CN103740977B - A kind of corrosion-resistant White Copper Tubes and preparation method thereof - Google Patents
A kind of corrosion-resistant White Copper Tubes and preparation method thereof Download PDFInfo
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- 229910000570 Cupronickel Inorganic materials 0.000 title claims abstract description 52
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- 230000007797 corrosion Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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- 229910045601 alloy Inorganic materials 0.000 claims abstract description 43
- 239000000956 alloy Substances 0.000 claims abstract description 43
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 27
- 229910052742 iron Inorganic materials 0.000 claims abstract description 26
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- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
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- 239000011701 zinc Substances 0.000 claims abstract description 20
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 17
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 16
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005864 Sulphur Substances 0.000 claims abstract description 8
- 238000010622 cold drawing Methods 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 8
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- 238000000034 method Methods 0.000 claims description 39
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910000563 Arsenical copper Inorganic materials 0.000 claims description 8
- 229910000906 Bronze Inorganic materials 0.000 claims description 7
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 claims description 7
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- 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
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- 229910052684 Cerium Inorganic materials 0.000 description 5
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
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Abstract
The present invention relates to corronel field, particularly relate to a kind of ocean corrosion-resistant White Copper Tubes and preparation method thereof.By weight percentage, its chemical composition and content 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.After adopting induction melting to obtain copper-nickel alloy pipe, dialogue copper tube billet carries out coil pipe and stretches and produce: founding → sawing → water seal extruding → tube rolling → disk stretchings → disk sword mould strips off the skin → and the stretching of disk stretchings → Shu Mage associating cold drawing bench stretching → vertical bar → anneal.It is limited that the present invention solves traditional cupronickel material lifetime, is difficult to adapt to the problems such as the coil pipe stretching mode of production because plasticity is low, its coil pipe stretched and is achieved.
Description
Technical field
The present invention relates to corronel field, particularly relate to a kind of ocean corrosion-resistant White Copper Tubes and preparation method thereof.
Background technology
Along with the development of marine cause and the process of reinforcement naval construction, the demand of Copper and its alloy prolong is in quick growth.Within 2011, domestic only electric power, shipbuilding, the demand of sea water desaltination three industries to high precision copper and cupronickel tubing have reached 60,000 tons, continuation also increases the demand of high precision Copper and its alloy tubing by domestic market, and expecting domestic needs amount in 2015 will more than 100,000 ton.
Develop the HSn70-1B adding boron the nineties in last century, add Mn, Ni and trace rare-earth element cerium HSn70-1AB, intensity and solidity to corrosion improve further, but brazed copper tube Dezincification corrosion and stress corrosion are all less than cupronickel, limit 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.BFe30-1-1 iron white copper is used for the condenser that works under high temperature, high pressure, high-speed condition in shipbuilding and thermostatted.Fe and Mn in BFe10-1-1 alloy adds the anti-etch performance considerably improving 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 widely used on the heat exchanger that power station, desalination, petrochemical factory etc. use seawater.
Cupronickel material is the common used material manufacturing sea water piping system, but cupronickel material lifetime is limited, needs periodic replacement.Compared with the prolong of other materials, titanium is not corroded in the sulfide of all concentration, in the polluted seawater of sulfur compound, have good solidity to corrosion.Meanwhile, titanium in water speed up to 20m/s and sand content up under the condition of 40g/L, all there is excellent corrosion resistance nature.But titanium is produced and processing difficulties, and output is very low, expensive, price is not preponderated compared with copper nickel pipe.
The production of existing copper alloy condensation tubes, vertical half-continuous process is adopted to produce solid ingot casting, length saw is cut to the long short ingot of 400 ~ 600mm, is heated to by short ingot 800 ~ 1000 DEG C (different depending on alloy species difference), obtains hollow bloom in the enterprising eleven punch 11 extruding of double-acting extruding machine.Pilger rolling is carried out after scale sawing, aligning, pickling are carried out to pipe.The short tube being cut into 4 ~ 6m is needed to rolling pipe, with after annealing, pickling, head processed, stretching; So 3 ~ 5 times repeatedly, technical process is long, and production passage is many; Extruding is heated, is repeatedly annealed, and 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 one and there is low cost, reduce metal loss, there is the environmentally friendly novel process of good corrosion resistance simultaneously.
Traditional technology generally adopts: founding → sawing → extruding (glass isolator lubrication) → sawing → rolling → sawing → annealing → pickling → vertical bar stretching → sword mould strips off the skin → and the processing method of vertical bar 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 operation such as pickling, glass isolator lubrication, to equipment and environmental pollution serious.
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 one and there is low cost, 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 ocean corrosion-resistant White Copper Tubes and preparation method thereof, solve traditional cupronickel material lifetime limited, be difficult to because plasticity is low adapt to the problems such as the coil pipe stretching mode of production.
Technical scheme of the present invention is:
A kind of corrosion-resistant White Copper Tubes, by weight percentage, its chemical composition and content 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, put into by copper raw material in line frequency furnace, charcoal insulating covering agent covers; Then, furnace temperature is raised to 1350 DEG C ~ 1400 DEG C, after furnace charge all melts, adds iron, cobalt, nickel, add master alloy successively: copper silicon, copper-manganese, zinc-copper, within before coming out of the stove 5 ~ 15 minutes, add master alloy: lead bronze, phosphor-copper, arsenical copper and Cu-15wt%RE; Finally, carry out composition adjustment, copper alloy molten metal is injected in crystallizer and 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:
Founding → sawing → water seal extruding → tube rolling → disk stretching → disk sword mould strips off the skin → and disk stretching → Shu Mage combines cold drawing bench stretchings → vertical bar and stretches → anneal.
Described anneal: be incubated 1 ~ 2 hour at 850 DEG C ~ 900 DEG C, furnace cooling.
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 resistant to sea water and erosion corrosion, anti-marine organism corrsion, excellent mechanical property and conductivity, and be easy to obtain, moderate cost.
2, because coil pipe stretching mode is mainly applicable to the splendid metal of plasticity, can utilize that the plasticity of alloy is carried out continuously, multi-pass high-speed stretch to the full extent, 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.Ocean of the present invention corrosion-resistant White Copper Tubes and preparation method thereof, alloying element and trace element is added: silicon 0.10 ~ 0.20 in White Copper Tubes, 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 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.Suitably reduce Ni content in the present invention, increase Fe content and Mn content, while reducing costs, intensity and erosion resistance can be improved, 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, improves copper and alloy property further.
Embodiment
The corrosion-resistant White Copper Tubes in ocean of the present invention, by weight percentage, its chemical composition and content 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.
The design philosophy of ocean of the present invention 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, partly can also replace nickel, while falling low nickel content, ensure good mechanical property; Manganese solubleness in copper can reach 20%, therefore in copper alloy, adds manganese 6.0 ~ 8.0% there will not be precipitated phase, little on plasticity impact, can suitably improve intensity and deoxidation effect simultaneously.
Iron Fe:3.0 ~ 4.0,950 DEG C time, the solubleness of iron in copper alloy is 4.8%; 300 DEG C time, the solubleness of iron in copper alloy is 0.1%; The iron exceeding solid solubility exists with Fe-riched phase particle, and its fusing point is high, can 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.
Due in copper alloy, iron level is 3.0 ~ 4.0%, and Fe content is Mn6.0 ~ 8.0%, and iron, the manganese solubleness in copper alloy is much larger than its actual content, therefore copper alloy is still single-phase α alloy, has good working plasticity.
Phosphorus P:0.15 ~ 0.20, phosphorus is the reductor the most effective, cost is minimum, and the existence of trace amounts of phosphorus, can improve the mobility of melt, improves the welding property of copper and alloy, corrosion resisting property, the anti-softening degree of raising.
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, solid solubility is very large in the alloy, has the effect of solution strengthening, improves intensity and hardness.
Plumbous Pb:0.20 ~ 0.40, containing a small amount of lead in copper alloy, copper and alloy conductive and heat conductivility are not made significant difference, undergo phase transition or recrystallize time, the brilliant lead be situated between can transfer to intracrystalline, but can increase oilness, improves wear resistance and improves machinability, especially hot workability is excellent, can bear large thermal distortion.
Rare earth elements RE: 0.15 ~ 0.20, effect in copper is rotten and purification, can desulfurization and deoxidation, and high melting compound can be formed with low-melting impurities, eliminate deleterious effect, improve the plasticity of copper and alloy, reduce cold worked crackle, obtain the good copper alloy of plasticity by rare earth Dy ions; 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 reducing its electric conductivity and heat conductivility in copper, the present invention adds the arsenic of trace, solidity to corrosion can be improved further, and the raw leakage accident of condenser can be prevented, arsenic adds in master alloy mode, and in arsenical copper master alloy, arsenic content can reach 15 ~ 20wt%.
In the present invention, the preparation method of ocean erosion resistance White Copper Tubes alloy is:
(1) melting
First, put into by copper raw material in line frequency furnace, charcoal insulating covering agent covers; Then, furnace temperature is raised to 1350 DEG C ~ 1400 DEG C, after furnace charge all melts, adds iron, cobalt, nickel, add master alloy successively: copper silicon, copper-manganese, zinc-copper, within before coming out of the stove 5 ~ 15 minutes, add master alloy: lead bronze, phosphor-copper, arsenical copper and Cu-15wt%RE; Finally, carry out composition adjustment, copper alloy molten metal is injected in crystallizer and 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 the scaling loss of lead, phosphorus, arsenic and RE.
(2) process
The production technique of tradition White Copper Tubes generally adopts: founding → sawing → extruding (glass isolator lubrication) → sawing → rolling → sawing → annealing → pickling → vertical bar stretching → sword mould strips off the skin → and the processing method of vertical bar 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 operation such as pickling, glass isolator lubrication, to equipment and environmental pollution serious.
Along with the continuous expansion of the White Copper Tubes market requirement, for improving product quality and production efficiency, reduce production cost, the present invention adopt founding → sawing → water seal extrusion technique → tube rolling → disk stretchings → disk sword mould strip off the skin → disk stretchings → Shu Mage combine cold drawing bench stretch (dish straightens) → vertical bar stretching → anneal production technique.Oxygen extruding under adopting water seal extrusion technique to replace traditional atmospheric environment, avoids tube surfaces to be oxidized, cancels pickling process, avoid environmental pollution.Wherein, anneal: be incubated 1 ~ 2 hour at 850 DEG C ~ 900 DEG C, furnace cooling.
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 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, put into by copper raw material in line frequency furnace, charcoal insulating covering agent covers; Then, furnace temperature is raised to 1350 DEG C, after furnace charge all melts, adds iron, cobalt, nickel, add master alloy successively: copper silicon, copper-manganese, zinc-copper, come out of the stove and add master alloy in first 10 minutes: lead bronze, phosphor-copper, arsenical copper and Cu-15wt% cerium; Finally, carry out composition adjustment, copper alloy molten metal is injected in crystallizer and prepares copper-nickel alloy pipe.
The present embodiment adopt founding → sawing → water seal extrusion technique → tube rolling → disk stretchings → disk sword mould strip off the skin → disk stretchings → Shu Mage combine cold drawing bench stretch (dish straightens) → vertical bar stretching → anneal production technique.Wherein, anneal: be incubated 2 hours at 850 DEG C, furnace cooling.
Prepare corrosion-resistant White Copper Tubes to use aforesaid method to test, tensile strength sigma b (MPa): 310 of this White Copper Tubes; Elongation δ (%): 35.
Embodiment 2
By weight percentage, its chemical composition and content 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, put into by copper raw material in line frequency furnace, charcoal insulating covering agent covers; Then, furnace temperature is raised to 1360 DEG C, after furnace charge all melts, adds iron, cobalt, nickel, add master alloy successively: copper silicon, copper-manganese, zinc-copper, come out of the stove and add master alloy in first 8 minutes: lead bronze, phosphor-copper, arsenical copper and Cu-15wt% cerium; Finally, carry out composition adjustment, copper alloy molten metal is injected in crystallizer and prepares copper-nickel alloy pipe.
The present embodiment adopt founding → sawing → water seal extrusion technique → tube rolling → disk stretchings → disk sword mould strip off the skin → disk stretchings → Shu Mage combine cold drawing bench stretch (dish straightens) → vertical bar stretching → anneal production technique.Wherein, anneal: be incubated 1 hour at 900 DEG C, furnace cooling.
Prepare corrosion-resistant White Copper Tubes to use aforesaid method to test, tensile strength sigma b (MPa): 325 of this White Copper Tubes; Elongation δ (%): 30.
Embodiment 3
By weight percentage, its chemical composition and content 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, put into by copper raw material in line frequency furnace, charcoal insulating covering agent covers; Then, furnace temperature is raised to 1380 DEG C, after furnace charge all melts, adds iron, cobalt, nickel, add master alloy successively: copper silicon, copper-manganese, zinc-copper, come out of the stove and add master alloy in first 12 minutes: lead bronze, phosphor-copper, arsenical copper and Cu-15wt% lanthanum; Finally, carry out composition adjustment, copper alloy molten metal is injected in crystallizer and prepares copper-nickel alloy pipe.
The present embodiment adopt founding → sawing → water seal extrusion technique → tube rolling → disk stretchings → disk sword mould strip off the skin → disk stretchings → Shu Mage combine cold drawing bench stretch (dish straightens) → vertical bar stretching → anneal production technique.Wherein, anneal: be incubated 1.5 hours at 880 DEG C, furnace cooling.
Prepare corrosion-resistant White Copper Tubes to use aforesaid method to test, tensile strength sigma b (MPa): 308 of this White Copper Tubes; Elongation δ (%): 38.
Embodiment 4
By weight percentage, its chemical composition and content 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, put into by copper raw material in line frequency furnace, charcoal insulating covering agent covers; Then, furnace temperature is raised to 1390 DEG C, after furnace charge all melts, adds iron, cobalt, nickel, add master alloy successively: copper silicon, copper-manganese, zinc-copper, come out of the stove and add master alloy in first 15 minutes: lead bronze, phosphor-copper, arsenical copper and Cu-15wt% lanthanum; Finally, carry out composition adjustment, copper alloy molten metal is injected in crystallizer and prepares copper-nickel alloy pipe.
The present embodiment adopt founding → sawing → water seal extrusion technique → tube rolling → disk stretchings → disk sword mould strip off the skin → disk stretchings → Shu Mage combine cold drawing bench stretch (dish straightens) → vertical bar stretching → anneal production technique.Wherein, anneal: be incubated 1.5 hours at 860 DEG C, furnace cooling.
Prepare corrosion-resistant White Copper Tubes to use aforesaid method to test, tensile strength sigma b (MPa): 296 of this White Copper Tubes; Elongation δ (%): 40.
Embodiment result shows, the corrosion-resistant White Copper Tubes in ocean of the present invention, there is stronger corrosion resistance nature in the seawater, and its tensile strength Ra:290MPa ~ 330MPa, elongation 30 ~ 40%, can meet plasticity requirements completely, be suitable for the coil pipe stretching mode of production, the technical process shortening of copper-alloy pipe-material, production efficiency raising, production cost reduce.
Claims (6)
1. the corrosion-resistant White Copper Tubes in ocean, is characterized in that, by weight percentage, its chemical composition and content 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 ~ 0.008; Copper Cu: surplus.
2. according to the corrosion-resistant White Copper Tubes in ocean according to claim 1, it is characterized in that, rare earth elements RE is lanthanum element and/or Ce elements.
3. according to the preparation method of ocean according to claim 1 by corrosion-resistant White Copper Tubes, it is characterized in that, comprise melting method and working method, described melting method is as follows:
First, put into by copper raw material in line frequency furnace, charcoal insulating covering agent covers; Then, furnace temperature is raised to 1350 DEG C ~ 1400 DEG C, after furnace charge all melts, adds iron, cobalt, nickel, add master alloy successively: copper silicon, copper-manganese, zinc-copper, within before coming out of the stove 5 ~ 15 minutes, add master alloy: lead bronze, phosphor-copper, arsenical copper and Cu-15wt%RE; Finally, carry out composition adjustment, copper alloy molten metal is injected in crystallizer and prepares copper-nickel alloy pipe.
4. according to the preparation method of ocean according to claim 3 by corrosion-resistant White Copper Tubes, 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 ocean according to claim 4 by corrosion-resistant White Copper Tubes, it is characterized in that, described coil pipe stretching is produced as follows:
Founding → sawing → water seal extruding → tube rolling → disk stretching → disk sword mould strips off the skin → and disk stretching → Shu Mage combines cold drawing bench stretchings → vertical bar and stretches → anneal.
6. according to the preparation method of ocean according to claim 5 by corrosion-resistant White Copper Tubes, it is characterized in that, anneal: at 850 DEG C ~ 900 DEG C, be incubated 1 ~ 2 hour, furnace cooling.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63230837A (en) * | 1987-03-18 | 1988-09-27 | Nippon Mining Co Ltd | Copper alloy for fuse |
| JP2006328542A (en) * | 2006-05-29 | 2006-12-07 | Dowa Holdings Co Ltd | Copper-based alloy material and manufacturing method therefor |
| CN101100714A (en) * | 2007-07-20 | 2008-01-09 | 中铝洛阳铜业有限公司 | Corrosion resistant brass alloy material for plate heat exchanger and processing technique thereof |
| CN101555561A (en) * | 2009-05-18 | 2009-10-14 | 大连理工大学 | Copper-nickel based multielement high corrosion resisting alloy |
| CN101698207A (en) * | 2009-10-20 | 2010-04-28 | 无锡隆达金属材料有限公司 | Method for producing copper alloy coil pipe |
| EP2573198A1 (en) * | 2011-09-22 | 2013-03-27 | KME Germany GmbH & Co. KG | Copper alloy for a silver coloured product having an antimicrobial surface |
| CN103403201A (en) * | 2011-02-01 | 2013-11-20 | 株式会社丰山 | Copper alloy material for seawater and method for preparing same |
-
2014
- 2014-01-16 CN CN201410018705.6A patent/CN103740977B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63230837A (en) * | 1987-03-18 | 1988-09-27 | Nippon Mining Co Ltd | Copper alloy for fuse |
| JP2006328542A (en) * | 2006-05-29 | 2006-12-07 | Dowa Holdings Co Ltd | Copper-based alloy material and manufacturing method therefor |
| CN101100714A (en) * | 2007-07-20 | 2008-01-09 | 中铝洛阳铜业有限公司 | Corrosion resistant brass alloy material for plate heat exchanger and processing technique thereof |
| CN101555561A (en) * | 2009-05-18 | 2009-10-14 | 大连理工大学 | Copper-nickel based multielement high corrosion resisting alloy |
| CN101698207A (en) * | 2009-10-20 | 2010-04-28 | 无锡隆达金属材料有限公司 | Method for producing copper alloy coil pipe |
| CN103403201A (en) * | 2011-02-01 | 2013-11-20 | 株式会社丰山 | Copper alloy material for seawater and method for preparing same |
| EP2573198A1 (en) * | 2011-09-22 | 2013-03-27 | KME Germany GmbH & Co. KG | Copper alloy for a silver coloured product having an antimicrobial surface |
Non-Patent Citations (1)
| Title |
|---|
| 超长白铜冷凝管生产新工艺研究;刘关强等;《第十二届中国有色金属学会材料科学与合金加工学术研讨会文集(2007)》;20071231;第22页右栏第2段 * |
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