CN103740977A - Corrosion-resistant white copper tube and manufacturing method thereof - Google Patents
Corrosion-resistant white copper tube and manufacturing method thereof Download PDFInfo
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- CN103740977A CN103740977A CN201410018705.6A CN201410018705A CN103740977A CN 103740977 A CN103740977 A CN 103740977A CN 201410018705 A CN201410018705 A CN 201410018705A CN 103740977 A CN103740977 A CN 103740977A
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- 229910000570 Cupronickel Inorganic materials 0.000 title claims abstract description 56
- 238000005260 corrosion Methods 0.000 title claims abstract description 39
- 230000007797 corrosion Effects 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000000956 alloy Substances 0.000 claims abstract description 42
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 23
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 17
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 14
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000009785 tube rolling Methods 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 59
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 24
- 239000011572 manganese Substances 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 20
- 239000011133 lead Substances 0.000 claims description 20
- 239000011701 zinc Substances 0.000 claims description 18
- 229910017052 cobalt Inorganic materials 0.000 claims description 16
- 239000010941 cobalt Substances 0.000 claims description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 229910000563 Arsenical copper Inorganic materials 0.000 claims description 8
- 229910000906 Bronze Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000005864 Sulphur Substances 0.000 claims description 7
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000010974 bronze Substances 0.000 claims description 7
- 239000003610 charcoal Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000010622 cold drawing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 claims description 7
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 claims description 7
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 7
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 abstract description 8
- 238000005266 casting Methods 0.000 abstract description 3
- 229910052745 lead Inorganic materials 0.000 abstract description 2
- 238000003723 Smelting Methods 0.000 abstract 1
- 230000006698 induction Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- 239000013535 sea water Substances 0.000 description 10
- 238000005275 alloying Methods 0.000 description 8
- 238000005554 pickling Methods 0.000 description 8
- 230000003628 erosive effect Effects 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- -1 first Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
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- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000009833 condensation Methods 0.000 description 2
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- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000023753 dehiscence Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000013505 freshwater Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Abstract
The invention relates to the field of copper-nickel alloys, in particular to a corrosion-resistant white copper tube and a manufacturing method thereof. The corrosion-resistant white copper tube comprises the following chemical components in percentage by weight: less than or equal to 0.03 percent of C, 0.10-0.20 percent of Si, 6.0-8.0 percent of Mn, less than or equal to 0.005 percent of S, 0.15-0.20 percent of P, 22.0-24.0 percent of Ni, 2.0-4.0 percent of Co, 2.0-4.0 percent of Zn, 0.20-0.40 percent of Pb, 3.0-4.0 percent of Fe, 0.15-0.20 percent of RE, 0.005-0.010 percent of As and the balance of Cu. The method comprises the following steps: manufacturing a white copper tube blank by performing induction smelting; performing coil stretching production on the white copper tube blank through the procedures of casting, sawing, water seal extrusion, tube rolling, disk stretching, disk blade die peeling, disk stretching, stretching by using a Schumag combined pulling machine, straight bar stretching and annealing. By adopting the corrosion-resistant white copper tube, the problems of limited service life of the conventional copper-nickel alloy material and non-adaptability to coil stretching production due to poor elasticity are solved, and coil stretching is realized.
Description
Technical field
The present invention relates to corronel field, relate in particular to a kind of corrosion-resistant White Copper Tubes and preparation method thereof for ocean.
Background technology
Along with the development of marine cause with strengthen the process of naval's construction, the demand of copper and copper alloy condenser pipe is at rapid growth.Within 2011, domestic only electric power, shipbuilding, three industries of sea water desaltination have reached 60,000 tons to the demand of high precision copper and cupronickel tubing, domestic market also will continue to increase to the demand of high precision copper and copper-alloy pipe-material, and expecting domestic needs amount in 2015 will be over 100,000 ton.
Develop the HSn70-1B that adds boron the nineties in last century, add Mn, Ni and trace rare-earth element cerium HSn70-1AB, intensity and solidity to corrosion further improve, but brazed copper tube Dezincification corrosion and stress corrosion are all less than cupronickel, have limited its application on naval vessel.
At present, prolong material in naval vessel mainly adopts BFe30-1-1 and BF10-1-1.Wherein, BFe30-1-1 iron white copper is structure cupronickel, has good mechanical property, have high solidity to corrosion, but machinability is poor in seawater, fresh water and steam.Condenser and thermostatted that BFe30-1-1 iron white copper is worked under high temperature, high pressure, high-speed condition for shipbuilding.Fe in BFe10-1-1 alloy and Mn add the anti-etch performance of greatly having improved this material, and in micro-salts solution, receptible top speed can reach 4m/s.This alloy, to cleaning or having the seawater of certain pollution and Jiang Wanshui to have good erosion resistance, is used on the heat exchanger of seawater by a large amount of use in power station, desalination, petrochemical factory etc.
Cupronickel material is the common used material of manufacturing sea water piping system, but cupronickel material lifetime is limited, needs periodic replacement.Compare with the prolong of other materials, titanium is not corroded in the sulfide of all concentration, has good solidity to corrosion in the polluted seawater of sulfur compound.Meanwhile, titanium under the condition up to 40g/L, all has good corrosion resistance nature up to 20m/s and sand content in water speed.But titanium is produced and processing difficulties, and output is very low, expensive, in price, compare and do not preponderate with copper nickel pipe.
The production of existing copper alloy condensation tubes, adopt vertical half-continuous process to produce solid ingot casting, length saw is cut to the long short ingot of 400～600mm, and short ingot is heated to 800～1000 ℃ (different and different depending on alloy species), in the enterprising eleven punch 11 extruding of double-acting extruding machine, obtains hollow bloom.Pipe is carried out carrying out Pilger rolling after scale sawing, aligning, pickling.To rolling pipe, need to be cut into the short tube of 4～6m, with after annealing, pickling, head processed, stretching; 3～5 times so repeatedly, technical process is long, and production passage is many; Extruding heating, annealing repeatedly, energy consumption is high; The loss of extrusion process frock is large, cost is high; Pickling process metal loss is large.Particularly product property is low, cannot produce super long copper alloy condensation tubes.Therefore, need to seek a kind of low cost that has, reduce metal loss, there is the environmentally friendly novel process of good corrosion resistance simultaneously.
Traditional technology generally adopts: the processing method of founding → sawing → extruding (glass isolator is lubricated) strip off the skin → vertical bar of → sawing → rolling → sawing → annealing → pickling → vertical bar stretching → sword mould stretching → scale sawing → annealing.Traditional method technical process is long, and production efficiency is low, and production cost is high, owing to there being the operations such as pickling, glass isolator lubricate, serious to equipment and environmental pollution.
And the technique of traditional cupronickel tubing has long flow path, production efficiency is low, and production cost is high, to environment and many drawbacks such as equipment contaminate is serious.Therefore, need to seek a kind of low cost that has, reduce metal loss, there is the environmentally friendly novel process of good corrosion resistance simultaneously.
Summary of the invention
The object of this invention is to provide a kind of corrosion-resistant White Copper Tubes and preparation method thereof for ocean, solve traditional cupronickel material lifetime limited, because plasticity is low, be difficult to adapt to the problems such as the coil pipe stretching mode of production.
Technical scheme of the present invention is:
A corrosion-resistant White Copper Tubes, by weight percentage, its chemical composition and content are as follows:
Carbon C :≤0.03; Silicon Si:0.10～0.20; Manganese Mn:6.0～8.0; Sulphur S :≤0.005; Phosphorus P:0.15～0.20; Nickel: 22.0～24.0; Cobalt Co:2.0～4.0; Zinc Zn:2.0～4.0; Plumbous Pb:0.20～0.40; Iron Fe:3.0～4.0; Rare earth elements RE: 0.15～0.20; Arsenic As:0.005～0.010; Copper Cu: surplus.
Described corrosion-resistant White Copper Tubes, rare earth elements RE is lanthanum element and/or Ce elements.
Described corrosion-resistant White Copper Tubes and preparation method thereof, comprises melting method and working method, and described melting method is as follows:
First, copper raw material is put in line frequency furnace, charcoal insulating covering agent covers; Then, furnace temperature is raised to 1350 ℃～1400 ℃, after furnace charge all melts, adds iron, cobalt, nickel, add successively master alloy: copper silicon, copper-manganese, zinc-copper, add master alloy for before coming out of the stove 5～15 minutes: lead bronze, phosphor-copper, arsenical copper and Cu-15wt%RE; Finally, carry out composition adjustment, copper alloy molten metal is injected into and in crystallizer, prepares copper-nickel alloy pipe.
Described working method is that dialogue copper tube billet carries out coil pipe stretching production.
Described coil pipe stretching is produced as follows:
Stretch → the annealing of strip off the skin → disk of founding → sawing → water seal extruding → tube rolling → disk stretching → disk sword mould stretching → Shu Mage associating cold drawing bench stretching → vertical bar.
Described anneal: be incubated 1～2 hour, furnace cooling at 850 ℃～900 ℃.
Advantage of the present invention and beneficial effect are:
1, corrosion-resistant White Copper Tubes of the present invention and preparation method thereof, can realize mechanical property and the conductivity of anti-seawater and erosion corrosion, anti-marine organism corrsion, excellence, and be easy to obtain, and cost is moderate.
2, because coil pipe stretching mode is mainly applicable to the splendid metal of plasticity, can utilize to the full extent the plasticity of alloy to carry out continuously, multi-pass high-speed stretch, reach energy-efficient object, but copper alloy intensity is high, preliminary work hardening rate is fast, and plasticity is low, therefore realizes copper alloy coil pipe and produces very difficult.Corrosion-resistant White Copper Tubes and preparation method thereof for ocean of the present invention, in White Copper Tubes, add alloying element and trace element: silicon 0.10～0.20, manganese 6.0～8.0, phosphorus 0.15～0.20, nickel 22.0～24.0, cobalt 2.0～4.0, zinc 2.0～4.0, plumbous 0.20～0.40, iron 3.0～4.0, rare earth elements RE 0.15～0.20% and arsenic 0.005～0.010 etc., improving alloy strength, toughness, under the over-all propertieies such as erosion resistance, particularly greatly improve alloy plasticity, its coil pipe is stretched to be achieved, the technical process of copper-alloy pipe-material is shortened, production efficiency improves, production cost reduces.
3, in prior art, the composition of copper-nickel alloy BFe30-1-1 is (wt%): Ni29.0～33.0, Fe0.4～1.0, Mn0.5～1.5, Cu surplus.In the present invention, suitably reduce Ni content, increase Fe content and Mn content, when reducing costs, can improve intensity and erosion resistance, especially increase Fe content and can increase seawater scouring corrosion resistant performance.In addition, in the present invention, add the trace alloying elements such as Si, P, Co, Zn, Pb, RE, As, can increase mobility, make interior tissue even, fine and close, internal stress is little, strengthens solution strengthening, further improves copper and alloy property.
Embodiment
The corrosion-resistant White Copper Tubes in ocean of the present invention, by weight percentage, its chemical composition and content are as follows:
Carbon C :≤0.03; Silicon Si:0.10～0.20; Manganese Mn:6.0～8.0; Sulphur S :≤0.005; Phosphorus P:0.15～0.20; Nickel: 22.0～24.0; Cobalt Co:2.0～4.0; Zinc Zn:2.0～4.0; Plumbous Pb:0.20～0.40; Iron Fe:3.0～4.0; Rare earth elements RE: 0.15～0.20; Arsenic As:0.005～0.010; Copper Cu: surplus.
Ocean of the present invention by the design philosophy of erosion resistance White Copper Tubes alloying constituent is:
Silicon Si:0.10～0.20, can improve intensity, hardness, casting fluidity, weldability.
Manganese Mn:6.0～8.0, can improve thermostability, intensity and hardness, particularly can significantly improve the solidity to corrosion in seawater, muriate and superheated vapour; Meanwhile, can also partly replace nickel, when falling low nickel content, guarantee good mechanical property; Manganese solubleness in copper can reach 20%, thus in copper alloy, add manganese 6.0～8.0% to there will not be precipitated phase, little on plasticity impact, can suitably improve intensity and deoxidation effect simultaneously.
Iron Fe:3.0～4.0, in the time of 950 ℃, the solubleness of iron in copper alloy is 4.8%; In the time of 300 ℃, the solubleness of iron in copper alloy is 0.1%; The iron that surpasses solid solubility exists with rich iron phase particle, and its fusing point is high, can be as nucleus crystal grain thinning, again can crystal grain thinning, stop recrystal grain to be grown up, thus put forward heavy alloyed mechanical property and processing performance, improve copper and alloy property.
In copper alloy, iron level is 3.0～4.0%, and manganese content is Mn6.0～8.0%, and iron, the solubleness of manganese in copper alloy are much larger than its actual content, therefore copper alloy is still single-phase α alloy, have good working plasticity.
Phosphorus P:0.15～0.20, phosphorus be the most effectively, reductor that cost is minimum, the existence of trace amounts of phosphorus, can improve the mobility of melt, improves the anti-softening degree of welding property, corrosion resisting property, raising of copper and alloy.
Nickel: 22.0～24.0 coordinate collaborative use with cobalt Co:2.0～4.0, can put forward heavy alloyed intensity, hardness, toughness and stress corrosion dehiscence resistant ability.
Zinc Zn:2.0～4.0, in alloy, solid solubility is very large, has the effect of solution strengthening, improves intensity and hardness.
Plumbous Pb:0.20～0.40, in copper alloy, contain a small amount of lead, copper and alloy conductive and heat conductivility are not made significant difference, undergoing phase transition or during recrystallize, the brilliant lead being situated between can be transferred to intracrystalline, but can increase oilness, improves wear resistance and improves machinability, especially hot workability is good, can bear large thermal distortion.
Rare earth elements RE: 0.15～0.20, effect in copper is rotten and purifies, can desulfurization and deoxidation, and can form high melting compound with low melting point impurity, eliminate deleterious effect, the plasticity that improves copper and alloy, reduces cold worked crackle, by RE Modified, is processed and is obtained the good copper alloy of plasticity; Rare earth element adds in Cu-15wt%RE master alloy mode, and rare earth elements RE is lanthanum element and/or Ce elements.
Arsenic As:0.005～0.010, consider that arsenic exists the problem that reduces its electric conductivity and heat conductivility in copper, the present invention adds micro-arsenic, can further improve solidity to corrosion, and can prevent the raw leakage accident of condenser, arsenic adds in master alloy mode, and in arsenical copper master alloy, arsenic content can reach 15～20wt%.
In the present invention, ocean by the preparation method of erosion resistance White Copper Tubes alloy is:
(1) melting
First, copper raw material is put in line frequency furnace, charcoal insulating covering agent covers; Then, furnace temperature is raised to 1350 ℃～1400 ℃, after furnace charge all melts, adds iron, cobalt, nickel, add successively master alloy: copper silicon, copper-manganese, zinc-copper, add master alloy for before coming out of the stove 5～15 minutes: lead bronze, phosphor-copper, arsenical copper and Cu-15wt%RE; Finally, carry out composition adjustment, copper alloy molten metal is injected into and in crystallizer, prepares copper-nickel alloy pipe.In the present invention, alloying element lead, phosphorus, arsenic and RE adopt the form of master alloy to add, and can effectively solve the problems such as scaling loss of lead, phosphorus, arsenic and RE.
(2) processing
The production technique of tradition White Copper Tubes generally adopts: the processing method of founding → sawing → extruding (glass isolator is lubricated) strip off the skin → vertical bar of → sawing → rolling → sawing → annealing → pickling → vertical bar stretching → sword mould stretching → scale sawing → annealing.Traditional method technical process is long, and production efficiency is low, and production cost is high, owing to there being the operations such as pickling, glass isolator lubricate, serious to equipment and environmental pollution.
Continuous expansion along with the White Copper Tubes market requirement, for improving product quality and production efficiency, reduce production costs, the present invention adopts the production technique of stretch → annealing of strip off the skin → disk of founding → sawing → water seal extrusion technique → tube rolling → disk stretching → disk sword mould stretching → Shu Mage associating cold drawing bench stretching (dish straightens) → vertical bar.Adopt water seal extrusion technique to replace the oxygen extruding under traditional atmospheric environment, avoid tube surfaces oxidation, cancel pickling process, avoid environmental pollution.Wherein, anneal: be incubated 1～2 hour, furnace cooling at 850 ℃～900 ℃.
In sum, copper alloy of the present invention has good Plastic Deformation from Metallkunde angle analysis, should be suitable for the coil pipe stretching mode of production.
Embodiment 1
By weight percentage, its chemical composition and content are as follows:
Carbon C:0.025; Silicon Si:0.15; Manganese Mn:7.0; Sulphur S:0.0045; Phosphorus P:0.18; Nickel: 23.0; Cobalt Co:3.0; Zinc Zn:3.8; Plumbous Pb:0.30; Iron Fe:3.5; Rare-earth element cerium: 0.18; Arsenic As:0.008; Copper Cu: surplus.
By the above alloying constituent, first, copper raw material to be put in line frequency furnace, charcoal insulating covering agent covers; Then, furnace temperature is raised to 1350 ℃, after furnace charge all melts, adds iron, cobalt, nickel, add successively master alloy: copper silicon, copper-manganese, zinc-copper, come out of the stove and within first 10 minutes, add master alloy: lead bronze, phosphor-copper, arsenical copper and Cu-15wt% cerium; Finally, carry out composition adjustment, copper alloy molten metal is injected into and in crystallizer, prepares copper-nickel alloy pipe.
The present embodiment adopts the production technique of stretch → annealing of strip off the skin → disk of founding → sawing → water seal extrusion technique → tube rolling → disk stretching → disk sword mould stretching → Shu Mage associating cold drawing bench stretching (dish straightens) → vertical bar.Wherein, anneal: be incubated 2 hours at 850 ℃, furnace cooling.
To using aforesaid method to prepare corrosion-resistant White Copper Tubes, test the tensile strength sigma b of this White Copper Tubes (MPa): 310; Elongation δ (%): 35.
Embodiment 2
By weight percentage, its chemical composition and content are as follows:
Carbon C:0.022; Silicon Si:0.12; Manganese Mn:6.5; Sulphur S:0.0035; Phosphorus P:0.16; Nickel: 22.5; Cobalt Co:2.5; Zinc Zn:3.5; Plumbous Pb:0.25; Iron Fe:3.8; Rare-earth element cerium: 0.16; Arsenic As:0.006; Copper Cu: surplus.
By the above alloying constituent, first, copper raw material to be put in line frequency furnace, charcoal insulating covering agent covers; Then, furnace temperature is raised to 1360 ℃, after furnace charge all melts, adds iron, cobalt, nickel, add successively master alloy: copper silicon, copper-manganese, zinc-copper, come out of the stove and within first 8 minutes, add master alloy: lead bronze, phosphor-copper, arsenical copper and Cu-15wt% cerium; Finally, carry out composition adjustment, copper alloy molten metal is injected into and in crystallizer, prepares copper-nickel alloy pipe.
The present embodiment adopts the production technique of stretch → annealing of strip off the skin → disk of founding → sawing → water seal extrusion technique → tube rolling → disk stretching → disk sword mould stretching → Shu Mage associating cold drawing bench stretching (dish straightens) → vertical bar.Wherein, anneal: be incubated 1 hour at 900 ℃, furnace cooling.
To using aforesaid method to prepare corrosion-resistant White Copper Tubes, test the tensile strength sigma b of this White Copper Tubes (MPa): 325; Elongation δ (%): 30.
Embodiment 3
By weight percentage, its chemical composition and content are as follows:
Carbon C:0.020; Silicon Si:0.10; Manganese Mn:6.0; Sulphur S:0.0028; Phosphorus P:0.15; Nickel: 22.0; Cobalt Co:4.0; Zinc Zn:4.0; Plumbous Pb:0.40; Iron Fe:3.0; Rare-earth elements of lanthanum: 0.15; Arsenic As:0.005; Copper Cu: surplus.
By the above alloying constituent, first, copper raw material to be put in line frequency furnace, charcoal insulating covering agent covers; Then, furnace temperature is raised to 1380 ℃, after furnace charge all melts, adds iron, cobalt, nickel, add successively master alloy: copper silicon, copper-manganese, zinc-copper, come out of the stove and within first 12 minutes, add master alloy: lead bronze, phosphor-copper, arsenical copper and Cu-15wt% lanthanum; Finally, carry out composition adjustment, copper alloy molten metal is injected into and in crystallizer, prepares copper-nickel alloy pipe.
The present embodiment adopts the production technique of stretch → annealing of strip off the skin → disk of founding → sawing → water seal extrusion technique → tube rolling → disk stretching → disk sword mould stretching → Shu Mage associating cold drawing bench stretching (dish straightens) → vertical bar.Wherein, anneal: be incubated 1.5 hours at 880 ℃, furnace cooling.
To using aforesaid method to prepare corrosion-resistant White Copper Tubes, test the tensile strength sigma b of this White Copper Tubes (MPa): 308; Elongation δ (%): 38.
Embodiment 4
By weight percentage, its chemical composition and content are as follows:
Carbon C:0.015; Silicon Si:0.20; Manganese Mn:8.0; Sulphur S:0.0016; Phosphorus P:0.20; Nickel: 24.0; Cobalt Co:2.0; Zinc Zn:2.0; Plumbous Pb:0.20; Iron Fe:4.0; Rare-earth elements of lanthanum: 0.20; Arsenic As:0.010; Copper Cu: surplus.
By the above alloying constituent, first, copper raw material to be put in line frequency furnace, charcoal insulating covering agent covers; Then, furnace temperature is raised to 1390 ℃, after furnace charge all melts, adds iron, cobalt, nickel, add successively master alloy: copper silicon, copper-manganese, zinc-copper, come out of the stove and within first 15 minutes, add master alloy: lead bronze, phosphor-copper, arsenical copper and Cu-15wt% lanthanum; Finally, carry out composition adjustment, copper alloy molten metal is injected into and in crystallizer, prepares copper-nickel alloy pipe.
The present embodiment adopts the production technique of stretch → annealing of strip off the skin → disk of founding → sawing → water seal extrusion technique → tube rolling → disk stretching → disk sword mould stretching → Shu Mage associating cold drawing bench stretching (dish straightens) → vertical bar.Wherein, anneal: be incubated 1.5 hours at 860 ℃, furnace cooling.
To using aforesaid method to prepare corrosion-resistant White Copper Tubes, test the tensile strength sigma b of this White Copper Tubes (MPa): 296; Elongation δ (%): 40.
Embodiment result shows, the corrosion-resistant White Copper Tubes in ocean of the present invention, in seawater, there is stronger corrosion resistance nature, and its tensile strength Ra:290MPa～330MPa, elongation 30～40%, can meet plasticity requirement completely, be suitable for the coil pipe stretching mode of production, the technical process shortening of copper-alloy pipe-material, production efficiency improve, production cost reduces.
Claims (6)
1. a corrosion-resistant White Copper Tubes, is characterized in that, by weight percentage, its chemical composition and content are as follows:
Carbon C :≤0.03; Silicon Si:0.10～0.20; Manganese Mn:6.0～8.0; Sulphur S :≤0.005; Phosphorus P:0.15～0.20; Nickel: 22.0～24.0; Cobalt Co:2.0～4.0; Zinc Zn:2.0～4.0; Plumbous Pb:0.20～0.40; Iron Fe:3.0～4.0; Rare earth elements RE: 0.15～0.20; Arsenic As:0.005～0.010; Copper Cu: surplus.
2. according to corrosion-resistant White Copper Tubes claimed in claim 1, it is characterized in that, rare earth elements RE is lanthanum element and/or Ce elements.
3. according to corrosion-resistant White Copper Tubes claimed in claim 1 and preparation method thereof, it is characterized in that, comprise melting method and working method, described melting method is as follows:
First, copper raw material is put in line frequency furnace, charcoal insulating covering agent covers; Then, furnace temperature is raised to 1350 ℃～1400 ℃, after furnace charge all melts, adds iron, cobalt, nickel, add successively master alloy: copper silicon, copper-manganese, zinc-copper, add master alloy for before coming out of the stove 5～15 minutes: lead bronze, phosphor-copper, arsenical copper and Cu-15wt%RE; Finally, carry out composition adjustment, copper alloy molten metal is injected into and in crystallizer, prepares copper-nickel alloy pipe.
4. according to the preparation method of corrosion-resistant White Copper Tubes claimed in claim 3, it is characterized in that, described working method is that dialogue copper tube billet carries out coil pipe stretching production.
5. according to the preparation method of corrosion-resistant White Copper Tubes claimed in claim 4, it is characterized in that, described coil pipe stretching is produced as follows:
Stretch → the annealing of strip off the skin → disk of founding → sawing → water seal extruding → tube rolling → disk stretching → disk sword mould stretching → Shu Mage associating cold drawing bench stretching → vertical bar.
6. according to the preparation method of corrosion-resistant White Copper Tubes claimed in claim 4, it is characterized in that anneal: at 850 ℃～900 ℃, be incubated 1～2 hour, furnace cooling.
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| CN107988524A (en) * | 2017-11-24 | 2018-05-04 | 重庆赛格尔汽车配件有限公司 | A kind of outdoor machine of air-conditioner corrosion-resistant copper pipe and production technology |
| CN108087996A (en) * | 2017-11-24 | 2018-05-29 | 重庆赛格尔汽车配件有限公司 | A kind of idle call resistance to deformation copper pipe and extrusion process |
| CN110306078A (en) * | 2019-08-05 | 2019-10-08 | 成都云鑫有色金属有限公司 | A kind of high strength and high conductivity Cutting free C97 alloy material and preparation method thereof |
| CN110899355A (en) * | 2019-11-29 | 2020-03-24 | 金川集团股份有限公司 | Production method of ultra-long high-conductivity copper tube |
| CN110961485A (en) * | 2019-11-29 | 2020-04-07 | 金川集团股份有限公司 | Seamless cupronickel large pipe and production method thereof |
| CN112296617A (en) * | 2020-10-14 | 2021-02-02 | 江苏隆达超合金股份有限公司 | Production method of high-fin cupronickel alloy high-efficiency tube |
| CN114850238A (en) * | 2022-04-27 | 2022-08-05 | 上海海亮铜业有限公司 | Preparation method of iron bronze pipe |
| CN114850238B (en) * | 2022-04-27 | 2023-12-05 | 上海海亮铜业有限公司 | Preparation method of iron bronze pipe |
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