CN116555773A - High-heat-conductivity high-electric-conductivity red copper alloy and preparation method thereof - Google Patents
High-heat-conductivity high-electric-conductivity red copper alloy and preparation method thereof Download PDFInfo
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- CN116555773A CN116555773A CN202310627935.1A CN202310627935A CN116555773A CN 116555773 A CN116555773 A CN 116555773A CN 202310627935 A CN202310627935 A CN 202310627935A CN 116555773 A CN116555773 A CN 116555773A
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 55
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052802 copper Inorganic materials 0.000 claims abstract description 53
- 238000005554 pickling Methods 0.000 claims abstract description 51
- 238000005096 rolling process Methods 0.000 claims abstract description 41
- 238000005266 casting Methods 0.000 claims abstract description 33
- 238000000137 annealing Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims description 49
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 8
- 239000012964 benzotriazole Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000005238 degreasing Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000002161 passivation Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 2
- 238000005452 bending Methods 0.000 abstract description 4
- 238000003801 milling Methods 0.000 description 25
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 238000010405 reoxidation reaction Methods 0.000 description 4
- 238000000265 homogenisation Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 241000220317 Rosa Species 0.000 description 1
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- JEMGLEPMXOIVNS-UHFFFAOYSA-N arsenic copper Chemical compound [Cu].[As] JEMGLEPMXOIVNS-UHFFFAOYSA-N 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010892 electric spark Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000008373 pickled product Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- 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
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Mechanical Engineering (AREA)
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Conductive Materials (AREA)
Abstract
The invention provides a high-heat-conductivity high-electric-conductivity red copper alloy and a preparation method thereof, and belongs to the technical field of copper alloy manufacturing. The preparation method of the high-heat-conductivity high-electric-conductivity red copper alloy provided by the invention comprises the following steps: firstly, sequentially performing blooming, pickling and pre-product rolling on a red copper casting blank to obtain a pre-product casting blank; the method comprises the steps of (1) carrying out bell jar annealing and secondary pickling on a pre-finished casting blank obtained in the step (2) in sequence to obtain an annealed sheet strip, (3) carrying out finished rolling and finished pickling on the annealed sheet strip obtained in the step (2) in sequence to obtain a high-heat-conductivity high-electric-conductivity red copper alloy, wherein the result of the embodiment shows that the tensile strength of the high-heat-conductivity high-electric-conductivity red copper alloy prepared by the preparation method is more than 280MPa, and the elongation A is higher than that of the high-heat-conductivity high-electric-conductivity red copper alloy 11.3 More than or equal to 11 percent, the hardness is more than or equal to 93HV, the conductivity is more than 98 percent IACS, and the bending is carried out at 90 degreesDoes not crack.
Description
Technical Field
The invention relates to the technical field of copper alloy manufacturing, in particular to a high-heat-conductivity high-electric-conductivity red copper alloy and a preparation method thereof.
Background
Red copper is an industrial pure copper, and is generally called red copper because it has a rose red color and is purple after an oxide film is formed on the surface. The red copper processing material can be divided into: common red copper (T1, T2 and T3), oxygen-free copper (TU 1 and TU2 and high-purity and vacuum oxygen-free copper), deoxidized copper (TUP and TUMn) and special copper (arsenic copper, tellurium copper and silver copper) added with a small amount of alloy elements. The red copper has good electrical conductivity and thermal conductivity, and simultaneously has good plasticity, and is easy to be processed by hot pressing and cold pressing, so that the red copper is widely used for manufacturing products with good electrical conductivity, such as wires, cables, electric brushes, special electric spark etching copper, and the like. At present, the tensile strength of the red copper in the market is only about 230MPa, which can not meet the increasingly developed demands of industry, and along with the development of technology, the red copper has higher requirements on the heat conductivity and the electric conductivity. Therefore, how to improve the strength and the heat conducting property of red copper is a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to provide the high-heat-conductivity high-electric-conductivity red copper alloy and the preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a high-heat-conductivity high-electric-conductivity red copper alloy, which comprises the following steps:
(1) Sequentially performing blooming, pickling and pre-product rolling on the red copper casting blank to obtain a pre-product casting blank;
(2) Sequentially carrying out bell-type annealing and secondary pickling on the pre-finished casting blank obtained in the step (1) to obtain an annealed plate strip;
(3) And (3) rolling and pickling the finished product of the annealed plate strip obtained in the step (2) to obtain the high-heat-conductivity high-electric-conductivity red copper alloy.
Preferably, the total deformation of the initial rolling in the step (1) is 70-80%, the initial rolling passes are 5-6, and the single-pass deformation of the initial rolling is 10-30%.
Preferably, the acid washing in the step (1) includes degreasing liquid washing, sulfuric acid washing, passivation liquid washing, water washing, grinding washing water and acid post-washing water which are sequentially performed.
Preferably, the mass concentration of the sulfuric acid solution used in the sulfuric acid washing is 15-20%; the passivating agent adopted by the passivating agent washing is benzotriazole aqueous solution; the mass concentration of the benzotriazole aqueous solution is 0.05-0.15%.
Preferably, the uncoiling tension of the acid washing in the step (1) is 10-15N/mm 2 The coiling tension of the acid washing is 10 to 20N/mm 2 The pickling speed of the pickling is 10-20 m/min.
Preferably, the total deformation of the rolling of the preform in the step (1) is 30-40%, the rolling pass of the preform is 4-5, and the single-pass deformation of the rolling of the preform is 10-20%.
Preferably, the temperature of the bell jar annealing in the step (2) is 380-450 ℃, the heat preservation time of the bell jar annealing is 8-12 h, and the atmosphere of the bell jar annealing is a full nitrogen atmosphere; the gas flow rate of the total nitrogen atmosphere is 15-28 m 3 /h。
Preferably, the temperature rising rate of the bell jar annealing in the step (2) is 80-100 ℃/h.
Preferably, the total deformation of the finished product rolling in the step (3) is 10-20%, and the pass of the finished product rolling is 1-2.
The invention provides a high-heat-conductivity high-electric-conductivity red copper alloy prepared by the preparation method, which comprises the following chemical components in percentage by mass: cu:99.90 to 99.99 percent, P:0.0005 to 0.002 percent, fe:0.0010 to 0.005 percent, pb less than or equal to 0.002 percent, cd less than or equal to 0.00045 percent, as less than or equal to 0.0018 percent, sb less than or equal to 0.0018 percent and Bi less than or equal to 0.0008 percent.
The invention provides a preparation method of a high-heat-conductivity high-electric-conductivity red copper alloy, which comprises the following steps:
(1) Sequentially performing blooming, pickling and pre-product rolling on the red copper casting blank to obtain a pre-product casting blank; (2) Sequentially carrying out bell-type annealing and secondary pickling on the pre-finished casting blank obtained in the step (1) to obtain an annealed plate strip; (3) And (3) rolling and pickling the finished product of the annealed plate strip obtained in the step (2) to obtain the high-heat-conductivity high-electric-conductivity red copper alloy. According to the invention, the red copper casting blank is rolled for multiple times, so that the cast ingot can form coiled materials, and the heat conducting property of the cast ingot is improved after the cast ingot is prepared into a punching structure; after rolling, the copper alloy is subjected to acid washing, so that an oxide layer on the surface of the copper alloy can be removed, and the surface is passivated to avoid reoxidation, thereby avoiding the influence of air on the heat conductivity and the electric conductivity of the copper alloy; residual stress in the alloy can be removed through bell jar annealing treatment, and meanwhile, the homogenization treatment effect can be achieved, so that the internal structure of the alloy is more uniform, and the strength, the electric conductivity and the thermal conductivity of red copper are further improved. The results of the examples show that the tensile strength of the high-heat-conductivity high-electric-conductivity red copper alloy prepared by the preparation method provided by the invention is more than 280MPa, and the elongation A is higher than that of the high-heat-conductivity high-electric-conductivity red copper alloy 11.3 More than or equal to 11 percent, the hardness is more than or equal to 93HV, the conductivity is more than 98 percent IACS, and the bending at 90 degrees does not crack.
Detailed Description
The invention provides a preparation method of a high-heat-conductivity high-electric-conductivity red copper alloy, which comprises the following steps:
(1) Sequentially performing blooming, pickling and pre-product rolling on the red copper casting blank to obtain a pre-product casting blank;
(2) Sequentially carrying out bell-type annealing and secondary pickling on the pre-finished casting blank obtained in the step (1) to obtain an annealed plate strip;
(3) And (3) rolling and pickling the finished product of the annealed plate strip obtained in the step (2) to obtain the high-heat-conductivity high-electric-conductivity red copper alloy.
According to the method, the red copper casting blank is subjected to blooming, pickling and pre-product rolling in sequence to obtain the pre-product casting blank. The specific source of the red copper casting blank is not particularly limited, and the chemical components of the red copper alloy with high heat conductivity and high electric conductivity can meet the requirements.
In the invention, the red copper casting blank is preferably subjected to surface milling treatment before blooming. In the invention, the surface milling treatment preferably comprises two surface milling steps, wherein the single-side milling quantity of the first surface milling step is preferably 0.4-0.5 mm, the single-side milling quantity of the first surface milling step is preferably less than or equal to 3mm, and the speed of the first surface milling step is preferably less than or equal to 12m/min; the single-side milling amount of the second milling surface is preferably 0.4-0.5 mm, the second milling surface is preferably not milling edges, and the speed of the second milling surface is preferably less than or equal to 15m/min. The invention can remove the oxide layer on the surface of the red copper casting blank through surface milling treatment.
In the invention, the thickness of the red copper casting blank is preferably 14-15 mm. The thickness of the red copper casting blank is controlled, so that subsequent rolling is facilitated.
In the present invention, the total deformation amount of the blooming is preferably 70 to 80%; the initial rolling passes are preferably 5-6 passes, more preferably 6 passes; the single-pass deformation of the blooming is preferably 10-30%; the thickness of the bloomed product is preferably 3 to 4mm. According to the invention, the thickness of the red copper casting blank can be greatly reduced through blooming, and coarse grains in the red copper casting blank can be crushed, so that the mechanical property of red copper is improved.
In the present invention, the acid washing preferably includes degreasing liquid washing, sulfuric acid washing, passivation liquid washing, water washing, polishing washing water and acid post-washing water which are sequentially performed.
In the invention, the mass concentration of the sulfuric acid solution used for sulfuric acid washing is preferably 15-20%, more preferably 16-18%; the passivating agent used for the passivating agent washing is preferably benzotriazole aqueous solution; the concentration of the benzotriazole aqueous solution is preferably 0.05 to 0.15% by mass, more preferably 0.1% by mass. The type and concentration of the degreasing liquid used in the degreasing liquid washing are not particularly limited, and commercially available products known to those skilled in the art may be used.
In the present invention, the unwinding tension of the pickling is preferably 10% to the maximum15N/mm 2 The method comprises the steps of carrying out a first treatment on the surface of the The coiling tension of the acid washing is preferably 10-20N/mm 2 The method comprises the steps of carrying out a first treatment on the surface of the The pickling speed of the pickling is preferably 10-20 m/min.
The invention can remove the oxide layer on the surface of the red copper alloy by acid washing, and simultaneously passivate the surface to avoid secondary oxidation.
In the present invention, the water used for the grinding rinse water and the acid post-rinse water is independently preferably tap water. The present invention can further remove impurities by performing the grinding rinse water and the acid post rinse water.
After the pickling is finished, the pickled product is preferably dried. The temperature and time of the drying are not particularly limited, and the drying may be performed according to the technical knowledge of those skilled in the art.
In the present invention, the total deformation of the preform rolling is preferably 30 to 40%; the number of passes of the preform rolling is preferably 4 to 5, more preferably 4; the single-pass deformation of the rolling of the preform is preferably 10-20%; the thickness of the rolled product of the preform is preferably 2.0 to 2.5mm. The thickness of the red copper coiled material can be further reduced by rolling the pre-finished product.
After a pre-finished casting blank is obtained, the pre-finished casting blank is subjected to bell jar annealing and secondary pickling in sequence to obtain an annealing plate strip.
In the invention, the temperature of the bell jar annealing is preferably 380-450 ℃, more preferably 430 ℃; the heat preservation time of the bell jar annealing is preferably 8-12 h, more preferably 10h; the temperature rising rate of the bell jar annealing is preferably 80-100 ℃/h; the bell jar annealing atmosphere is preferably a full nitrogen atmosphere; the gas flow rate of the total nitrogen atmosphere is preferably 15-28 m 3 And/h. According to the invention, through bell jar annealing treatment, on one hand, residual stress in the alloy can be removed, and meanwhile, the homogenization treatment effect can be realized, so that the internal structure of the alloy is more uniform, and the strength, electric conductivity and thermal conductivity of red copper are further improved.
In the invention, the uncoiling tension of the secondary acid washing is preferably 8-12N/mm 2 The method comprises the steps of carrying out a first treatment on the surface of the The coiling tension of the secondary acid washing is preferably 20-25N/mm 2 The method comprises the steps of carrying out a first treatment on the surface of the The pickling speed of the secondary pickling is preferably 10-20 m/min. In the present invention, the specific operation of the secondary pickling is preferably the same as that of the pickling described above, and will not be described here again. The method removes the oxide layer on the surface of the red copper alloy through secondary acid washing, simultaneously passivates the surface and avoids reoxidation.
After the annealed plate strip is obtained, the annealed plate strip is rolled into a finished product and pickled into a finished product in sequence, so that the high-heat-conductivity high-electric-conductivity red copper alloy is obtained.
In the present invention, the total deformation amount of the finish rolling is preferably 10 to 20%, more preferably 12 to 15%; the pass of the finished product rolling is preferably 1-2 passes, more preferably 1 pass; the thickness of the high-heat-conductivity high-electric-conductivity red copper alloy is preferably 2.0mm. The thickness of red copper can directly reach the required technical requirement through rolling finished products.
In the invention, the uncoiling tension of the finished product pickling is preferably 10-15N/mm 2 The method comprises the steps of carrying out a first treatment on the surface of the The coiling tension of the finished product pickling is preferably 20-30N/mm 2 The method comprises the steps of carrying out a first treatment on the surface of the The pickling speed of the finished product pickling is preferably 10-20 m/min. In the present invention, the specific operation of the pickling of the finished product is preferably the same as the pickling described above, and will not be described herein. The invention removes the oxide layer on the surface of the red copper alloy through the acid washing of the finished product, and simultaneously passivates the surface to avoid reoxidation.
After the high-heat-conductivity high-electric-conductivity red copper alloy is obtained, the coiled material punching can be preferably performed on the red copper alloy. The specific operation of punching the web is not particularly limited in the present invention, and may be performed by a process well known to those skilled in the art.
According to the invention, the red copper casting blank is rolled for multiple times, so that the cast ingot can form coiled materials, and the heat conducting property of the cast ingot is improved after the cast ingot is prepared into a punching structure; after rolling, the copper alloy is subjected to acid washing, so that an oxide layer on the surface of the copper alloy can be removed, and the surface is passivated to avoid reoxidation, thereby avoiding the influence of air on the heat conductivity and the electric conductivity of the copper alloy; residual stress in the alloy can be removed through bell jar annealing treatment, and meanwhile, the homogenization treatment effect can be achieved, so that the internal structure of the alloy is more uniform, and the strength, the electric conductivity and the thermal conductivity of red copper are further improved.
The invention provides a high-heat-conductivity high-electric-conductivity red copper alloy prepared by the preparation method, which comprises the following chemical components in percentage by mass: cu:99.90 to 99.99 percent, P:0.0005 to 0.002 percent, fe:0.0010 to 0.005 percent, pb less than or equal to 0.002 percent, cd less than or equal to 0.00045 percent, as less than or equal to 0.0018 percent, sb less than or equal to 0.0018 percent and Bi less than or equal to 0.0008 percent.
The high-heat-conductivity high-electric-conductivity red copper alloy provided by the invention comprises the following components in percentage by mass: 99.90 to 99.99 percent. The invention uses Cu element as matrix element, which can ensure the high heat conduction and high electric conduction of red copper.
The high-heat-conductivity high-electric-conductivity red copper alloy provided by the invention comprises the following components in percentage by mass: 0.0005 to 0.002%, preferably 0.001 to 0.0015%. The invention can play a role in deoxidizing by controlling the content of the P element, reduce the content of impurity oxygen in the red copper, and simultaneously reduce the influence of the P element on the conductivity of the red copper.
The high-heat-conductivity high-electric-conductivity red copper alloy provided by the invention comprises the following components in percentage by mass: 0.0010 to 0.005%, preferably 0.0018 to 0.002%. The strength of the red copper can be improved by controlling the content of Fe element, and meanwhile, the negative influence on the heat conductivity and the electric conductivity of the red copper can be avoided.
The high-heat-conductivity high-electric-conductivity red copper alloy provided by the invention comprises less than or equal to 0.002% of Pb by mass percent.
The high-heat-conductivity high-electric-conductivity red copper alloy provided by the invention comprises less than or equal to 0.00045% of Cd by mass percent.
The high-heat-conductivity high-electric-conductivity red copper alloy provided by the invention comprises less than or equal to 0.0018% of As in percentage by mass.
The high-heat-conductivity high-electric-conductivity red copper alloy provided by the invention comprises less than or equal to 0.0018% of Sb in percentage by mass.
The high-heat-conductivity high-electric-conductivity red copper alloy provided by the invention comprises less than or equal to 0.0008% of Bi by mass percent.
According to the invention, trace P element is introduced into red copper, so that the deoxidization effect can be realized, the content of impurity oxygen in the red copper is reduced, and meanwhile, the content of the P element is strictly controlled, so that the influence on the conductivity of the red copper is reduced; the Fe element can improve the strength of the red copper, and meanwhile, the content of the Fe element is strictly controlled, so that negative influence on the heat conductivity and the electric conductivity of the red copper can be avoided; pb, cd, as, sb and Bi are unavoidable impurity elements, and the content thereof needs to be strictly controlled.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of a high-heat-conductivity high-electric-conductivity red copper alloy comprises the following steps:
(1) Milling a red copper casting blank with the thickness of 14.5mm, and then sequentially performing blooming, pickling and pre-finished product rolling to obtain a pre-finished product casting blank; the surface milling treatment is two times of surface milling, wherein the single-side milling amount of the first surface milling is 0.5mm, the single-side milling amount of the first surface milling is 3mm, and the speed of the first surface milling is 12m/min; the single-side milling amount of the second milling surface is 0.5mm, and the speed of the second milling surface is 15m/min; the total deformation of the blooming is 75.17%; the thickness trend of the red copper casting blank along with the rolling pass during initial rolling is as follows: 14.5mm-11mm-8mm-6.2mm-4.8mm-3.6mm; the acid washing is degreasing liquid washing, sulfuric acid washing, passivation liquid washing, water washing, grinding washing water and acid back washing water which are sequentially carried out; the mass concentration of the sulfuric acid solution adopted in the sulfuric acid washing is 17.5%; the passivating agent adopted by the passivating agent washing is benzotriazole aqueous solution; the mass concentration of the benzotriazole aqueous solution is 0.15%; the uncoiling tension of the pickling is 12N/mm 2 The method comprises the steps of carrying out a first treatment on the surface of the The coiling tension of the acid washing is 15N/mm 2 The method comprises the steps of carrying out a first treatment on the surface of the The pickling speed of the pickling is 18m/min; rolling of said preformIs 34.72%; the thickness trend of the red copper casting blank along with the rolling pass when the pre-finished product is rolled is as follows: 3.6mm-2.98mm-2.6mm-2.35mm;
(2) Sequentially carrying out bell-type annealing and secondary pickling on the pre-finished casting blank obtained in the step (1) to obtain an annealed plate strip; the temperature of the bell jar annealing is 430 ℃, the heat preservation time of the bell jar annealing is 10 hours, and the temperature rising rate of the bell jar annealing is 100 ℃/h; the bell jar annealing atmosphere is a full nitrogen atmosphere; the gas flow rate of the total nitrogen atmosphere is 25m 3 /h; the uncoiling tension of the secondary pickling is 12N/mm 2 The method comprises the steps of carrying out a first treatment on the surface of the The coiling tension of the secondary acid washing is 23N/mm 2 The method comprises the steps of carrying out a first treatment on the surface of the The pickling speed of the secondary pickling is 20m/min, and other conditions are the same as those of the pickling in the step (1);
(3) Sequentially carrying out finished product rolling and finished product pickling on the annealed plate strip obtained in the step (2) to obtain the high-heat-conductivity high-electric-conductivity red copper alloy; the total deformation of the finished product rolling is 14.89%; the pass of the rolling of the finished product is 1 pass; the thickness of the high-heat-conductivity high-electric-conductivity red copper alloy is 2.0mm; the uncoiling tension of the finished product pickling is 15N/mm 2 The method comprises the steps of carrying out a first treatment on the surface of the The coiling tension of the finished product pickling is 28N/mm 2 The method comprises the steps of carrying out a first treatment on the surface of the The pickling speed of the finished product pickling is 20m/min, and the specific operation of the finished product pickling is the same as that of the pickling in the step (1).
Examples 2 to 4
The chemical compositions of the red copper alloys prepared in examples 2 to 4 are shown in Table 1;
other conditions were the same as in example 1.
Comparative example 1
The chemical composition of the T2 red copper is more than 99.9wt.% of Cu+Ag, the conductivity is 56% IACS, the tensile strength is 195MPa, and the hardness is less than or equal to 70HV.
The chemical compositions of the high-heat-conductivity high-electric-conductivity red copper alloy prepared in the examples 1 to 4 are shown in the table 1:
TABLE 1 chemical compositions of highly thermally conductive and highly electrically conductive Red copper alloys prepared in examples 1 to 4
| Cu/％ | P/％ | Fe/％ | Pb/％ | Cd/％ | As/％ | Sb/％ | Bi/％ | Impurity/% | |
| Example 1 | 99.987 | 0.002 | 0.0015 | 0.0018 | 0.0001 | 0.0002 | 0.0005 | 0.0007 | Allowance of |
| Example 2 | 99.985 | 0.0017 | 0.0014 | 0.0012 | 0.0001 | 0.0002 | 0.0005 | 0.0008 | Allowance of |
| Example 3 | 99.986 | 0.0008 | 0.0018 | 0.0008 | 0.0001 | 0.0002 | 0.0005 | 0.0008 | Allowance of |
| Example 4 | 99.990 | 0.0010 | 0.0013 | 0.0009 | 0.0001 | 0.0002 | 0.0004 | 0.0006 | Allowance of |
The properties of the high heat and high electric conductivity red copper alloys prepared in examples 1 to 4 were tested, and the results are shown in table 2:
TABLE 2 Properties of highly thermally conductive and highly electrically conductive Red copper alloys prepared in examples 1 to 4
The tensile strength testing method comprises the following steps: GB/T34505-2017 room temperature tensile test method;
the elongation testing method comprises the following steps: GB/T22834505-2017 room temperature tensile test method;
the method for testing the thermal conductivity comprises the following steps: test method for measuring solid thermal diffusivity by flash method according to ASTM E1461-13;
the hardness test method comprises the following steps: GB/T4340.1-2009 method for the Vickers hardness of metal materials;
the conductivity test method comprises the following steps: YS/T478-2005 copper and copper alloy conductivity vortex detection method;
the 90-degree bending test method specifically comprises the following steps: GB/T232-2010 metal material bending test method.
As can be seen from Table 2, compared with the existing T2 red copper, the high-heat-conductivity and high-electric-conductivity red copper alloy prepared by the preparation method provided by the invention has the advantages of obviously improved tensile strength and hardness, and excellent heat conductivity and electric conductivity.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A preparation method of a high-heat-conductivity high-electric-conductivity red copper alloy comprises the following steps:
(1) Sequentially performing blooming, pickling and pre-product rolling on the red copper casting blank to obtain a pre-product casting blank;
(2) Sequentially carrying out bell-type annealing and secondary pickling on the pre-finished casting blank obtained in the step (1) to obtain an annealed plate strip;
(3) And (3) rolling and pickling the finished product of the annealed plate strip obtained in the step (2) to obtain the high-heat-conductivity high-electric-conductivity red copper alloy.
2. The method according to claim 1, wherein the total deformation amount of the initial rolling in the step (1) is 70-80%, the initial rolling passes are 5-6, and the single-pass deformation amount of the initial rolling is 10-30%.
3. The production method according to claim 1, wherein the acid washing in the step (1) includes degreasing liquid washing, sulfuric acid washing, passivation liquid washing, water washing, polishing washing water and acid post-washing water which are sequentially performed.
4. The preparation method according to claim 3, wherein the mass concentration of the sulfuric acid solution used in the sulfuric acid washing is 15-20%; the passivating agent adopted by the passivating agent washing is benzotriazole aqueous solution; the mass concentration of the benzotriazole aqueous solution is 0.05-0.15%.
5. The method according to claim 1, wherein the acid-washed in the step (1) has an uncoiling tension of 10 to 15N/mm 2 The coiling tension of the acid washing is 10 to 20N/mm 2 The pickling speed of the pickling is 10-20 m/min.
6. The method according to claim 1, wherein the total deformation of the preform in the step (1) is 30-40%, the number of passes of the preform is 4-5, and the single pass deformation of the preform is 10-20%.
7. The preparation method according to claim 1, wherein the temperature of the bell jar annealing in the step (2) is 380-450 ℃, the heat preservation time of the bell jar annealing is 8-12 h, and the atmosphere of the bell jar annealing is a total nitrogen atmosphere; the gas flow rate of the total nitrogen atmosphere is 15-28 m 3 /h。
8. The method according to claim 1 or 7, wherein the temperature rise rate of the bell jar annealing in the step (2) is 80 to 100 ℃/h.
9. The method according to claim 1, wherein the total deformation of the finished product in the step (3) is 10-20%, and the pass of the finished product is 1-2.
10. The high-heat-conductivity high-electric-conductivity red copper alloy prepared by the preparation method of any one of claims 1 to 9 comprises the following chemical components in percentage by mass: cu:99.90 to 99.99 percent, P:0.0005 to 0.002 percent, fe:0.0010 to 0.005 percent, pb less than or equal to 0.002 percent, cd less than or equal to 0.00045 percent, as less than or equal to 0.0018 percent, sb less than or equal to 0.0018 percent and Bi less than or equal to 0.0008 percent.
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