CN102634691B - Manufacturing method of high-strength and high-corrosion-resistance cupronickel alloy - Google Patents
Manufacturing method of high-strength and high-corrosion-resistance cupronickel alloy Download PDFInfo
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Abstract
The invention relates to a high-strength and high-corrosion-resistance cupronickel alloy and a manufacturing method thereof. The high-strength and high-corrosion-resistance cupronickel alloy is characterized by comprising cathode copper and electrolytic nickel as main components, less zirconium sponge and metallic silicon powder, and less than or equal to 2.0% of impurities. According to the manufacturing method provided by the invention, a soft alloy end-product is formed by performing the steps of electrically smelting, refining, condensing and crusting, casting and molding, in a vacuum induction furnace, and the like. The high-strength and high-corrosion-resistance cupronickel alloy has high strength and high corrosion resistance, 670-770 MPa tensile strength and 38-45% extension property, so that the property is 40% higher than B19 property, the corrosion resistance is increased by 3 times and the machining property is excellent. The high-strength and high-corrosion-resistance cupronickel alloy has the characteristics of wide application, long service life and the like, and can be used for producing plates, belts, pipes, bars, lines and forging pieces. The high-strength and high-corrosion-resistance cupronickel alloy is widely applied to the industries, such as shipbuilding, chemical industry, manufacturing and metallurgy. The manufacturing method provided by the invention also has the advantages of simple steps of the cupronickel alloy processing technology, low processing cost, easiness in production, and meeting the demands of various application fields on the high-strength and high-corrosion-resistance cupronickel alloy.
Description
Technical field
The present invention relates to a kind of cupronickel technical field, specifically a kind of have high strength high corrosion resistance copper-nickel alloy alloy and a manufacture method thereof.
Background technology
The advantages such as because copper-nickel alloy erosion resistance is high, elasticity is large, intensity high (fine copper relatively), are widely used in shipbuilding, chemical industry, the industries such as electronics.For the manufacture of military project corrosion-resistant element, various springs and plug-in unit.
Cu and Ni high temperature are unlimited solid solution while dissolving, face-centered cube lattice.The long-time sea water immersion of B19 copper-nickel alloy tensile strength 400 σ b/MPa extension property 35 δ/% of domestic production at present can produce certain corrosion.How to put forward the high performance copper-nickel alloy erosion resistance that simultaneously improves is the problem that this professional science and technology personnel concentrate on studies for a long time always, but fails so far to see the relevant relevant report of breaking through.
Summary of the invention
The object of the invention is for above-mentioned existing technical problem, and a kind of high strength high corrosion resistance copper-nickel alloy alloy and manufacture method thereof are provided.The present invention had both increased substantially intensity, increased substantially again erosion resistance, wear resistance.
The object of the invention is to be achieved through the following technical solutions: the weight percent of this copper-nickel alloy alloying constituent consists of:
Metallic nickel 44-46%, zirconium sponge 0.1-0.5%, silicon 1-2.5%, metallic copper is surplus, inevitably impurity≤2.0%.
The preferred weight percent of copper-nickel alloy alloying constituent of the present invention consists of: metallic nickel 44-46%, and zirconium sponge 0.2-0.4%, silicon 1.5-2.0%, metallic copper is surplus, inevitably impurity≤2.0%.
The present invention also comprises a kind of manufacture method with high strength high corrosion resistance copper-nickel alloy alloy, it is characterized in that: first take electrolytic copper, electrolytic nickel, zirconium sponge, silicon is preparation of raw material alloy material, each grouping is by following weight percent designing quality, respectively by a certain amount of electrolytic copper, electrolytic nickel, zirconium sponge, silica flour packs in vacuum induction furnace step by step; Its specified operational procedure is as follows: nickel, copper, silicon are put into Magnesia crucible zirconium sponge and put into intake chute power transmission fusing after vacuumizing, when vacuum tightness reaches 0.9～1.0Pa, Modulating Power is 30～45KW, and then through refining after 30～40 minutes, through having a power failure to condensation, crust, send into again the electrofusion that power is 15～25KW, through refining after 20～30 minutes applying argon gas to vacuum tightness 0.08～0.09MPa, add zirconium sponge turndown to stir 3～5 times, now temperature is: 1380～1420 ℃, charged cast molding, within cooling 10～20 minutes, aftershaping ingot bar is separated with mould; Moulding ingot bar is processed post-heating through milling face and is become band to 950-1050 ℃ of split rolling method, and general working rate control is between 70-90%, is annealed into soft state through 750-800 ℃, is alloy finished product;
The weight percent of this alloying constituent consists of: metallic nickel 44-46%, and zirconium sponge 0.1-0.5%, silicon 1-2.5%, metallic copper is surplus, inevitably impurity≤2.0%.
The present invention, when improving erosion resistance, increases substantially the intensity of product.Through great many of experiments, finally take to add zirconium (Zr) silicon (Si) mode.Why selecting the reason of zirconium, silicon, is that the gases such as a large amount of absorption oxygen of zirconium energy when heating, hydrogen, nitrogen are that desirable getter has the solidity to corrosion of zirconium to approach well niobium, tantalum than titanium again.Adding of silicon is conducive to promote metallicity by solution strengthening crystal grain thinning.
The present invention compares and has the following advantages with existing copper-nickel alloy:
1, tensile strength 670-770 σ
b/ MPa, extends 38-45 δ/%, than the B19 intensity of the current production of China, improves more than 40%, extends and improves 20%, and erosion resistance improves nearly 3 times.
2, the present invention has and is widely used, and the features such as long service life, can produce plate, band, pipe, rod, line, forging.In industries such as shipbuilding, chemical industry, machinofacture, metallurgy, be applied.The present invention also has that the processibility of copper-nickel alloy alloy is good, and complete processing link is simple, and tooling cost is low, is easy to produce, and has been suitable for the requirement of each Application Areas to high strength high corrosion resistance copper-nickel alloy alloy.
Manufacture method of the present invention has changed original non-true fusion-casting process, adopts vacuum melting to reduce the quality that the gas content in metal has further improved metal, simultaneously because zirconium sponge cannot melt and join in the metal melt of copper nickel under non-vacuum condition.
This manufacture method has changed the technique that adopts antivacuum annealing between original passage, adopts vacuum nitrogen gas protection annealing to improve greatly the surface quality of band.(because band after antivacuum annealing need pass through cleanup acid treatment.Be that contaminate environment has increased again cost)
To the present invention, be described in further detail by example below, but following example is only the present invention's example wherein, do not represent the rights protection scope that the present invention limits, the scope of the present invention is as the criterion with claims.
embodiment:
embodiment 1
(1) take electrolytic copper, electrolytic nickel, zirconium sponge, silicon is preparation of raw material alloy material, each echelon design quality is respectively 10.7 kilograms of electrolytic coppers, 8.9 kilograms of electrolytic nickels, 0.015 kilogram of zirconium sponge, 0.1 kilogram of metallic silicon power (packing step by step 25 kilograms of vacuum induction furnaces into).Schedule of operation is as follows: nickel+copper+silicon put into Magnesia crucible zirconium sponge put into intake chute → vacuumize → power transmission fusing (Modulating Power is 30-45KW when vacuum tightness reaches 0.9～1.0Pa) → refining 30-40 minute → have a power failure to the power transmission fusing (power is 15～25KW) of condensation crust → again after → refining 20-30 minute applying argon gas to vacuum tightness 0.08～0.09MPa again, add zirconium sponge turndown to stir 3-5 time → thermometric (1380-1420 ℃) → charged casting, mould molding, gets ingot → sampling for cooling 10～20 minutes.
(2) ingot bar is processed post-heating through milling face and is become band to 950-1050 ℃ of split rolling method, and general working rate control is between 70-90%, is annealed into soft state through 750-800 ℃, is alloy finished product.
Each specification:
1. raw material need be selected high-quality electrolytic copper, electrolytic nickel, zirconium sponge, metallic silicon power;
2. vacuum melting vacuum tightness will reach 1Pa, heats to a 1380-1420 ℃ of refining 20-30 minute applying argon gas protective casting and comes out of the stove;
3. analysis of components: nickel (44-46%) zirconium (0.2-0.4%) silicon (1.5-2.0%) copper surplus, impurity≤2.0%, analytical procedure is slightly;
4. through milling face thickness, be ingot bar 40*200*300(mm) that 30-35 (mm) is as the criterion with surperficial zero defect.
5. low power penetration inspection zero defect;
6. 950-1050 ℃ of insulation of ingot bar heating is 2 hours, and hot rolling cogging is rolled to 7.5mm and processes to 7.0mm through milling face;
7. in, between mill train time, vacuum annealing 750-800 ℃ of insulation is rolled to 2.0mm through 3 passages from 7.0mm in 4 hours.
embodiment 2:
(1) take electrolytic copper, electrolytic nickel, zirconium sponge, silicon is preparation of raw material alloy material, each echelon design quality is respectively 10.9 kilograms of electrolytic coppers, 8.7 kilograms of electrolytic nickels, 0.02 kilogram of zirconium sponge, 0.13 kilogram of metallic silicon power (packing successively step by step 25 kilograms of vacuum induction furnaces into).Schedule of operation is as follows: nickel+copper+silicon put into Magnesia crucible zirconium sponge put into intake chute → vacuumize → power transmission fusing (Modulating Power is 30-45KW when vacuum tightness reaches 0.9～1.0Pa) → refining 30-40 minute → have a power failure to the power transmission fusing (power is 15～25KW) of condensation crust → again after → refining 20-30 minute applying argon gas to vacuum tightness 0.08～0.09MPa, add again zirconium sponge turndown to stir 3-5 time → thermometric (1380-1420 ℃) → charged casting, mould molding, gets ingot → sampling for cooling 10～20 minutes.
(2) ingot bar is processed post-heating through milling face and is become band to 950-1050 ℃ of split rolling method, and general working rate control is between 70-90%, is annealed into soft state through 750-800 ℃, is alloy finished product.
embodiment 3:
(1) take electrolytic copper, electrolytic nickel, zirconium sponge, silicon is preparation of raw material alloy material, each echelon design quality is respectively 11 kilograms of electrolytic coppers, 8.6 kilograms of electrolytic nickels, 0.025 kilogram of zirconium sponge, 0.15 kilogram of metallic silicon power (packing step by step 25 kilograms of vacuum induction furnaces into).Schedule of operation is as follows: nickel+copper+silicon put into Magnesia crucible zirconium sponge put into intake chute → vacuumize → power transmission fusing (Modulating Power is 30-45KW when vacuum tightness reaches 0.9～1.0Pa) → refining 30-40 minute → have a power failure to the power transmission fusing (power is 15～25KW) of condensation crust → again after → refining 20-30 minute applying argon gas to vacuum tightness 0.08～0.09MPa, add again zirconium sponge turndown to stir 3-5 time → thermometric (1380-1420 ℃) → charged casting, mould molding, gets ingot → sampling for cooling 10～20 minutes.
(2) ingot bar is processed post-heating through milling face ingot and is become band to 950-1050 ℃ of split rolling method, and general working rate control is between 70-95%, is annealed into soft state through 750-800 ℃, is alloy finished product.
embodiment 4:
(1) take electrolytic copper, electrolytic nickel, zirconium sponge, silicon is preparation of raw material alloy material, each echelon design quality is respectively 10.6 kilograms of electrolytic coppers, 8.8 kilograms of electrolytic nickels, 0.03 kilogram of zirconium sponge, 0.17 kilogram of metallic silicon power (packing step by step 25 kilograms of vacuum induction furnaces into).Schedule of operation is as follows: nickel+copper+silicon put into Magnesia crucible zirconium sponge put into intake chute → vacuumize → power transmission fusing (Modulating Power is 30-45KW when vacuum tightness reaches 0.9～1.0Pa) → refining 30-40 minute → have a power failure to the power transmission fusing (power is 15～25KW) of condensation crust → again after → refining 20-30 minute applying argon gas to vacuum tightness 0.08～0.09MPa, add again zirconium sponge turndown to stir 3-5 time → thermometric (1380-1420 ℃) → charged casting, mould molding, gets ingot → sampling for cooling 10～20 minutes.
(2) ingot bar is processed post-heating through milling face and is become band to 950-1050 ℃ of split rolling method, and general working rate control is between 70-90%, is annealed into soft state through 750-800 ℃, is alloy finished product.
embodiment 5:
(1) take electrolytic copper, electrolytic nickel, zirconium sponge, silicon is preparation of raw material alloy material, each echelon design quality is respectively 10.7 kilograms of electrolytic coppers, 9.0 kilograms of electrolytic nickels, 0.035 kilogram of zirconium sponge, 0.19 kilogram of metallic silicon power (packing step by step 25 kilograms of vacuum induction furnaces into).Schedule of operation is as follows: nickel+copper+silicon put into Magnesia crucible zirconium sponge put into intake chute → vacuumize → power transmission fusing (Modulating Power is 30-45KW when vacuum tightness reaches 0.9～1.0Pa) → refining 30-40 minute → have a power failure to the power transmission fusing (power is 15～25KW) of condensation crust → again after → refining 20-30 minute applying argon gas to vacuum tightness 0.08～0.09MPa, add again zirconium sponge turndown to stir 3-5 time → thermometric (1380-1420 ℃) → charged casting, mould molding, gets ingot → sampling for cooling 10～20 minutes.
(2) ingot bar is processed post-heating through milling face and is become band to 950-1050 ℃ of split rolling method, and general working rate control is between 70-90%, is annealed into soft state through 750-800 ℃, is alloy finished product.
embodiment 6:
(1) take electrolytic copper, electrolytic nickel, zirconium sponge, silicon is preparation of raw material alloy material, each echelon design quality is respectively 10.8 kilograms of electrolytic coppers, 8.7 kilograms of electrolytic nickels, 0.04 kilogram of zirconium sponge, 0.21 kilogram of metallic silicon power (packing step by step 25 kilograms of vacuum induction furnaces into).Schedule of operation is as follows: nickel+copper+silicon put into Magnesia crucible zirconium sponge put into intake chute → vacuumize → power transmission fusing (Modulating Power is 30-45KW when vacuum tightness reaches 0.9～1.0Pa) → refining 30-40 minute → have a power failure to the power transmission fusing (power is 15～25KW) of condensation crust → again after → refining 20-30 minute applying argon gas to vacuum tightness 0.08～0.09MPa, add again zirconium sponge turndown to stir 3-5 time → thermometric (1380-1420 ℃) → charged casting, mould molding, gets ingot → sampling for cooling 10～20 minutes.
(2) ingot bar is processed post-heating through milling face and is become band to 950-1050 ℃ of split rolling method, and general working rate control is between 70-90%, is annealed into soft state through 750-800 ℃, is alloy finished product.
embodiment 7:
1) take electrolytic copper, electrolytic nickel, zirconium sponge, silicon is preparation of raw material alloy material, each echelon design quality is respectively 11.1 kilograms of electrolytic coppers, 8.6 kilograms of electrolytic nickels, 0.045 kilogram of zirconium sponge, 0.23 kilogram of metallic silicon power (packing step by step 25 kilograms of vacuum induction furnaces into).Schedule of operation is as follows: nickel+copper+silicon put into Magnesia crucible zirconium sponge put into intake chute → vacuumize → power transmission fusing (Modulating Power is 30-45KW when vacuum tightness reaches 0.9～1.0Pa) → refining 30-40 minute → have a power failure to the power transmission fusing (power is 15～25KW) of condensation crust → again after → refining 20-30 minute applying argon gas to vacuum tightness 0.08～0.09MPa, add again zirconium sponge turndown to stir 3-5 time → thermometric (1380-1420 ℃) → charged casting, mould molding, gets ingot → sampling for cooling 10～20 minutes.
(2) ingot bar is processed post-heating through milling face and is become band to 950-1050 ℃ of split rolling method, and general working rate control is between 70-90%, is annealed into soft state through 750-800 ℃, is alloy finished product.
embodiment 8:
(1) take electrolytic copper, electrolytic nickel, zirconium sponge, silicon is preparation of raw material alloy material, each echelon design quality is respectively 11 kilograms of electrolytic coppers, 8.7 kilograms of electrolytic nickels, 0.05 kilogram of zirconium sponge, 0.25 kilogram of metallic silicon power (packing step by step 25 kilograms of vacuum induction furnaces into).Schedule of operation is as follows: nickel+copper+silicon put into Magnesia crucible zirconium sponge put into intake chute → vacuumize → power transmission fusing (Modulating Power is 30-45KW when vacuum tightness reaches 0.9～1.0Pa) → refining 30-40 minute → have a power failure to the power transmission fusing (power is 15～25KW) of condensation crust → again after → refining 20-30 minute applying argon gas to vacuum tightness 0.08～0.09MPa, add again zirconium sponge turndown to stir 3-5 time → thermometric (1380-1420 ℃) → charged casting, mould molding, gets ingot → sampling for cooling 10～20 minutes.
(2) ingot bar is processed post-heating through milling face and is become band to 950-1050 ℃ of split rolling method, and general working rate control is between 70-90%, is annealed into soft state through 750-800 ℃, is alloy finished product.
B19 copper-nickel alloy and invention material mechanical performance, anticorrosive contrast table:
This material is raw-material 3 times through chemical industry and shipbuilding industry to B19 copper-nickel alloy material contrast work-ing life, believes that this type material also can be widely used in other industry.
Claims (2)
1. the manufacture method of a high strength highly corrosive copper-nickel alloy alloy, it is characterized in that: first take electrolytic copper, electrolytic nickel, zirconium sponge, silica flour is preparation of raw material alloy material, each component is by following weight percent designing quality, respectively by a certain amount of electrolytic copper, electrolytic nickel, zirconium sponge, silica flour packs in vacuum induction furnace step by step, its specified operational procedure is as follows: electrolytic nickel, electrolytic copper, silica flour is put into Magnesia crucible, zirconium sponge is put into intake chute power transmission fusing after vacuumizing, when vacuum tightness reaches 0.9～1.0Pa, Modulating Power is 30～45kW, and then through refining after 30～40 minutes, through having a power failure to condensation, crust, send into again the electrofusion that power is 15～25kW, through refining after 20～30 minutes applying argon gas to vacuum tightness 0.08～0.09MPa, add zirconium sponge turndown to stir 3～5 times, now temperature is: 1380～1420 ℃, charged cast molding, within cooling 10～20 minutes, aftershaping ingot bar is separated with mould, moulding ingot bar is processed post-heating through milling face and is become band to 950-1050 ℃ of split rolling method, and general working rate control is between 70-90%, is annealed into soft state through 750-800 ℃, is alloy finished product,
The weight percent of this alloying constituent consists of: nickel 44-46%, and zirconium 0.1-0.5%, silicon 1-2.5%, copper is surplus, inevitably impurity≤2.0%.
2. the manufacture method of high strength highly corrosive copper-nickel alloy alloy according to claim 1, it is characterized in that the weight percent that is this alloying constituent consists of: nickel 44-46%, zirconium 0.2-0.4%, silicon 1.5-2.0%, copper is surplus, inevitably impurity≤2.0%.
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| CN102925753B (en) * | 2012-10-30 | 2014-10-15 | 沈阳难熔金属研究所 | Nickel-copper alloy with high strength and high corrosion resistance and manufacturing method thereof |
| CN104694779B (en) * | 2015-01-16 | 2017-06-20 | 中国船舶重工集团公司第七二五研究所 | A kind of B30 materials and preparation method thereof |
| CN110004321B (en) | 2018-01-05 | 2021-04-20 | 比亚迪股份有限公司 | Copper-based microcrystalline alloy, preparation method thereof and electronic product |
| CN110042319A (en) * | 2019-05-20 | 2019-07-23 | 广州广钢新材料股份有限公司 | A kind of low temperature screw-thread steel and its production technology |
| CN110669960B (en) * | 2019-11-08 | 2021-04-20 | 无锡金卫星铜业有限公司 | Wear-resistant cupronickel wire and forming method thereof |
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Address after: 110000 No. 223-1, Chun Ying Street, Sujiatun District, Liaoning, Shenyang Patentee after: Shenyang Non Ferrous Metals Research Institute Co Ltd Address before: Shenyang city Shengzhen Lin village in Sujiatun District of Shenyang City, Liaoning province 110101 Refractory Metals Research Institute Patentee before: Shenyang Institute of Refractory Metal |