CN113774250A - High-strength high-heat-conductivity high-corrosion-resistance copper alloy and preparation method thereof - Google Patents
High-strength high-heat-conductivity high-corrosion-resistance copper alloy and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- 238000010622 cold drawing Methods 0.000 claims abstract description 56
- 239000010949 copper Substances 0.000 claims abstract description 52
- 238000005096 rolling process Methods 0.000 claims abstract description 45
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 44
- 239000000956 alloy Substances 0.000 claims abstract description 44
- 238000009749 continuous casting Methods 0.000 claims abstract description 34
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 claims abstract description 30
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 30
- 229910052718 tin Inorganic materials 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000005260 corrosion Methods 0.000 claims abstract description 19
- 230000007797 corrosion Effects 0.000 claims abstract description 19
- 238000001953 recrystallisation Methods 0.000 claims description 44
- 238000002844 melting Methods 0.000 claims description 29
- 230000008018 melting Effects 0.000 claims description 29
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- 239000012535 impurity Substances 0.000 claims description 22
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 238000005097 cold rolling Methods 0.000 claims description 11
- 239000000498 cooling water Substances 0.000 claims description 11
- 238000003801 milling Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 8
- 238000000265 homogenisation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 238000005275 alloying Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 238000005266 casting Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
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- 238000010586 diagram Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
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- 229910052905 tridymite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0236—Cold rolling
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0273—Final recrystallisation annealing
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- C22C9/04—Alloys based on copper with zinc as the next major constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
Abstract
The invention discloses a high-strength high-heat-conductivity high-corrosion-resistance copper alloy and a preparation method thereof, and the formula comprises the following components: zn, Sn, Si, Ge, P, Ca and Cu, wherein the preparation method comprises the steps of preparing an alloy melt; step two, horizontal continuous casting; step three, homogenizing and annealing; step four, finish rolling and cold drawing; and step five, annealing at low temperature. Compared with the existing copper alloy, the invention can form compact oxide in corrosive medium by adding micro alloying elements in the formula, thereby improving the corrosion resistance of the alloy. Meanwhile, alloying elements can strengthen the alloy, improve the strength of the material and keep higher heat-conducting property. By reasonably setting the process steps and optimizing the process parameters, the prepared copper alloy has the advantages of high strength, good corrosion resistance, good plasticity and good heat-conducting property. The preparation method has the advantages of short process flow, simple operation and low production cost, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of high-performance copper alloys, in particular to a high-strength high-heat-conductivity high-corrosion-resistance copper alloy and a preparation method thereof.
Background
The copper alloy is favored by various industries due to excellent mechanical property and heat-conducting property, and along with the development of industries such as ocean engineering, air-conditioning condenser tubes, electric water heaters and the like, the demand on the high-strength high-heat-conductivity high-corrosion-resistance copper alloy is increasingly urgent, so that the design development and the corrosion-resistant mechanism research of the novel high-strength high-heat-conductivity high-corrosion-resistance copper alloy under severe service conditions are developed on the basis of the traditional copper alloy, and the copper alloy has important significance on the basic theoretical research and the engineering application of the high-strength high-heat-conductivity high-corrosion-resistance copper alloy for service in special environments in China.
Disclosure of Invention
The invention aims to provide a high-strength high-heat-conductivity high-corrosion-resistance copper alloy and a preparation method thereof, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following components in percentage by weight: zn, Sn, Si, Ge, P, Ca and Cu, wherein the weight percentage of each component is as follows: 0.001-0.5% of Zn, 0.001-0.5% of Sn, 0.001-0.5% of Si, 0.001-0.5% of Ge, 0.001-0.15% of P and 0.001-0.15% of Ca, and the balance of Cu and inevitable impurities.
A preparation method of a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following steps of preparing an alloy melt; step two, horizontal continuous casting; step three, homogenizing and annealing; step four, finish rolling and cold drawing; step five, annealing at low temperature;
in the first step, the components in percentage by weight are as follows: 0.001-0.5% of Zn, 0.001-0.5% of Sn, 0.001-0.5% of Si, 0.001-0.5% of Ge, 0.001-0.15% of P, 0.001-0.15% of Ca and the balance of Cu and inevitable impurities, weighing according to the sum of the weight percentage of 1, then putting the weighed Cu, Si and Ge into a heating furnace for melting, adding Sn, Zn, Ca and P, and forming an alloy melt after uniform melting;
in the second step, firstly transferring the alloy melt prepared in the first step into a horizontal continuous casting machine to obtain a plate blank or a tube blank, and then carrying out surface milling treatment on the plate blank or the tube blank;
in the third step, firstly, the plate blank or the pipe blank prepared in the second step is subjected to homogenizing annealing, a plate or a drawn pipe is obtained after multi-pass cold rolling or cold drawing, and then the plate or the drawn pipe is subjected to recrystallization annealing treatment;
in the fourth step, the plate subjected to the recrystallization annealing treatment in the third step is subjected to finish rolling treatment, or the tube subjected to the recrystallization annealing treatment is subjected to cold drawing treatment;
and in the fifth step, performing low-temperature annealing treatment on the plate subjected to finish rolling treatment in the fourth step or the pipe subjected to cold drawing treatment to obtain the high-strength high-heat-conductivity high-corrosion-resistance copper alloy plate or the drawn pipe.
Preferably, in the first step, the weighed Cu, Si and Ge are put into a heating furnace for melting, the melting temperature is controlled to be 1200-1300 ℃, the temperature is reduced to 1150-1210 ℃ after the Cu, Si and Ge are completely melted, and then the Sn, Zn, Ca and P are added and melted uniformly to form the alloy melt.
Preferably, in the second step, the temperature of horizontal continuous casting is 1050-; the pull-out length is 8-15 mm; stopping for 1-3 seconds, wherein the temperature of the outlet of the strip blank is 300-; the pressure of the cooling water is 0.05-0.40 MPa.
Preferably, in the third step, the homogenization annealing temperature is 640-700 ℃, the deformation amount is 50-80%, and the recrystallization annealing treatment temperature is 500-600 ℃.
Preferably, in the fourth step, the deformation amount of the finish rolling treatment or the cold drawing treatment is 30 to 80%.
Preferably, in the fifth step, the temperature of the low-temperature annealing treatment is 200-250 ℃, and the time is 1-2 h.
Preferably, in the fifth step, the maximum tensile strength of the high-strength high-thermal-conductivity high-corrosion-resistance copper alloy is 200-400MPa, the yield strength is 80-250MPa, the elongation after fracture is 20-45%, the thermal conductivity is 350-380watt/m, and the corrosion rate in a 3.5% NaCl solution is 0.04-0.05 mm/a.
Compared with the prior art, the invention has the beneficial effects that: compared with the existing copper alloy, the copper alloy can form compact oxide in a corrosive medium by adding the micro-alloying elements in the formula, so that the corrosion resistance of the alloy is improved, and meanwhile, the solid-dissolved alloying elements can strengthen the alloy, improve the strength of the material and keep higher heat conductivity.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a scanning electron microscope photograph of a high-strength, high-thermal-conductivity and high-corrosion-resistance copper alloy sheet prepared in example 2 of the present invention corroded in a 3.5% NaCl solution for 30 days;
fig. 3 is a scanning electron microscope photograph of a tensile fracture of the high-strength, high-thermal-conductivity and high-corrosion-resistance copper alloy sheet prepared in embodiment 4 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-3, a technical solution provided by the present invention is:
example 1:
a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following components in percentage by weight: zn, Sn, Si, Ge, P, Ca and Cu, wherein the weight percentage of each component is as follows: 0.001% of Zn, 0.001% of Sn, 0.001% of Si, 0.001% of Ge, 0.001% of P, and 0.001% of Ca, the balance being Cu and inevitable impurities.
A preparation method of a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following steps of preparing an alloy melt; step two, horizontal continuous casting; step three, homogenizing and annealing; step four, finish rolling and cold drawing; step five, annealing at low temperature;
in the first step, the components in percentage by weight are as follows: 0.001% of Zn, 0.001% of Sn, 0.001% of Si, 0.001% of Ge, 0.001% of P and 0.001% of Ca, and the balance of Cu and inevitable impurities, wherein the raw materials are weighed according to the sum of the weight percentages of 1, then the weighed Cu, Si and Ge are put into a heating furnace to be melted, the melting temperature is controlled to be 1200 ℃, the temperature is reduced to 1150 ℃ after the Cu, Si, Ca and P are completely melted, and an alloy melt is formed after the Sn, Zn, Ca and P are uniformly melted;
in the second step, firstly transferring the alloy melt prepared in the first step into a horizontal continuous casting machine to obtain a plate blank or a tube blank, and then carrying out surface milling treatment on the plate blank or the tube blank, wherein the temperature of the horizontal continuous casting is 1050 ℃, the casting blank speed is 150m/h, and the reverse thrust is 0.1 mm; the pull-out length is 8 mm; stopping for 1 second, wherein the temperature of the strip billet outlet is 300 ℃; the pressure of the cooling water is 0.05 MPa;
in the third step, firstly, the plate blank or the pipe blank prepared in the second step is subjected to homogenizing annealing, a plate or a drawn pipe is obtained after multi-pass cold rolling or cold drawing, and then the plate or the drawn pipe is subjected to recrystallization annealing treatment, wherein the homogenizing annealing temperature is 640 ℃, the deformation is 50%, and the recrystallization annealing treatment temperature is 500 ℃;
in the fourth step, the plate subjected to the recrystallization annealing treatment in the third step is subjected to finish rolling treatment, or the tube subjected to the recrystallization annealing treatment is subjected to cold drawing treatment, wherein the deformation of the finish rolling treatment or the cold drawing treatment is 30%;
and in the fifth step, performing low-temperature annealing treatment on the plate subjected to the finish rolling treatment in the fourth step or the pipe subjected to the cold drawing treatment to obtain the high-strength high-heat-conductivity high-corrosion-resistance copper alloy plate or the drawn pipe, wherein the temperature of the low-temperature annealing treatment is 200 ℃, the time is h, the maximum tensile strength of the high-strength high-heat-conductivity high-corrosion-resistance copper alloy is 200MPa, the yield strength is 80MPa, the elongation after fracture is 45%, the heat conductivity coefficient is 380watt/m, and the corrosion rate in a 3.5% NaCl solution is 0.050 mm/a.
Example 2:
a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following components in percentage by weight: zn, Sn, Si, Ge, P, Ca and Cu, wherein the weight percentage of each component is as follows: 0.05% of Zn, 0.05% of Sn, 0.001% of Si, 0.001% of Ge, 0.001% of P and 0.001% of Ca, and the balance of Cu and inevitable impurities.
A preparation method of a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following steps of preparing an alloy melt; step two, horizontal continuous casting; step three, homogenizing and annealing; step four, finish rolling and cold drawing; step five, annealing at low temperature;
in the first step, the components in percentage by weight are as follows: 0.05% of Zn, 0.05% of Sn, 0.001% of Si, 0.001% of Ge, 0.001% of P and 0.001% of Ca, and the balance of Cu and inevitable impurities, preparing materials, weighing according to the sum of the weight percentage of 1, then putting the weighed Cu, Si and Ge into a heating furnace for melting, controlling the melting temperature to 1250 ℃, cooling to 1160 ℃ after the materials are completely melted, adding Sn, Zn, Ca and P, and uniformly melting to form an alloy melt;
in the second step, firstly transferring the alloy melt prepared in the first step into a horizontal continuous casting machine to obtain a plate blank or a tube blank, and then carrying out surface milling treatment on the plate blank or the tube blank, wherein the temperature of the horizontal continuous casting is 1080 ℃, the casting blank speed is 155m/h, and the reverse thrust is 0.12 mm; the pull-out length is 8 mm; stopping for 1.5 seconds, and controlling the temperature of a strip billet outlet to be 320 ℃; the pressure of the cooling water is 0.08 MPa;
in the third step, firstly, the plate blank or the pipe blank prepared in the second step is subjected to homogenizing annealing, a plate or a drawn pipe is obtained after multi-pass cold rolling or cold drawing, and then the plate or the drawn pipe is subjected to recrystallization annealing treatment, wherein the homogenizing annealing temperature is 650 ℃, the deformation amount is 60%, and the recrystallization annealing treatment temperature is 520 ℃;
in the fourth step, the plate subjected to the recrystallization annealing treatment in the third step is subjected to finish rolling treatment, or the tube subjected to the recrystallization annealing treatment is subjected to cold drawing treatment, wherein the deformation of the finish rolling treatment or the cold drawing treatment is 40%;
and in the fifth step, performing low-temperature annealing treatment on the plate subjected to the finish rolling treatment in the fourth step or the pipe subjected to the cold drawing treatment to obtain the high-strength high-heat-conductivity high-corrosion-resistance copper alloy plate or the drawn pipe, wherein the temperature of the low-temperature annealing treatment is 220 ℃, the time is 1h, the maximum tensile strength of the high-strength high-heat-conductivity high-corrosion-resistance copper alloy is 325MPa, the yield strength is 180MPa, the elongation after fracture is 25%, the heat conductivity coefficient is 362watt/m, and the corrosion rate in a 3.5% NaCl solution is 0.042 mm/a.
Example 3:
a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following components in percentage by weight: zn, Sn, Si, Ge, P, Ca and Cu, wherein the weight percentage of each component is as follows: 0.005% of Zn, 0.05% of Sn, 0.002% of Si, 0.002% of Ge, 0.002% of P and 0.001% of Ca, and the balance of Cu and inevitable impurities.
A preparation method of a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following steps of preparing an alloy melt; step two, horizontal continuous casting; step three, homogenizing and annealing; step four, finish rolling and cold drawing; step five, annealing at low temperature;
in the first step, the components in percentage by weight are as follows: 0.005% of Zn, 0.05% of Sn, 0.002% of Si, 0.002% of Ge, 0.002% of P and 0.001% of Ca, and the balance of Cu and inevitable impurities are prepared, weighed according to the sum of the weight percentage of 1, then the weighed Cu, Si and Ge are put into a heating furnace to be melted, the melting temperature is controlled to be 1200 ℃, the temperature is reduced to 1150 ℃ after the Cu, Si, Ca and P are completely melted, and an alloy melt is formed after the Sn, Zn, Ca and P are uniformly melted;
in the second step, firstly transferring the alloy melt prepared in the first step into a horizontal continuous casting machine to obtain a plate blank or a tube blank, and then carrying out surface milling treatment on the plate blank or the tube blank, wherein the temperature of the horizontal continuous casting is 1060 ℃, the casting blank speed is 150m/h, and the reverse thrust is 0.1 mm; the pull-out length is 8 mm; stopping for 2 seconds, wherein the temperature of the outlet of the strip blank is 300 ℃; the pressure of the cooling water is 0.2 MPa;
in the third step, firstly, the plate blank or the pipe blank prepared in the second step is subjected to homogenizing annealing, a plate or a drawn pipe is obtained after multi-pass cold rolling or cold drawing, and then the plate or the drawn pipe is subjected to recrystallization annealing treatment, wherein the homogenizing annealing temperature is 650 ℃, the deformation amount is 80%, and the recrystallization annealing treatment temperature is 550 ℃;
in the fourth step, the plate subjected to the recrystallization annealing treatment in the third step is subjected to finish rolling treatment, or the tube subjected to the recrystallization annealing treatment is subjected to cold drawing treatment, wherein the deformation of the finish rolling treatment or the cold drawing treatment is 80%;
and in the fifth step, performing low-temperature annealing treatment on the plate subjected to the finish rolling treatment in the fourth step or the pipe subjected to the cold drawing treatment to obtain the high-strength high-heat-conductivity high-corrosion-resistance copper alloy plate or the drawn pipe, wherein the temperature of the low-temperature annealing treatment is 250 ℃, the time is 1h, the maximum tensile strength of the high-strength high-heat-conductivity high-corrosion-resistance copper alloy is 250MPa, the yield strength is 100MPa, the elongation after fracture is 40%, the heat conductivity coefficient is 360watt/m, and the corrosion rate in a 3.5% NaCl solution is 0.044 mm/a.
Example 4:
a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following components in percentage by weight: zn, Sn, Si, Ge, P, Ca and Cu, wherein the weight percentage of each component is as follows: 0.001% of Zn, 0.001% of Sn, 0.05% of Si, 0.002% of Ge, 0.002% of P, and 0.002% of Ca, the balance being Cu and unavoidable impurities.
A preparation method of a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following steps of preparing an alloy melt; step two, horizontal continuous casting; step three, homogenizing and annealing; step four, finish rolling and cold drawing; step five, annealing at low temperature;
in the first step, the components in percentage by weight are as follows: 0.001% of Zn, 0.001% of Sn, 0.05% of Si, 0.002% of Ge, 0.002% of P and 0.002% of Ca, and the balance of Cu and inevitable impurities, preparing materials, weighing according to the sum of the weight percentage of 1, then putting the weighed Cu, Si and Ge into a heating furnace for melting, controlling the melting temperature to 1250 ℃, cooling to 1150 ℃ after the materials are completely melted, adding Sn, Zn, Ca and P, and uniformly melting to form an alloy melt;
in the second step, firstly transferring the alloy melt prepared in the first step into a horizontal continuous casting machine to obtain a plate blank or a tube blank, and then carrying out surface milling treatment on the plate blank or the tube blank, wherein the temperature of the horizontal continuous casting is 1120 ℃, the casting blank speed is 152m/h, and the reverse thrust is 1 mm; the pull-out length is 9 mm; stopping for 1.5 seconds, and controlling the temperature of a strip billet outlet to be 320 ℃; the pressure of the cooling water is 0.5 MPa;
in the third step, firstly, the plate blank or the pipe blank prepared in the second step is subjected to homogenizing annealing, a plate or a drawn pipe is obtained after multi-pass cold rolling or cold drawing, and then the plate or the drawn pipe is subjected to recrystallization annealing treatment, wherein the homogenizing annealing temperature is 640 ℃, the deformation amount is 60%, and the recrystallization annealing treatment temperature is 500 ℃;
in the fourth step, the plate subjected to the recrystallization annealing treatment in the third step is subjected to finish rolling treatment, or the tube subjected to the recrystallization annealing treatment is subjected to cold drawing treatment, wherein the deformation of the finish rolling treatment or the cold drawing treatment is 50%;
and in the fifth step, performing low-temperature annealing treatment on the plate subjected to the finish rolling treatment in the fourth step or the pipe subjected to the cold drawing treatment to obtain the high-strength high-heat-conductivity high-corrosion-resistance copper alloy plate or the drawn pipe, wherein the temperature of the low-temperature annealing treatment is 220 ℃, the time is 1.5h, the maximum tensile strength of the high-strength high-heat-conductivity high-corrosion-resistance copper alloy is 260MPa, the yield strength is 140MPa, the elongation after fracture is 30%, the heat conductivity coefficient is 365watt/m, and the corrosion rate in a 3.5% NaCl solution is 0.043 mm/a.
Example 5:
a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following components in percentage by weight: zn, Sn, Si, Ge, P, Ca and Cu, wherein the weight percentage of each component is as follows: 0.5% of Zn, 0.5% of Sn, 0.001% of Si, 0.002% of Ge, 0.002% of P and 0.002% of Ca, and the balance of Cu and inevitable impurities.
A preparation method of a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following steps of preparing an alloy melt; step two, horizontal continuous casting; step three, homogenizing and annealing; step four, finish rolling and cold drawing; step five, annealing at low temperature;
in the first step, the components in percentage by weight are as follows: 0.5% of Zn, 0.5% of Sn, 0.001% of Si, 0.002% of Ge, 0.002% of P and 0.002% of Ca, and the balance of Cu and inevitable impurities, preparing materials, weighing according to the sum of the weight percentage of 1, then putting the weighed Cu, Si and Ge into a heating furnace for melting, controlling the melting temperature to 1280 ℃, cooling to 1200 ℃ after the materials are completely melted, adding Sn, Zn, Ca and P, and melting uniformly to form an alloy melt;
in the second step, firstly transferring the alloy melt prepared in the first step into a horizontal continuous casting machine to obtain a plate blank or a tube blank, and then carrying out surface milling treatment on the plate blank or the tube blank, wherein the temperature of the horizontal continuous casting is 1200 ℃, the casting blank speed is 160m/h, and the reverse thrust is 0.1 mm; the pull-out length is 8 mm; stopping for 1 second, wherein the temperature of the strip billet outlet is 350 ℃; the pressure of the cooling water is 0.4 MPa;
in the third step, firstly, the plate blank or the pipe blank prepared in the second step is subjected to homogenizing annealing, a plate or a drawn pipe is obtained after multi-pass cold rolling or cold drawing, and then the plate or the drawn pipe is subjected to recrystallization annealing treatment, wherein the homogenizing annealing temperature is 700 ℃, the deformation amount is 80%, and the recrystallization annealing treatment temperature is 600 ℃;
in the fourth step, the plate subjected to the recrystallization annealing treatment in the third step is subjected to finish rolling treatment, or the tube subjected to the recrystallization annealing treatment is subjected to cold drawing treatment, wherein the deformation of the finish rolling treatment or the cold drawing treatment is 80%;
and in the fifth step, performing low-temperature annealing treatment on the plate subjected to the finish rolling treatment in the fourth step or the pipe subjected to the cold drawing treatment to obtain the high-strength high-heat-conductivity high-corrosion-resistance copper alloy plate or the drawn pipe, wherein the temperature of the low-temperature annealing treatment is 250 ℃, the time is 2 hours, the maximum tensile strength of the high-strength high-heat-conductivity high-corrosion-resistance copper alloy is 370MPa, the yield strength is 240MPa, the elongation after fracture is 25%, the heat conductivity coefficient is 355watt/m, and the corrosion rate in a 3.5% NaCl solution is 0.041 mm/a.
Example 6:
a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following components in percentage by weight: zn, Sn, Si, Ge, P, Ca and Cu, wherein the weight percentage of each component is as follows: 0.001% of Zn, 0.001% of Sn, 0.5% of Si, 0.5% of Ge, 0.15% of P, and 0.15% of Ca, the balance being Cu and unavoidable impurities.
A preparation method of a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following steps of preparing an alloy melt; step two, horizontal continuous casting; step three, homogenizing and annealing; step four, finish rolling and cold drawing; step five, annealing at low temperature;
in the first step, the components in percentage by weight are as follows: 0.001% of Zn, 0.001% of Sn, 0.5% of Si, 0.5% of Ge, 0.15% of P and 0.15% of Ca, and the balance of Cu and inevitable impurities, preparing materials, weighing according to the sum of the weight percentage of 1, then putting the weighed Cu, Si and Ge into a heating furnace for melting, controlling the melting temperature to 1300 ℃, cooling to 1210 ℃ after the materials are completely melted, adding Sn, Zn, Ca and P, and melting uniformly to form an alloy melt;
in the second step, firstly transferring the alloy melt prepared in the first step into a horizontal continuous casting machine to obtain a plate blank or a tube blank, and then carrying out surface milling treatment on the plate blank or the tube blank, wherein the temperature of the horizontal continuous casting is 1250 ℃, the casting blank speed is 160m/h, and the reverse thrust is 2 mm; the pull-out length is 15 mm; stopping for 3 seconds, wherein the temperature of the outlet of the strip blank is 350 ℃; the pressure of the cooling water is 0.3 MPa;
in the third step, firstly, the plate blank or the pipe blank prepared in the second step is subjected to homogenizing annealing, a plate or a drawn pipe is obtained after multi-pass cold rolling or cold drawing, and then the plate or the drawn pipe is subjected to recrystallization annealing treatment, wherein the homogenizing annealing temperature is 700 ℃, the deformation amount is 60%, and the recrystallization annealing treatment temperature is 600 ℃;
in the fourth step, the plate subjected to the recrystallization annealing treatment in the third step is subjected to finish rolling treatment, or the tube subjected to the recrystallization annealing treatment is subjected to cold drawing treatment, wherein the deformation of the finish rolling treatment or the cold drawing treatment is 50%;
and in the fifth step, performing low-temperature annealing treatment on the plate subjected to the finish rolling treatment in the fourth step or the pipe subjected to the cold drawing treatment to obtain the high-strength high-heat-conductivity high-corrosion-resistance copper alloy plate or the drawn pipe, wherein the temperature of the low-temperature annealing treatment is 240 ℃, the time is 2 hours, the maximum tensile strength of the high-strength high-heat-conductivity high-corrosion-resistance copper alloy is 400MPa, the yield strength is 250MPa, the elongation after fracture is 20%, the heat conductivity coefficient is 350watt/m, and the corrosion rate in a 3.5% NaCl solution is 0.040 mm/a.
Comparative example 1:
a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following components in percentage by weight: zn, Sn, Si, Ge, P, Ca and Cu, wherein the weight percentage of each component is as follows: 0.001% of Zn, 0.001% of Sn, 0.001% of Si, 0.001% of Ge, 0.001% of P, and 0.001% of Ca, the balance being Cu and inevitable impurities.
A preparation method of a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following steps of preparing an alloy melt; step two, horizontal continuous casting; step three, homogenizing and annealing; step four, finish rolling and cold drawing; step five, annealing at low temperature;
in the first step, the components in percentage by weight are as follows: 0.001% of Zn, 0.001% of Sn, 0.001% of Si, 0.001% of Ge, 0.001% of P and 0.001% of Ca, and the balance of Cu and inevitable impurities, wherein the raw materials are weighed according to the sum of the weight percentages of 1, then the weighed Cu, Si and Ge are put into a heating furnace to be melted, the melting temperature is controlled to be 1200 ℃, the temperature is reduced to 1150 ℃ after the Cu, Si, Ca and P are completely melted, and an alloy melt is formed after the Sn, Zn, Ca and P are uniformly melted;
in the second step, firstly transferring the alloy melt prepared in the first step into a horizontal continuous casting machine to obtain a plate blank or a tube blank, and then carrying out surface milling treatment on the plate blank or the tube blank, wherein the temperature of the horizontal continuous casting is 1010 ℃, the casting blank speed is 200m/h, and the reverse thrust is 0.1 mm; the pull-out length is 8 mm; stopping for 1 second, wherein the temperature of the strip billet outlet is 300 ℃; the pressure of the cooling water is 0.01 MPa;
in the third step, firstly, the plate blank or the pipe blank prepared in the second step is subjected to homogenizing annealing, a plate or a drawn pipe is obtained after multi-pass cold rolling or cold drawing, and then the plate or the drawn pipe is subjected to recrystallization annealing treatment, wherein the homogenizing annealing temperature is 640 ℃, the deformation is 50%, and the recrystallization annealing treatment temperature is 500 ℃;
in the fourth step, the plate subjected to the recrystallization annealing treatment in the third step is subjected to finish rolling treatment, or the tube subjected to the recrystallization annealing treatment is subjected to cold drawing treatment, wherein the deformation of the finish rolling treatment or the cold drawing treatment is 30%;
and in the fifth step, performing low-temperature annealing treatment on the plate subjected to the finish rolling treatment in the fourth step or the pipe subjected to the cold drawing treatment to obtain the high-strength high-heat-conductivity high-corrosion-resistance copper alloy plate or the drawn pipe, wherein the temperature of the low-temperature annealing treatment is 200 ℃, the time is 1h, the maximum tensile strength of the high-strength high-heat-conductivity high-corrosion-resistance copper alloy is 140MPa, the yield strength is 75MPa, the elongation after fracture is 46%, the heat conductivity coefficient is 375watt/m, and the corrosion rate in a 3.5% NaCl solution is 0.049 mm/a.
Comparative example 2:
a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following components in percentage by weight: zn, Sn, Si, Ge, P, Ca and Cu, wherein the weight percentage of each component is as follows: 0.05% of Zn, 0.05% of Sn, 0.001% of Si, 0.001% of Ge, 0.001% of P and 0.001% of Ca, and the balance of Cu and inevitable impurities.
A preparation method of a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following steps of preparing an alloy melt; step two, horizontal continuous casting; step three, homogenizing and annealing; step four, finish rolling and cold drawing; step five, annealing at low temperature;
in the first step, the components in percentage by weight are as follows: 0.05% of Zn, 0.05% of Sn, 0.001% of Si, 0.001% of Ge, 0.001% of P and 0.001% of Ca, and the balance of Cu and inevitable impurities, preparing materials, weighing according to the sum of the weight percentage of 1, then putting the weighed Cu, Si and Ge into a heating furnace for melting, controlling the melting temperature to 1250 ℃, cooling to 1160 ℃ after the materials are completely melted, adding Sn, Zn, Ca and P, and uniformly melting to form an alloy melt;
in the second step, firstly transferring the alloy melt prepared in the first step into a horizontal continuous casting machine to obtain a plate blank or a tube blank, and then carrying out surface milling treatment on the plate blank or the tube blank, wherein the temperature of the horizontal continuous casting is 1080 ℃, the casting blank speed is 155m/h, and the reverse thrust is 0.12 mm; the pull-out length is 8 mm; stopping for 1.5 seconds, and controlling the temperature of a strip billet outlet to be 320 ℃; the pressure of the cooling water is 0.08 MPa;
in the third step, firstly, the plate blank or the pipe blank prepared in the second step is subjected to homogenizing annealing, a plate or a drawn pipe is obtained after multi-pass cold rolling or cold drawing, and then the plate or the drawn pipe is subjected to recrystallization annealing treatment, wherein the homogenizing annealing temperature is 500 ℃, the deformation is 90%, and the recrystallization annealing treatment temperature is 450 ℃;
in the fourth step, the plate subjected to the recrystallization annealing treatment in the third step is subjected to finish rolling treatment, or the tube subjected to the recrystallization annealing treatment is subjected to cold drawing treatment, wherein the deformation of the finish rolling treatment or the cold drawing treatment is 40%;
and in the fifth step, performing low-temperature annealing treatment on the plate subjected to the finish rolling treatment in the fourth step or the pipe subjected to the cold drawing treatment to obtain the high-strength high-heat-conductivity high-corrosion-resistance copper alloy plate or the drawn pipe, wherein the temperature of the low-temperature annealing treatment is 220 ℃, the time is 1h, the maximum tensile strength of the high-strength high-heat-conductivity high-corrosion-resistance copper alloy is 250MPa, the yield strength is 121MPa, the elongation after fracture is 35%, the heat conductivity coefficient is 360watt/m, and the corrosion rate in a 3.5% NaCl solution is 0.041 mm/a.
Comparative example 3:
a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following components in percentage by weight: zn, Sn, Si, Ge, P, Ca and Cu, wherein the weight percentage of each component is as follows: 0.5% Zn, 0.0001% Sn, 0.001% Si, 0.002% Ge, 0.002% P and 0.002% Ca, the remainder being Cu and unavoidable impurities.
A preparation method of a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following steps of preparing an alloy melt; step two, horizontal continuous casting; step three, homogenizing and annealing; step four, finish rolling and cold drawing; step five, annealing at low temperature;
in the first step, the components in percentage by weight are as follows: 0.5% of Zn, 0.0001% of Sn, 0.001% of Si, 0.002% of Ge, 0.002% of P and 0.002% of Ca, and the balance of Cu and inevitable impurities, preparing materials, weighing according to the sum of the weight percentage of 1, then putting the weighed Cu, Si and Ge into a heating furnace for melting, controlling the melting temperature to 1280 ℃, cooling to 1200 ℃ after the materials are completely melted, adding Sn, Zn, Ca and P, and melting uniformly to form an alloy melt;
in the second step, firstly transferring the alloy melt prepared in the first step into a horizontal continuous casting machine to obtain a plate blank or a tube blank, and then carrying out surface milling treatment on the plate blank or the tube blank, wherein the temperature of the horizontal continuous casting is 1200 ℃, the casting blank speed is 160m/h, and the reverse thrust is 0.1 mm; the pull-out length is 8 mm; stopping for 1 second, wherein the temperature of the strip billet outlet is 350 ℃; the pressure of the cooling water is 0.4 MPa;
in the third step, firstly, the plate blank or the pipe blank prepared in the second step is subjected to homogenizing annealing, a plate or a drawn pipe is obtained after multi-pass cold rolling or cold drawing, and then the plate or the drawn pipe is subjected to recrystallization annealing treatment, wherein the homogenizing annealing temperature is 700 ℃, the deformation amount is 80%, and the recrystallization annealing treatment temperature is 600 ℃;
in the fourth step, the plate subjected to the recrystallization annealing treatment in the third step is subjected to finish rolling treatment, or the tube subjected to the recrystallization annealing treatment is subjected to cold drawing treatment, wherein the deformation of the finish rolling treatment or the cold drawing treatment is 80%;
and in the fifth step, performing low-temperature annealing treatment on the plate subjected to finish rolling treatment in the fourth step or the pipe subjected to cold drawing treatment to obtain the high-strength high-heat-conductivity high-corrosion-resistance copper alloy plate or the drawn pipe, wherein the temperature of the low-temperature annealing treatment is 250 ℃, the time is 2 hours, the maximum tensile strength of the high-strength high-heat-conductivity high-corrosion-resistance copper alloy is 320MPa, the yield strength is 256MPa, the elongation after fracture is 28%, the heat conductivity coefficient is 355watt/m, and the corrosion rate in a 3.5% NaCl solution is 0.055 mm/a.
The following table shows the properties of the examples and comparative examples:
based on the above, the invention reasonably designs the alloy components and the content thereof, so that the alloy mainly comprises micro-alloying elements such as Zn, Sn, Si, Ge, P, Ca and the like, and solute atoms can be formed, thereby achieving a better solid solution strengthening effect. And through reasonable setting of process steps and optimization of process parameters, the supersaturation degree of solute atoms in the thermomechanical treatment process of the alloy is increased, and finally the high-strength high-heat-conduction high-corrosion-resistance copper alloy with high strength, high electric conductivity and good corrosion resistance is obtained. SnO may be generated by adding Sn, Si, Ge or the like2、SiO2、GeO2And the like, which are compact and can block the further oxidation and corrosion of the material, so that the corrosion resistance of the obtained alloy is obviously improved. Prepared by the method of the inventionThe obtained high-strength high-heat-conductivity high-corrosion-resistance copper alloy has a uniform structure and has higher tensile strength, yield strength, elongation, heat conductivity and corrosion resistance.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (8)
1. A high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following components in percentage by weight: zn, Sn, Si, Ge, P, Ca and Cu, characterized in that: the weight percentage of each component is as follows: 0.001-0.5% of Zn, 0.001-0.5% of Sn, 0.001-0.5% of Si, 0.001-0.5% of Ge, 0.001-0.15% of P and 0.001-0.15% of Ca, and the balance of Cu and inevitable impurities.
2. A preparation method of a high-strength high-heat-conductivity high-corrosion-resistance copper alloy comprises the following steps of preparing an alloy melt; step two, horizontal continuous casting; step three, homogenizing and annealing; step four, finish rolling and cold drawing; step five, annealing at low temperature; the method is characterized in that:
in the first step, the components in percentage by weight are as follows: 0.001-0.5% of Zn, 0.001-0.5% of Sn, 0.001-0.5% of Si, 0.001-0.5% of Ge, 0.001-0.15% of P, 0.001-0.15% of Ca and the balance of Cu and inevitable impurities, weighing according to the sum of the weight percentage of 1, then putting the weighed Cu, Si and Ge into a heating furnace for melting, adding Sn, Zn, Ca and P, and forming an alloy melt after uniform melting;
in the second step, firstly transferring the alloy melt prepared in the first step into a horizontal continuous casting machine to obtain a plate blank or a tube blank, and then carrying out surface milling treatment on the plate blank or the tube blank;
in the third step, firstly, the plate blank or the pipe blank prepared in the second step is subjected to homogenizing annealing, a plate or a drawn pipe is obtained after multi-pass cold rolling or cold drawing, and then the plate or the drawn pipe is subjected to recrystallization annealing treatment;
in the fourth step, the plate subjected to the recrystallization annealing treatment in the third step is subjected to finish rolling treatment, or the tube subjected to the recrystallization annealing treatment is subjected to cold drawing treatment;
and in the fifth step, performing low-temperature annealing treatment on the plate subjected to finish rolling treatment in the fourth step or the pipe subjected to cold drawing treatment to obtain the high-strength high-heat-conductivity high-corrosion-resistance copper alloy plate or the drawn pipe.
3. The method for preparing the high-strength high-thermal-conductivity high-corrosion-resistance copper alloy according to claim 2, wherein the method comprises the following steps: in the first step, the weighed Cu, Si and Ge are put into a heating furnace for melting, the melting temperature is controlled to be 1200-1300 ℃, the temperature is reduced to 1150-1210 ℃ after the Cu, Si and Ge are completely melted, and then the Sn, Zn, Ca and P are added and melted uniformly to form an alloy melt.
4. The method for preparing the high-strength high-thermal-conductivity high-corrosion-resistance copper alloy according to claim 2, wherein the method comprises the following steps: in the second step, the temperature of horizontal continuous casting is 1050-; the pull-out length is 8-15 mm; stopping for 1-3 seconds, wherein the temperature of the outlet of the strip blank is 300-; the pressure of the cooling water is 0.05-0.40 MPa.
5. The method for preparing the high-strength high-thermal-conductivity high-corrosion-resistance copper alloy according to claim 2, wherein the method comprises the following steps: in the third step, the homogenization annealing temperature is 640-700 ℃, the deformation amount is 50-80%, and the recrystallization annealing treatment temperature is 500-600 ℃.
6. The method for preparing the high-strength high-thermal-conductivity high-corrosion-resistance copper alloy according to claim 2, wherein the method comprises the following steps: in the fourth step, the deformation of the finish rolling treatment or the cold drawing treatment is 30-80%.
7. The method for preparing the high-strength high-thermal-conductivity high-corrosion-resistance copper alloy according to claim 2, wherein the method comprises the following steps: in the fifth step, the temperature of the low-temperature annealing treatment is 200-250 ℃, and the time is 1-2 h.
8. The method for preparing the high-strength high-thermal-conductivity high-corrosion-resistance copper alloy according to claim 2, wherein the method comprises the following steps: in the fifth step, the maximum tensile strength of the high-strength high-heat-conductivity high-corrosion-resistance copper alloy is 200-400MPa, the yield strength is 80-250MPa, the elongation after fracture is 20-45%, the heat conductivity coefficient is 350-380watt/m, and the corrosion rate in a 3.5% NaCl solution is 0.04-0.05 mm/a.
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