CN103866157B - A kind of manufacture method of high strength anti-corrosion microalloying copper pipe - Google Patents
A kind of manufacture method of high strength anti-corrosion microalloying copper pipe Download PDFInfo
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Abstract
The manufacture method of a kind of high strength anti-corrosion microalloying copper pipe: phosphorus is 0.005～0.04% weight, stannum is 0.2～1.0% weight, lanthanum is 0.005～0.008% weight, cerium is 0.005～0.009% weight, nickel is 0～0.1% weight, and zinc is 0～0.1% weight, and cobalt is 0～0.05% weight, manganese is 0～0.1% weight, zirconium is 0～0.05% weight, and surplus is copper。By cathode copper, nickel, manganese, cobalt, phosphor copper, zirconium lanthanum alloy, Rare Earth Lanthanum and cerium, zinc ingot metal and tin slab are sequentially added in electric furnace Linesless charcoal and cover intensification melting, and horizontal cast becomes copper alloy ingot, and three-roll planetary rolling is combined and is drawn into copper pipe。Phosphorus and Rare Earth Lanthanum and cerium are combined into melting copper deoxidizer and reduce the content refined grain structure of oxygen in melt, improve ductility and the heat conductivity of copper；Stannum improves surface layer oxide film, improves matrix strength and resistance to corrosion；The zinc of trace, nickel, manganese, cobalt and zirconium improve Copper substrate intensity and thermostability, and combined effect is higher than oxygen-free copper pipe or single phosphorous deoxidize copper tube performance and result of use。
Description
Technical field
The present invention relates to a kind of copper alloy tube material, particularly a kind of micro-alloying copper tube material and manufacture method thereof。
Background technology
Copper alloy has the characteristics such as good conductivity of heat, corrosion resistance, is widely used in heat exchanger, such as the field such as air-conditioning, water heater。At present, heat exchanger material mostly is oxygen-free copper pipe or phosphorous deoxidize copper tube (TP2), but when special environment is on active service, as high pressure, corrosive atmosphere, general T P2 or oxygen-free copper pipe cannot meet service demand。If TP2 copper pipe is in welding process, owing to weld temperature sharply raises, causing that recrystallization, abnormal grain growth occur weld tissue, cause that the welding heat affected zone strength of materials is on the low side, when critical pressure is on active service, material easily occurs leakage to cause product failure。Simultaneously as TP2 or its surface of oxygen-free copper pipe are CuO, it is amphoteric oxide, can with acid or alkali reaction, and in daily life, the many deviation neutrality of water quality in environment, in such circumstances, easily there is corrosion thus causing perforation leakage in TP2 or oxygen-free copper pipe surface layer oxide film。For solving the drawbacks described above of pure copper tube, each research institution has done big quantity research, have developed some high-strength or anti-corrosion copper pipes, and many employing unrelated diversification improve, as added the elements such as Al, Ni, Mn。But all cannot realize having the overall characteristics such as high-strength, anti-corrosion, efficient concurrently。Such as a kind of copper alloy tube for heat exchanger that patent 201110174411.9 proposes, its composition: Sn0.5-1.0wt%, P0.05-0.1wt%, Al2.2-8.5wt%, Mn0.5-1.8wt%, Fe0.15-0.35wt%, surplus is copper and inevitable impurity composition, although this alloy has good intensity and thermostability, but plasticity is relatively low, causes that processing cost is too high。Meanwhile, this kind of material thermal conductivity is on the low side, has a strong impact on the heat exchange efficiency of material, it is impossible to realize ideal effect cheap, efficient。
Along with developing rapidly of supercritical heat exchanger, anti-corrosion, the intensity of material have been had higher requirement by it, and market in urgent need is a has tubing well anti-corrosion, high intensity, high thermal efficiency performance。
Summary of the invention
The technical problem to be solved in the present invention is for current phosphorous deoxidize copper tube/oxygen-free copper pipe defect existing for heat exchanger, designed by composition and postchannel process optimization is to reach high intensity, corrosion-resistant and high thermal efficiency, adapt to the needs of supercritical heat exchanger development。
A kind of manufacture method of high strength anti-corrosion microalloying copper pipe, its feature comprises the following steps:
A, weigh by micro-alloying copper tube material compositing formula: phosphorus is 0.005～0.04% weight, stannum is 0.2～1.0% weight, lanthanum is 0.005～0.008% weight, cerium is 0.005～0.009% weight, nickel is 0～0.1% weight, zinc is 0～0.1% weight, and cobalt is 0～0.05% weight, and manganese is 0～0.1% weight, zirconium is 0～0.05% weight, and surplus is copper；
B, then it is sequentially added in line frequency furnace intensification melting by cathode copper, electrolytic nickel, electrolytic manganese, electrolytic cobalt, phosphor copper, zirconium copper alloy, Rare Earth Lanthanum and cerium, zinc ingot metal and tin slab；
C, employing Linesless charcoal cover melting, and smelting temperature 1150～1250 DEG C, after whole metal moltens, being incubated 5～50 minutes, then carry out horizontal cast, casting speed is that 150～360mm/ divides, outlet temperature is 40～80 DEG C, cast temperature 1100 ~ 1200 DEG C, pulls into Φ 92 × 25mm copper alloy ingot standby；
D, by above-mentioned copper alloy ingot adopt three-roll planetary rolling combine draw dial intermediate annealing dish draw finished products, scale, inspection finished product copper pipe, the main frame speed of three-roller planetary rolling mill is 950～1350 revs/min, subsidiary engine speed is 350～850 revs/min, 6～10 degree of dog inclination angle, mill speed is that 0.5～1.0mm/ divides。
Phosphorus is deoxidizer, it is possible to decrease oxygen content in melt, improves melt cleanliness。Meanwhile, phosphorus suitable in melt can improve its mobility, improves slab quality。Rare Earth Lanthanum and cerium have very strong reproducibility, can react formation high melting compound with the impurity such as the oxygen in melt, produce to purify melt effect, simultaneously also can as heterogeneous forming core heart crystal grain thinning。
Stannum is by solution strengthening and improves superficial oxidation film properties, to improve the strength of materials and resistance to corrosion, Sn deposits in the base in the way of solid solution, not only can produce the effect of solution strengthening, form the SnO film of densification at product surface simultaneously, this SnO film relatively CuO has better acid corrosion-resistant ability, and Sn is also present in CuO film with the form of displacement, improves the corrosion resistance of CuO film further。
Zinc, nickel and manganese are all transition elements, all being present in Copper substrate with the form of solid solution, improve the intensity of Copper substrate, Zn, Ni can form the oxide-film of densification and improve corrosion resistance, Mn can react formation passivating film with chlorinated organics in copper melts, it is suppressed that surface pass, ant cave property are corroded。
Cobalt and zirconium all do not dissolve in copper, and Dispersed precipitate, in Copper substrate, produces the effect of precipitation strength, plays raising Copper substrate intensity and thermostability, and Zr can also react formation passivating film with chlorine-containing organic compounds in Copper substrate and suppress the corrosion of pass, ant cave property。
The present invention, by the deoxidizer being combined into melting copper of phosphorus with Rare Earth Lanthanum and/or cerium, reduces the content of oxygen in melt, refined grain structure further, improves recrystallization temperature and stops weld structure abnormal grain growth, improves ductility and the heat conductivity of copper further。By the solution strengthening of stannum with improve surface layer oxide film, improve matrix strength and resistance to corrosion。By adding the zinc of trace, nickel, manganese be solid-solution in Copper substrate to improve the intensity of Copper substrate, improving Copper substrate intensity and thermostability in Copper substrate by adding cobalt or zirconium Dispersed precipitate, combinations of the above effect is higher than existing oxygen-free copper pipe or single phosphorous deoxidize copper tube performance and result of use。
Detailed description of the invention
Embodiment 1
Composition content: phosphorus is 0.005wt% weight, and stannum is 0.3wt% weight, and lanthanum is 0.008wt% weight, and nickel is 0.1wt% weight, and zinc is 0.05wt% weight, and manganese is 0.05wt% weight, and surplus is copper。
The manufacture method of microalloying copper pipe comprises the following steps:
A, weigh by micro-alloying copper tube material compositing formula, be then sequentially added in line frequency furnace intensification melting by cathode copper, electrolytic nickel, electrolytic manganese, phosphor copper, Rare Earth Lanthanum, zinc ingot metal and tin slab；
B, melting adopt Linesless charcoal to cover melting, smelting temperature 1150～1250 DEG C, after whole metal moltens, it is incubated 5～50 minutes, then carrying out horizontal cast, casting speed is that 150～360mm/ divides, cast temperature 1100 ~ 1200 DEG C, outlet temperature is 40～80 DEG C, pulls into Φ 92 × 25mm copper alloy ingot standby；
C, by above-mentioned copper alloy ingot adopt three-roller planetary rolling mill, combine draw dial intermediate annealing dish draw finished products, scale, inspection copper pipe finished product。
Described phosphor copper, prepares by P:Cu=14.2wt%:85.8wt% mass ratio, it is possible to adopt commercially available prod。
Described surplus copper is cathode copper。
The main frame speed that described three-roller planetary rolls is 950～1350 revs/min, and subsidiary engine speed is 350～850 revs/min, 6～10 degree of dog inclination angle, and mill speed is that 0.5～1.0mm/ divides。
Described intermediate anneal temperature is 500～600 DEG C, temperature retention time 1～5 hour。
Described finished products temperature is divided into half-hard state annealing and the annealing of soft state according to product mechanical performance index, corresponding cold working rate, tube blank size, wherein half-hard state is annealed into 230～360 DEG C, being incubated 1～5 hour, soft state annealing temperature is 480～560 DEG C, is incubated 1～5 hour。
Embodiment 2
Composition content: phosphorus is 0.018wt% weight, and stannum is 0.5wt% weight, and cerium is 0.009wt% weight, and cobalt is 0.2wt% weight, and manganese is 0.05wt% weight, and surplus is copper。
The manufacture method of microalloying copper pipe comprises the following steps:
A, weigh by micro-alloying copper tube material compositing formula, be then sequentially added in line frequency furnace intensification melting by cathode copper, electrolytic manganese, electrolytic cobalt, phosphor copper, cerium, zinc ingot metal and tin slab；
B, melting adopt Linesless charcoal to cover melting, smelting temperature 1150～1250 DEG C, after whole metal moltens, it is incubated 5～50 minutes, then carrying out horizontal cast, casting speed is that 150～360mm/ divides, cast temperature 1100 ~ 1200 DEG C, outlet temperature is 40～80 DEG C, pulls into Φ 92 × 25 copper alloy ingot standby；
C, by above-mentioned copper alloy ingot adopt three-roller planetary rolling mill, combine draw dial intermediate annealing dish draw finished products, scale, inspection copper pipe finished product。
Described phosphor copper, prepares by P:Cu=14.2wt%:85.8wt% mass ratio, it is possible to adopt commercially available prod。
Described surplus copper is cathode copper。
The main frame speed that described three-roller planetary rolls is 950～1350 revs/min, and subsidiary engine speed is 350～850 revs/min, 6～10 degree of dog inclination angle, and mill speed is that 0.5～1.0mm/ divides。
Described intermediate anneal temperature is 500～600 DEG C, temperature retention time 1～5 hour。
Described finished products temperature is divided into half-hard state annealing and the annealing of soft state according to product mechanical performance index, corresponding cold working rate, tube blank size, wherein half-hard state is annealed into 230～360 DEG C, being incubated 1～5 hour, soft state annealing temperature is 480～560 DEG C, is incubated 1～5 hour。
Embodiment 3
Composition content: phosphorus is 0.025wt% weight, and stannum is 0.8wt% weight, and lanthanum is 0.005wt% weight, and cerium is 0.005wt% weight, and zirconium is 0.01wt% weight, and surplus is copper。
The manufacture method of microalloying copper pipe comprises the following steps:
A, weigh by micro-alloying copper tube material compositing formula, be then sequentially added in electromagnetic agitation line frequency furnace intensification melting by cathode copper, phosphor copper, zirconium copper alloy, Rare Earth Lanthanum and cerium, zinc ingot metal and tin slab；
B, melting adopt Linesless charcoal to cover melting, smelting temperature 1150～1250 DEG C, after whole metal moltens, it is incubated 5～50 minutes, then carrying out horizontal cast, casting speed is that 150～360mm/ divides, cast temperature 1100 ~ 1200 DEG C, outlet temperature is 40～80 DEG C, pulls into Φ 92 × 25 copper alloy ingot standby；
C, by above-mentioned copper alloy ingot adopt three-roller planetary rolling mill, combine draw dial intermediate annealing dish draw finished products, scale, inspection copper pipe finished product。
Described phosphor copper, prepares by P:Cu=14.2%:85.8% mass ratio, it is possible to adopt commercially available prod。
In described zirconium copper alloy, zirconium: copper=75～90%:25～10% mass, adopt fine copper and pure zirconium to prepare in vacuum melting mode。
Described surplus copper is cathode copper。
The main frame speed that described three-roller planetary rolls is 950～1350 revs/min, and subsidiary engine speed is 350～850 revs/min, 6～10 degree of dog inclination angle, and mill speed is that 0.5～1.0mm/ divides。
Described intermediate anneal temperature is 500～600 DEG C, temperature retention time 1～5 hour。
Described finished products temperature is divided into half-hard state annealing and the annealing of soft state according to product mechanical performance index, corresponding cold working rate, tube blank size, wherein half-hard state is annealed into 230～360 DEG C, being incubated 1～5 hour, soft state annealing temperature is 480～560 DEG C, is incubated 1～5 hour。
Testing result compares with TP2 pipe, as shown in the table:
The tensile strength of the embodiment of the present invention 1～3, yield strength, recrystallization temperature and decay resistance are all significantly improved than the TP2 pipe of comparison, embody good combination property
Yield strength is to judge the key index whether material meets service condition in engineer applied, when Service Environment exceedes the yield strength value of material, material generation plastic deformation, cause local plastic deformation, thus causing inefficacy, local macroscopic cracking occurring, causing revealing。The yield strength of the present embodiment is far above TP2, and its corrosion resisting property is greatly improved。
Grain growth speed and the high temperature creep rate of material are had highly important impact by recrystallization temperature, when material welds, can inhibiting grain growth speed and high temperature creep rate, improve material elevated temperature strength。
Meanwhile, by table it can be seen that under sour environment, the embodiment of the present invention has better corrosive nature。In sum, material of the present invention has the combination property of high strength anti-corrosion。
Claims (5)
1. a manufacture method for high strength anti-corrosion microalloying copper pipe, its feature comprises the following steps:
A, weigh by micro-alloying copper tube material compositing formula: phosphorus is 0.005～0.04% weight, stannum is 0.2～1.0% weight, lanthanum is 0.005～0.008% weight, cerium is 0.005～0.009% weight, nickel is 0～0.1% weight, zinc is 0～0.1% weight, and cobalt is 0～0.05% weight, and manganese is 0～0.1% weight, zirconium is 0～0.05% weight, and surplus is copper；
B, then it is sequentially added in line frequency furnace intensification melting by cathode copper, electrolytic nickel, electrolytic manganese, electrolytic cobalt, phosphor copper, zirconium copper alloy, Rare Earth Lanthanum and cerium, zinc ingot metal and tin slab；
C, employing Linesless charcoal cover melting, and smelting temperature 1150～1250 DEG C, after whole metal moltens, being incubated 5～50 minutes, then carry out horizontal cast, casting speed is that 150～360mm/ divides, outlet temperature is 40～80 DEG C, cast temperature 1100 ~ 1200 DEG C, pulls into Φ 92 × 25mm copper alloy ingot standby；
D, by above-mentioned copper alloy ingot adopt three-roll planetary rolling combine draw dial intermediate annealing dish draw finished products, scale, inspection finished product copper pipe, the main frame speed of three-roller planetary rolling mill is 950～1350 revs/min, subsidiary engine speed is 350～850 revs/min, 6～10 degree of dog inclination angle, mill speed is that 0.5～1.0mm/ divides。
2. the manufacture method of a kind of high strength anti-corrosion microalloying copper pipe according to claim 1, it is characterised in that described phosphor copper, prepares by P:Cu=14.2%:85.8% mass ratio, it is possible to adopt commercially available prod。
3. the manufacture method of a kind of high strength anti-corrosion microalloying copper pipe according to claim 1, it is characterised in that in described zirconium copper alloy, zirconium: copper=75～90%:25～10% mass, adopt fine copper and pure zirconium to prepare with vacuum smelting method。
4. the manufacture method of a kind of high strength anti-corrosion microalloying copper pipe according to claim 1, it is characterised in that described intermediate anneal temperature is 500～600 DEG C, temperature retention time 1～5 hour。
5. the manufacture method of a kind of high strength anti-corrosion microalloying copper pipe according to claim 1, it is characterized in that described finished products temperature is divided into half-hard state annealing and the annealing of soft state according to product mechanical performance index, corresponding cold working rate, tube blank size, wherein half-hard state is annealed into 230～360 DEG C, it is incubated 1～5 hour, soft state annealing temperature is 480～560 DEG C, is incubated 1～5 hour。
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| JPH09296238A (en) * | 1996-04-28 | 1997-11-18 | Nikko Kinzoku Kk | Metallic substrate material for semiconductor packaging |
| JP4538813B2 (en) * | 2006-05-29 | 2010-09-08 | Ｄｏｗａホールディングス株式会社 | Connector and charging socket using copper-based alloy material |
| JP4629080B2 (en) * | 2007-11-05 | 2011-02-09 | 株式会社コベルコ マテリアル銅管 | Copper alloy tube for heat exchanger |
| CN101619404B (en) * | 2009-08-11 | 2011-05-11 | 路达(厦门)工业有限公司 | Easy-cutting lead-free brass alloy for forging and preparation method thereof |
| CN102260840B (en) * | 2011-07-26 | 2012-10-17 | 北京科技大学 | Short-flow efficient production method for brass tubes |
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