hafnium is separated from the aqueous solution, hafnium oxide can be produced by a solvent extraction separation method by using isohexide as a solvent, then hafnium oxide is heated to 900 ℃ in the presence of carbon, then zirconium tetrachloride is produced by chlorination, and then purification is carried out.
The invention is not limited to the embodiments described, but a person skilled in the art may make modifications or changes without departing from the spirit of the invention, i.e. the scope of the disclosure, and the scope of the invention is defined by the claims.
Claims (6)
1. The high-resistance electrothermal alloy Cr20Ni80Zr is characterized in that the electrothermal alloy Cr20Ni80Zr comprises the following elements in percentage by weight: c is less than or equal to 0.075; mn is less than or equal to 0.55%; p is less than or equal to 0.018 percent; s is less than or equal to 0.013 percent; si:0.85-1.50%; cr:20.0-23.0%; fe is less than or equal to 1.0 percent; al is less than or equal to 0.5%; zr:0.3-0.55%; ni: the balance.
2. The high-resistance electrothermal alloy Cr20Ni80Zr according to claim 1, wherein the electrothermal alloy Cr20Ni80Zr comprises the following elements in percentage by weight: 0.055% of C, 1.25% of Si, 0.30% of Mn, 0.009% of P, 0.010% of S, 21.7% of Cr, 0.30% of AL and Fe:0.8 percent of Zr, 0.45 percent of Zr and the balance of Ni.
3. The high-resistance electrothermal alloy Cr20Ni80Zr according to claim 1, wherein the electrothermal alloy Cr20Ni80Zr comprises the following elements in percentage by weight: 0.065% of C, 1.30% of Si, 0.35% of Mn, 0.015% of P, 0.009% of S and 20.3% of Cr; AL 0.29%, fe:0.7%, ti 0.10%, zr 0.50%, and the balance Ni.
4. The high-resistance electrothermal alloy Cr20Ni80Zr and the preparation method thereof according to claim 1, wherein the preparation method comprises the steps of:
smelting: adding Ni, cr, mn, fe, si, AL, P, S, C and other raw materials, and the temperature is as follows: 1400-1600 ℃ for a period of time: not less than 1h;
refining: adding raw material Zr for refining, wherein the temperature is 1852-1900 ℃ and the duration is as follows: not less than 1h;
forging: the hot forging is adopted, the radiation heat transfer is mainly adopted, the heat energy is converted into radiation energy through high-temperature gas and a hearth, and after the radiation energy transmitted in an electric microwave mode is absorbed by metal, the radiation energy is converted into heat energy to heat the metal;
and (3) hot rolling: the rolling process comprises a biting stage, a dragging stage, a stable rolling stage and a rolling finishing stage, wherein the starting rolling temperature is as follows: 1150 ℃, finishing temperature: 930 ℃;
annealing: completely annealing at 1050 ℃;
acid washing: and (3) removing surface oxide skin and adhesion salts by using a sulfuric acid aqueous solution with the concentration of 5% -20%.
5. The method for producing high-resistance electrothermal alloy Cr20Ni80Zr according to claim 4, wherein, before adding raw material Zr in the refining step, the steps for producing Zr are as follows:
heating: heating zircon and carbon together by an electric furnace to generate zirconium carbide;
chlorination: introducing chlorine into zirconium carbide, and the temperature is as follows: zirconium tetrachloride can be produced at 500 ℃;
purifying: zirconium is reduced with magnesium at about 850 ℃, and magnesium chloride byproduct can be removed by vacuum distillation at about 900 ℃ to finally obtain spongy zirconium.
6. The high-resistance electrothermal alloy Cr20Ni80Zr and its production according to claim 5, wherein the zirconium tetrachloride is produced by dissolving zirconium tetrachloride in water before purification, separating hafnium from the aqueous solution, producing hafnium oxide by solvent extraction separation using isohexide as a solvent, heating the hafnium oxide to 900 ℃ in the presence of carbon, and then chlorinating it to produce zirconium tetrachloride, followed by purification.
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| US3723107A (en) * | 1969-03-07 | 1973-03-27 | Int Nickel Co | Nickel-chromium-cobalt alloys for use at relatively high temperatures |
| CN101899593A (en) * | 2010-04-06 | 2010-12-01 | 江苏立新合金实业总公司 | Nickel-chromium high-resistance electrothermal alloy |
| CN102191409A (en) * | 2011-04-22 | 2011-09-21 | 江苏新华合金电器有限公司 | New high-resistance electrical heating alloy material and preparation method thereof |
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| CN109055824A (en) * | 2018-07-02 | 2018-12-21 | 江苏新华合金电器有限公司 | Improved high-resistance electrothermic alloy Cr20Ni80Zr and preparation method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3723107A (en) * | 1969-03-07 | 1973-03-27 | Int Nickel Co | Nickel-chromium-cobalt alloys for use at relatively high temperatures |
| CN101899593A (en) * | 2010-04-06 | 2010-12-01 | 江苏立新合金实业总公司 | Nickel-chromium high-resistance electrothermal alloy |
| CN102191409A (en) * | 2011-04-22 | 2011-09-21 | 江苏新华合金电器有限公司 | New high-resistance electrical heating alloy material and preparation method thereof |
| CN206241251U (en) * | 2016-12-13 | 2017-06-13 | 浙江国石磁业有限公司 | A kind of reclaimer for Industry Waste zirconium powder |
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