CN116694953A - Copper alloy plate strip for electromagnetic shielding and preparation method thereof - Google Patents
Copper alloy plate strip for electromagnetic shielding and preparation method thereof Download PDFInfo
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 214
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000010949 copper Substances 0.000 claims abstract description 37
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 31
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 239000000956 alloy Substances 0.000 claims description 96
- 229910045601 alloy Inorganic materials 0.000 claims description 93
- 238000010438 heat treatment Methods 0.000 claims description 80
- 238000005266 casting Methods 0.000 claims description 71
- 238000005097 cold rolling Methods 0.000 claims description 53
- 238000005275 alloying Methods 0.000 claims description 47
- 239000002994 raw material Substances 0.000 claims description 43
- 238000005098 hot rolling Methods 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 32
- 238000002844 melting Methods 0.000 claims description 27
- 230000008018 melting Effects 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 23
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 14
- 238000005242 forging Methods 0.000 claims description 13
- 229910052746 lanthanum Inorganic materials 0.000 claims description 12
- 229910052684 Cerium Inorganic materials 0.000 claims description 10
- 238000007712 rapid solidification Methods 0.000 claims description 8
- 229910017945 Cu—Ti Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 12
- 230000005307 ferromagnetism Effects 0.000 abstract description 8
- 230000002829 reductive effect Effects 0.000 abstract description 8
- 238000004220 aggregation Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 230000005684 electric field Effects 0.000 abstract description 5
- 230000036961 partial effect Effects 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 60
- 150000002910 rare earth metals Chemical class 0.000 description 15
- 238000003723 Smelting Methods 0.000 description 13
- 238000004321 preservation Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910017827 Cu—Fe Inorganic materials 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 238000003801 milling Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000010309 melting process Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000005672 electromagnetic field Effects 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000004891 communication Methods 0.000 description 3
- 230000007123 defense Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- 229910005438 FeTi Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000007545 Vickers hardness test Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000004663 powder metallurgy Methods 0.000 description 1
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- -1 rare earth compounds Chemical class 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
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Classifications
-
- 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
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
Abstract
The application provides a copper alloy plate strip for electromagnetic shielding and a preparation method thereof. The copper alloy plate strip for electromagnetic shielding comprises, by weight, 5-10wt% of Fe, 0.05-0.4wt% of Ti, 0.02-0.2wt% of Co, 0.02-0.3wt% of RE and the balance of Cu and unavoidable impurities; wherein RE is rare earth element, and the sum of Ti and Co is less than or equal to 0.5wt%. According to the application, the Fe element content in the copper alloy plate and strip material for electromagnetic shielding is controlled in a specific range, so that air holes can be effectively avoided during preparation, and the optimal balance of conductivity and ferromagnetism of the material is realized; meanwhile, the synergistic effect of Ti and Co with specific content and a small amount of RE is added, so that the problems of partial aggregation and coarse components can be solved, the material cost is reduced, good conductivity and mechanical property can be simultaneously considered, and the broadband electromagnetic shielding effect of the copper alloy plate and strip in high-frequency electric field and low-frequency electromagnetic can be improved.
Description
Technical Field
The application relates to the technical field of nonferrous metal processing, in particular to a copper alloy plate strip for electromagnetic shielding and a preparation method thereof.
Background
The Cu-Fe deformation in-situ composite material (Fe content is 5-50wt%) has the characteristics of high strength, high conductivity, high elasticity, ferromagnetism and the like, and the high conductivity enables the Cu-Fe deformation in-situ composite material to have a good shielding effect on a high-frequency electromagnetic field, and the ferromagnetism also has a good shielding effect on a low-frequency magnetic field, so that the Cu-Fe deformation in-situ composite material becomes a broadband electromagnetic shielding material with a great application prospect, and is widely applied to the fields requiring electromagnetic shielding such as electronics, communication, national defense, aerospace and the like. However, the Fe element has the characteristics of higher melting point, lower density compared with Cu, mutual incompatibility with copper and the like, so that the Cu-Fe deformation in-situ composite material is easy to inhale in the smelting preparation process, the specific gravity segregation and aggregation of the Fe element are caused to grow, the second phase of the Fe element is difficult to prepare a uniformly distributed and fine cast ingot material through smelting, meanwhile, the conductivity of the alloy is greatly reduced due to the increase of the content of the Fe element, and the higher conductivity is difficult to maintain. At present, the preparation methods of the Cu-Fe deformation in-situ composite material mainly comprise a casting method and a powder metallurgy method, and the casting method is a preferred method which has low cost and can realize mass preparation.
In order to solve the problems of element segregation and coarse phase in the casting process of Cu-Fe alloy, rapid solidification and rare earth element addition are widely adopted in the prior art for carrying out tissue refinement; in order to maintain high conductivity, the following method is generally adopted: firstly, the solubility of Fe is reduced by adding other alloy elements, and secondly, the precipitation of Fe is promoted by a proper thermomechanical treatment process. CN 110699571B discloses a preparation method of copper-iron alloy material with electromagnetic shielding property, which adopts an intermediate frequency induction furnace for smelting, degassing, deoxidizing and matching with electromagnetic stirring. CN111636010a discloses a high-strength high-conductivity copper-iron alloy and a preparation method thereof, C and Mo are added for strengthening, and La and Ce are added for inhibiting component segregation. CN 101775520B, CN 111549253B and CN 100532600C disclose rare earth-containing Cu-Fe deformed in-situ composites and methods of making the same. In the prior art, in order to refine the Cu-Fe alloy structure, a large amount of rare earth needs to be added, and excessive rare earth is easy to aggregate rare earth compounds, so that the comprehensive performance of the material is influenced, and meanwhile, the material cost is increased.
Disclosure of Invention
The application mainly aims to provide a copper alloy plate strip for electromagnetic shielding and a preparation method thereof, which are used for solving the problem that the copper alloy material for electromagnetic shielding is difficult to achieve both low cost and high performance in the prior art.
In order to achieve the above object, according to one aspect of the present application, there is provided a copper alloy sheet for electromagnetic shielding, comprising, by weight, 5 to 10% of Fe, 0.05 to 0.4% of Ti, 0.02 to 0.2% of Co, 0.02 to 0.3% of RE, and the balance Cu and unavoidable impurities; wherein RE is rare earth element, and the sum of Ti and Co is less than or equal to 0.5wt%.
Further, the alloy comprises 7.5-9wt% of Fe, 0.05-0.3wt% of Ti, 0.02-0.1wt% of Co, 0.06-0.2wt% of RE and the balance of Cu and unavoidable impurities; wherein the weight ratio of Ti to Co is (0.5-7): 1.
Further, RE includes one or more of Y, la, ce, and Pr; preferably, RE includes La, ce and Pr; more preferably, RE comprises 45-55wt% of La, 35-45wt% of Ce and 5-15wt% of Pr, based on 100% by weight of RE.
Further, the tensile strength of the copper alloy plate strip for electromagnetic shielding is 550-700 MPa, the elongation is more than or equal to 3%, and the conductivity is 50-65% IACS.
According to another aspect of the present application, there is provided the above-mentioned method for producing a copper alloy sheet strip for electromagnetic shielding, comprising the steps of: step S1, sequentially melting and alloying raw materials of a copper alloy plate strip for electromagnetic shielding to obtain a copper alloy melt; step S2, casting the copper alloy melt to obtain a copper alloy casting blank; step S3, carrying out hot rolling or hot forging on the copper alloy casting blank to obtain a copper alloy plate strip blank; s4, cold rolling the copper alloy plate strip blank to obtain a copper alloy cold rolled blank; and S5, performing heat treatment on the copper alloy cold-rolled blank to obtain the copper alloy plate strip for electromagnetic shielding.
Further, step S1 includes: melting raw material Cu, adding raw material Fe and raw material Co for first alloying, and adding raw material Ti and raw material RE for second alloying to obtain copper alloy melt; preferably, the raw material Cu, the raw material Fe and the raw material Co are all added in the form of pure metal sheets, the raw material Ti is added in the form of Cu-Ti intermediate alloy, and the raw material RE is added in the form of Cu-RE intermediate alloy; preferably, the weight percentage of Ti in the Cu-Ti master alloy is 10wt%; and/or the weight percentage of RE in the Cu-RE master alloy is 5-15wt%; preferably, the Cu-RE intermediate alloy is divided into two parts, namely a first Cu-RE intermediate alloy and a second Cu-RE intermediate alloy, wherein the weight ratio of the first Cu-RE intermediate alloy to the second Cu-RE intermediate alloy is 1:2, the first Cu-RE intermediate alloy is added before the raw material Fe is added, and the second Cu-RE intermediate alloy is added in the second alloying; preferably, the melting temperature is 1180-1220 ℃; and/or the temperature of the first alloying is 1300-1330 ℃; and/or the temperature of the second alloying is 1250-1300 ℃.
Further, in step S2, the casting includes rapid solidification casting; preferably, electromagnetic field assisted casting is employed; preferably, the temperature of the rapid solidification casting is 1250-1300 ℃, and the speed is 30-80 mm/min.
Further, in the step S3, the temperature of hot rolling or hot forging is 900-980 ℃ and the time is 2-8 hours; preferably, the deformation amount of the hot rolling is more than or equal to 70%, and preferably 80-95%.
Further, in step S4, the deformation amount of the cold rolling is 50 to 95%, preferably 70 to 95%.
Further, in step S5, the temperature of the heat treatment is 300-600 ℃ and the time is 1-6 hours.
By adopting the technical scheme of the application, the Fe element content in the copper alloy plate and strip material for electromagnetic shielding is controlled within a specific range, so that air holes can be effectively avoided during preparation, the alloy structure is uniform, and the optimal balance of the conductivity and ferromagnetism of the material is realized. Meanwhile, ti and Co with specific contents are added to form synergistic effect with a small amount of RE, so that Cu matrix and Fe phase in the copper alloy plate and strip material can be thinned, and the problems of partial aggregation and coarse components are effectively solved. In conclusion, the copper alloy plate strip with specific components does not need to be added with a large amount of rare earth elements, so that the material cost can be effectively reduced, good conductivity and mechanical properties can be simultaneously considered, the broadband electromagnetic shielding effect of the copper alloy plate strip in high-frequency electric fields and low-frequency electromagnetic fields is improved, and the copper alloy plate strip is convenient to apply in the fields of electronics, communication, national defense, aerospace and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
fig. 1 shows a flowchart of a process for producing a copper alloy sheet for electromagnetic shielding according to embodiment 1 of the present application;
FIG. 2 shows SEM (500X) topography of a copper alloy billet cross-section structure according to example 1 of the present application; and
fig. 3 shows SEM morphology (5000×) of a cross-sectional structure of a copper alloy billet according to example 1 of the present application.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The application will be described in detail below with reference to the drawings in connection with embodiments.
As described in the background art of the present application, the prior art has a problem that it is difficult to combine low cost and high performance with the copper alloy material for electromagnetic shielding. In order to solve the above problems, in an exemplary embodiment of the present application, a copper alloy strip for electromagnetic shielding is provided, which comprises, by weight, 5 to 10% of Fe, 0.05 to 0.4% of Ti, 0.02 to 0.2% of Co, 0.02 to 0.3% of RE, and the balance Cu and unavoidable impurities; wherein RE is rare earth element, and the sum of Ti and Co is less than or equal to 0.5wt%. Wherein the impurities include, but are not limited to, one or more of Mg, sn, zn, O, S, H, etc., and the total amount of impurities is controlled in accordance with conventional levels in the art. The copper alloy plate strip refers to a copper alloy plate or a copper alloy strip, which are common preparation forms of copper alloy in the field, and are only different in thermal deformation process, and those skilled in the art can understand the process, and are not described herein.
The inventor unexpectedly discovers that when the content of Fe element in the copper alloy plate and strip for electromagnetic shielding is 5-10wt%, on one hand, the content of Fe element in the copper is lower in melting point, and the complete solid solution of Fe element can be realized during preparation, so that serious air suction caused by overhigh temperature of copper melt can not occur, and air holes appear during casting to reduce the uniformity of alloy structure; on the other hand, the copper alloy plate and strip material for electromagnetic shielding with the Fe element content in the range has higher conductivity, has comprehensive balance of conductivity and ferromagnetism, and is beneficial to realizing the broadband electromagnetic shielding effect of a high-frequency electric field and low-frequency electromagnetic. If the content of Fe element is less than 5%, the electromagnetic shielding effect of the copper alloy strip is poor, and if the content of Fe element is more than 10%, the conductivity of the copper alloy strip is rapidly reduced, so that the content of Fe element is limited to be within the specific range.
When Ti and Co elements with specific contents are added into the copper alloy plate strip for electromagnetic shielding, feTi compounds and CoTi compounds can be formed to be distributed between the solidification front and dendrites of Fe elements, so that the size of Fe phases in the alloy can be thinned, and the distribution uniformity can be improved; meanwhile, co is dissolved in Fe and not dissolved in Cu, which is favorable for the precipitation of Fe phase from a copper matrix and becomes a fiber reinforced phase, so that the conductivity of the alloy is further improved while the alloy is further reinforced.
Meanwhile, when the rare earth element with specific content is added into the copper alloy plate and strip for electromagnetic shielding, the refining of Fe phase can be promoted in cooperation with Ti and Co elements, oxygen and other impurities in a melt can be reduced in the preparation process, and the fusion of Fe element is promoted.
In addition, the inventors have unexpectedly found during the course of the study that too low contents of Ti, co and rare earth elements result in poor effects such as the above-mentioned refining, and too high contents result in rapid decrease in conductivity of the copper alloy strip, while causing increase in cost and deterioration in workability, so that the present application limits the contents of Ti, co and rare earth elements to be within the above-mentioned specific ranges. In addition, in view of the influence of Ti and Co on the conductivity of the copper alloy strip for electromagnetic shielding of the present application, the present application is particularly limited to the sum of Ti and Co of 0.5wt% or less in order to ensure a higher conductivity of the copper alloy strip.
According to the application, the Fe element content in the copper alloy plate and strip material for electromagnetic shielding is controlled within a specific range, so that air holes can be effectively avoided during preparation, and the optimal balance of conductivity and ferromagnetism of the material is realized. Meanwhile, ti and Co are added to synergistically act with a small amount of RE, so that Cu matrix and Fe phases in the copper alloy plate and strip material can be thinned, and the problems of partial aggregation and coarse components are effectively solved. In conclusion, the copper alloy plate strip with specific components does not need to be added with a large amount of rare earth elements, so that the material cost can be effectively reduced, good conductivity and mechanical properties can be simultaneously considered, the broadband electromagnetic shielding effect of the copper alloy plate strip for electromagnetic shielding in high-frequency electric fields and low-frequency electromagnetism is improved, and the copper alloy plate strip is convenient to apply in fields requiring electromagnetic shielding such as electronics, communication, national defense, aerospace and the like.
For the purpose of enabling the material to have better conductivity and ferromagnetism, in a preferred embodiment, the material comprises 7.5-9wt% of Fe, 0.05-0.3wt% of Ti, 0.02-0.1wt% of Co, 0.06-0.2wt% of RE, and the balance of Cu and unavoidable impurities; wherein the weight ratio of Ti to Co is (0.5-7): 1, so that rare earth, ti and Co elements can jointly promote Fe phase refinement, and the best matching of the strength and the conductivity of the Cu-Fe in-situ composite material is achieved.
The rare earth RE element is conventional rare earth in the field, and in order to further improve the synergistic refining effect of the rare earth element and Ti and Co elements on the copper alloy plate strip, in a preferred embodiment, RE comprises one or more of Y, la, ce and Pr; preferably, RE includes La, ce and Pr; more preferably, the RE comprises 45-55wt% of La, 35-45wt% of Ce and 5-15wt% of Pr, calculated by the weight percentage of RE as 100%, so that the preparation of materials can be more convenient, the rapid melting of rare earth elements and the homogenization in a melt can be realized.
As described above, the copper alloy sheet and strip with specific components of the application can achieve good electrical conductivity and mechanical properties, and in a preferred embodiment, the tensile strength of the copper alloy sheet and strip for electromagnetic shielding is 550-700 MPa, and the elongation is more than or equal to 3%, wherein the elongation is measured at room temperature, and the room temperature is 20-30 ℃; the conductivity is 50-65% IACS, and the comprehensive performance is better.
In still another exemplary embodiment of the present application, there is also provided a method for manufacturing the above-mentioned copper alloy sheet strip for electromagnetic shielding according to the present application, including the steps of: step S1, sequentially melting and alloying raw materials of a copper alloy plate strip for electromagnetic shielding to obtain a copper alloy melt; step S2, casting the copper alloy melt to obtain a copper alloy casting blank; step S3, carrying out hot rolling or hot forging on the copper alloy casting blank to obtain a copper alloy plate strip blank; s4, cold rolling the copper alloy plate strip blank to obtain a copper alloy cold rolled blank; and S5, performing heat treatment on the copper alloy cold-rolled blank to obtain the copper alloy plate strip for electromagnetic shielding. Wherein, step S1 can use covering agent to accelerate melting, and the covering agent is flake graphite or charcoal.
According to the method, raw materials of the copper alloy plate strip for electromagnetic shielding are melted and alloyed in sequence according to component limitation, so that a copper alloy melt is obtained. The application limits the content of Fe element in a specific range, so that the complete solid solution of Fe element can be realized in the melting and alloying process, and serious air suction caused by overhigh temperature of copper melt can not occur, air holes occur in casting, and the structure can be thinned.
And secondly, casting the copper alloy melt to obtain a copper alloy casting blank, and carrying out hot rolling or hot forging to obtain a copper alloy plate strip blank. The thermal deformation method can be adjusted accordingly according to different target forms of the copper alloy, for example, the copper alloy casting blank is hot rolled to obtain a copper alloy slab, or the copper alloy casting blank is hot forged to obtain a copper alloy strip blank, which are understood by those skilled in the art and are not described herein.
And finally, carrying out cold rolling and heat treatment on the copper alloy plate strip blank to obtain the copper alloy plate strip for electromagnetic shielding. Wherein the cold rolling process and the heat treatment process can be selected one or more times as required. The copper alloy plate strip for electromagnetic shielding obtained by the preparation method can give consideration to good conductivity and mechanical property, has simple process, low cost and easy operation, and is more suitable for industrial mass production.
Specifically, in a preferred embodiment, step S1 includes: melting raw material Cu, adding raw material Fe and raw material Co for first alloying, and adding raw material Ti and raw material RE for second alloying to obtain copper alloy melt; preferably, the raw material Cu, the raw material Fe and the raw material Co are all added in the form of pure metal sheets, the raw material Ti is added in the form of a Cu-Ti master alloy, and the raw material RE is added in the form of a Cu-RE master alloy.
For the purpose of enabling further rapid melting of Ti and rare earth elements into the melt and achieving homogenization in the melt, the Cu-Ti master alloy preferably has a Ti content of 10 wt.%; and/or the weight percentage of RE in the Cu-RE master alloy is 5-15wt%.
Preferably, the Cu-RE intermediate alloy is divided into two parts, namely a first Cu-RE intermediate alloy and a second Cu-RE intermediate alloy, wherein the weight ratio of the first Cu-RE intermediate alloy to the second Cu-RE intermediate alloy is 1:2, the first Cu-RE intermediate alloy is added before the raw material Fe is added, and the second Cu-RE intermediate alloy is added in the second alloying. The first Cu-RE intermediate alloy can better reduce oxygen and other impurities in a melt when the Fe raw material is added, and promote the fusion of Fe element; the second Cu-RE intermediate alloy can be cooperated with Ti and Co elements to further refine Fe phase, thereby further improving the mechanical property of the alloy.
Preferably, the melting temperature is 1180-1220 ℃; and/or the temperature of the first alloying is 1300-1330 ℃; and/or the temperature of the second alloying is 1250-1300 ℃, so that the rapid melting of Fe, co, ti and rare earth elements and the uniform melt structure can be better realized.
To further promote uniformity of element distribution in the copper alloy strip material and to improve strip mechanical properties, in a preferred embodiment, the casting comprises rapid solidification casting in step S2; preferably, electromagnetic field assisted casting is employed; for the purpose of further reducing melt suction and reducing ingot defects, preferably, the temperature of rapid solidification casting is 1250-1300 ℃, and the speed is 30-80 mm/min by mainly adopting a vertical semi-continuous casting mode.
In a preferred embodiment, in the step S3, the temperature of hot rolling or hot forging is 900-980 ℃ and the time is 2-8 hours; the temperature of the hot working is better matched with the properties of the raw materials, so that the thermal deformation effect can be further improved; the heat preservation time can further ensure that the temperature in the casting blank is uniform and the tissue is not deteriorated. Preferably, the deformation of the hot rolling is more than or equal to 70%, preferably 80-95%, and the hot rolling is more convenient to prepare. The deformation amount refers to the total deformation amount of hot rolling or hot forging, the pass reduction deformation amount is related to the equipment capacity, the strict limitation is not made, and the person skilled in the art can carry out targeted adjustment according to the actual preparation condition.
In a preferred embodiment, the deformation amount of the cold rolling in step S4 is 50 to 95% for the purpose of further improving the overall properties of the copper alloy sheet and strip, and preferably 70 to 95% for obtaining a more excellent fiber-reinforced effect.
In a preferred embodiment, in step S5, the heat treatment is performed at a temperature of 300 to 600 ℃ for a time of 1 to 6 hours. The main element Fe added in the copper alloy plate and strip provided by the application has extremely low solubility in a Cu matrix at room temperature, and through the temperature heat treatment, the Fe element can be ensured to be precipitated out of the Cu matrix as much as possible, and is combined and deformed into a fiber reinforced phase, so that the alloy is further reinforced and the conductivity is further improved. The above heat treatment temperature is too high or too long, which may cause softening of the alloy, and the temperature is too low or insufficient, which may not promote precipitation of Fe element, resulting in reduction of the electrical conductivity of the alloy, so the heat treatment parameters are limited to the above specific ranges.
Typically, but not limited to, the electromagnetic shielding copper alloy strip comprises, in weight percent, a range of values consisting of Fe 5wt%, 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt%, 9.5wt%, 10wt%, or any two thereof, a range of values consisting of Ti 0.05wt%, 0.1wt%, 0.15wt%, 0.2wt%, 0.25wt%, 0.3wt%, 0.35wt%, 0.4wt%, or any two thereof, a range of values consisting of Co 0.02wt%, 0.05wt%, 0.08wt%, 0.1wt%, 0.12wt%, 0.15wt%, 0.18wt%, 0.2wt%, or any two thereof, and a range of values consisting of RE 0.02wt%, 0.06wt%, 0.1wt%, 0.15wt%, 0.2wt%, 0.25wt%, 0.3wt%, or any two thereof.
Typically, but not limited to, the sum of the weights of Ti and Co is 0.07wt%, 0.1wt%, 0.15wt%, 0.2wt%, 0.25wt%, 0.3wt%, 0.35wt%, 0.4wt%, 0.45wt%, 0.5wt%, or any two values thereof; the weight ratio of Ti to Co is a range of values consisting of 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, or any two values thereof.
Typically, but not limited to, RE comprises, in terms of weight percent RE of 100%, 45wt%, 48wt%, 50wt%, 52wt%, 55wt% or any two thereof, 35wt%, 38wt%, 40wt%, 42wt%, 45wt% or any two thereof, pr 5wt%, 8wt%, 10wt%, 12wt%, 15wt% or any two thereof.
Typically, but not limited to, in step S1, the melting temperature is 1180 ℃, 1190 ℃, 1200 ℃, 1210 ℃, 1220 ℃ or any two values thereof; the temperature of the first alloying is 1300 ℃, 1305 ℃, 1310 ℃, 1315 ℃, 1320 ℃, 1325 ℃, 1330 ℃ or any two values of the range; the second alloying temperature is 1250 ℃, 1255 ℃, 1260 ℃, 1265 ℃, 1270 ℃, 1275 ℃, 1280 ℃, 1285 ℃, 1290 ℃, 1295 ℃, 1300 ℃ or any two values thereof.
Typically, but not limited to, in step S2, the rapid solidification casting temperature is 1250 ℃, 1260 ℃, 1270 ℃, 1280 ℃, 1290 ℃, 1300 ℃, or any two thereof, and the speed is 30mm/min, 40mm/min, 50mm/min, 60mm/min, 70mm/min, 80mm/min, or any two thereof.
Typically, but not limited to, in step S3, the hot rolling or hot forging temperature is 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, 950 ℃, 960 ℃, 970 ℃, 980 ℃ or any two values thereof, and the time is 2h, 3h, 4h, 5h, 6h, 7h, 8h or any two values thereof; the deformation amount of the hot rolling is 70%, 75%, 80%, 85%, 90%, 95% or a range of values consisting of any two values thereof.
Typically, but not limited to, in step S4, the cold rolling is performed with a deformation of 50%, 60%, 70%, 80%, 90%, 95% or any two values thereof.
Typically, but not limited to, in step S5, the heat treatment is performed at a temperature of 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃ or any two values thereof, and the time is 1h, 2h, 3h, 4h, 5h, 6h or any two values thereof.
The application is described in further detail below in connection with specific examples which are not to be construed as limiting the scope of the application as claimed.
Example 1
The components of the copper alloy plate strip for electromagnetic shielding are shown in table 1, and the preparation process flow chart is shown in fig. 1.
The rare earth RE raw material used a Cu-5wt% RE master alloy, where RE comprises 50wt% La,40 wt% Ce and 10wt% Pr, according to the first Cu-RE master alloy: the second Cu-RE master alloy weight ratio = 1:2 is split into two parts.
(1) Melting and alloying: putting the Cu metal sheet into a smelting device to be melted at 1200 ℃; adding a first Cu-RE intermediate alloy, then heating to 1330 ℃, and adding Fe metal sheets and Co metal sheets for first alloying; cooling to 1250 ℃, and then adding Cu-10wt% of Ti intermediate alloy and a second Cu-RE intermediate alloy for second alloying to obtain a copper alloy melt; the melting process is assisted by using a covering agent which is crystalline flake graphite;
(2) Casting: under the assistance of an externally applied magnetic field, casting copper alloy melt with the components reaching standards at the temperature of 1255 ℃ and the speed of 70mm/min to obtain a copper alloy casting blank;
(3) And (3) hot rolling: heating a copper alloy casting blank, and then carrying out hot rolling to obtain a copper alloy hot rolled plate blank, wherein the heating temperature is 900 ℃, the heat preservation time is 6h, and the thermal deformation is 80%;
(4) Cold rolling: milling and cold rolling the copper alloy hot-rolled plate blank, wherein the cold rolling deformation is 95%, and the copper alloy cold-rolled plate blank is obtained;
(5) And (3) heat treatment: performing heat treatment on the copper alloy cold-rolled plate blank to obtain a copper alloy plate blank; the heat treatment temperature is 350 ℃ and the time is 5 hours;
(6) And (3) a finished product: after 4 times of cold rolling and 3 times of heat treatment are alternately performed, the copper alloy plate for broadband electromagnetic shielding with the thickness of 0.12mm is obtained after the last time of cold rolling.
Example 2
The composition of the copper alloy sheet and strip for electromagnetic shielding is shown in Table 1.
The rare earth RE raw material uses Cu-10wt% RE master alloy, wherein RE comprises 50wt% La,40 wt% Ce and 10wt% Pr, according to the first Cu-RE master alloy: the second Cu-RE master alloy weight ratio = 1:2 is split into two parts.
(1) Melting and alloying: putting the Cu metal sheet into a smelting device to be melted at 1200 ℃; adding a first Cu-RE intermediate alloy, then heating to 1330 ℃, and adding Fe metal sheets and Co metal sheets for first alloying; cooling to 1265 ℃, and then adding Cu-10wt% of Ti intermediate alloy and a second Cu-RE intermediate alloy for second alloying to obtain a copper alloy melt; the melting process is assisted by using a covering agent which is crystalline flake graphite;
(2) Casting: under the assistance of an externally applied magnetic field, casting a copper alloy melt with the components reaching standards at the temperature of 1265 ℃ and the speed of 60mm/min to obtain a copper alloy casting blank;
(3) And (3) hot rolling: heating a copper alloy casting blank, and then carrying out hot rolling to obtain a copper alloy hot rolled blank, wherein the heating temperature is 940 ℃, the heat preservation time is 4 hours, and the thermal deformation is 80%;
(4) Cold rolling: milling and cold rolling the copper alloy hot-rolled plate blank, wherein the cold rolling deformation is 90%, and obtaining the copper alloy cold-rolled plate blank;
(5) And (3) heat treatment: performing heat treatment on the copper alloy cold-rolled plate blank to obtain a copper alloy plate blank; the heat treatment temperature is 400 ℃ and the time is 3 hours;
(6) And (3) a finished product: after 3 times of cold rolling and 2 times of heat treatment are alternately performed, the copper alloy plate for broadband electromagnetic shielding with the thickness of 0.15mm is obtained after the last time of cold rolling.
Example 3
The composition of the copper alloy sheet and strip for electromagnetic shielding is shown in Table 1.
The rare earth RE raw material uses Cu-10wt% RE master alloy, wherein RE comprises 50wt% La,40 wt% Ce and 10wt% Pr, according to the first Cu-RE master alloy: the second Cu-RE master alloy weight ratio = 1:2 is split into two parts.
(1) Melting and alloying: putting the Cu metal sheet into a smelting device to be melted at 1200 ℃; adding a first Cu-RE intermediate alloy, then heating to 1330 ℃, and adding Fe metal sheets and Co metal sheets for first alloying; cooling to 1280 ℃, and then adding Cu-10wt% of Ti intermediate alloy and a second Cu-RE intermediate alloy for second alloying to obtain a copper alloy melt; the melting process is assisted by using a covering agent which is crystalline flake graphite;
(2) Casting: under the assistance of an externally applied magnetic field, casting a copper alloy melt with the components reaching standards at 1280 ℃ and at a speed of 55mm/min to obtain a copper alloy casting blank;
(3) And (3) hot rolling: heating a copper alloy casting blank, and then carrying out hot rolling to obtain a copper alloy hot rolled blank, wherein the heating temperature is 950 ℃, the heat preservation time is 3h, and the thermal deformation is 80%;
(4) Cold rolling: milling and cold rolling the copper alloy hot-rolled plate blank, wherein the cold rolling deformation is 85%, and the copper alloy cold-rolled plate blank is obtained;
(5) And (3) heat treatment: performing heat treatment on the copper alloy cold-rolled plate blank to obtain a copper alloy plate blank; the heat treatment temperature is 450 ℃ and the time is 2 hours;
(6) And (3) a finished product: after 3 times of cold rolling and 2 times of heat treatment are alternately performed, the copper alloy plate for broadband electromagnetic shielding with the thickness of 0.15mm is obtained after the last time of cold rolling.
Example 4
The composition of the copper alloy sheet and strip for electromagnetic shielding is shown in Table 1.
The rare earth RE feedstock used a Cu-15wt% RE master alloy, where RE comprises 50wt% La,40 wt% Ce and 10wt% Pr, according to the first Cu-RE master alloy: the second Cu-RE master alloy weight ratio = 1:2 is split into two parts.
(1) Melting and alloying: putting the Cu metal sheet into a smelting device to be melted at 1200 ℃; adding a first Cu-RE intermediate alloy, then heating to 1330 ℃, and adding Fe metal sheets and Co metal sheets for first alloying; cooling to 1290 ℃, and then adding Cu-10wt% of Ti intermediate alloy and a second Cu-RE intermediate alloy for second alloying to obtain a copper alloy melt; the melting process is assisted by using a covering agent which is crystalline flake graphite;
(2) Casting: casting copper alloy melt with the components reaching standards under the assistance of an external magnetic field at 1290 ℃ and at the speed of 50mm/min to obtain a copper alloy casting blank;
(3) And (3) hot rolling: heating a copper alloy casting blank, and then carrying out hot rolling to obtain a copper alloy hot rolled blank, wherein the heating temperature is 960 ℃, the heat preservation time is 2h, and the thermal deformation is 80%;
(4) Cold rolling: milling and cold rolling the copper alloy hot-rolled plate blank, wherein the cold rolling deformation is 70%, and the copper alloy cold-rolled plate blank is obtained;
(5) And (3) heat treatment: performing heat treatment on the copper alloy cold-rolled plate blank to obtain a copper alloy plate blank; the heat treatment temperature is 500 ℃ and the time is 1h;
(6) And (3) a finished product: after 3 times of cold rolling and 2 times of heat treatment are alternately performed, the copper alloy plate for broadband electromagnetic shielding with the thickness of 0.20mm is obtained after the last time of cold rolling.
Example 5
The composition of the copper alloy sheet and strip for electromagnetic shielding is shown in Table 1.
The rare earth RE feedstock used a Cu-15wt% RE master alloy, where RE comprises 50wt% La,40 wt% Ce and 10wt% Pr, according to the first Cu-RE master alloy: the second Cu-RE master alloy weight ratio = 1:2 is split into two parts.
(1) Melting and alloying: putting the Cu metal sheet into a smelting device to be melted at 1200 ℃; adding a first Cu-RE intermediate alloy, then heating to 1330 ℃, and adding Fe metal sheets and Co metal sheets for first alloying; cooling to 1300 ℃, and then adding Cu-10wt% of Ti intermediate alloy and a second Cu-RE intermediate alloy for second alloying to obtain a copper alloy melt; the melting process is assisted by using a covering agent which is crystalline flake graphite;
(2) Casting: under the assistance of an externally applied magnetic field, casting a copper alloy melt with the components reaching standards at the temperature of 1300 ℃ and the speed of 45mm/min to obtain a copper alloy casting blank;
(3) And (3) hot rolling: heating a copper alloy casting blank, and then carrying out hot rolling to obtain a copper alloy hot rolled plate blank, wherein the heating temperature is 980 ℃, the heat preservation time is 2h, and the thermal deformation is 90%;
(4) Cold rolling: milling and cold rolling the copper alloy hot-rolled plate blank, wherein the cold rolling deformation is 60%, and the copper alloy cold-rolled plate blank is obtained;
(5) And (3) heat treatment: performing heat treatment on the copper alloy cold-rolled plate blank to obtain a copper alloy plate blank; the heat treatment temperature is 550 ℃ and the time is 1h;
(6) And (3) a finished product: after 4 times of cold rolling and 3 times of heat treatment are alternately performed, the copper alloy plate for broadband electromagnetic shielding with the thickness of 0.25mm is obtained after the last time of cold rolling.
Examples 6 to 9
The difference from example 1 is that the composition of the copper alloy sheet and strip for electromagnetic shielding is different, and the details are shown in Table 1.
Example 10
The difference from example 1 is that rare earth RE comprises 45wt% La,45 wt% Ce and 10wt% Pr.
Example 11
The difference from example 1 is that the rare earth RE comprises 55wt% La,35 wt% Ce and 10% Pr by weight.
Example 12
The difference from example 1 is that in step (1), melting and alloying: putting the Cu metal sheet into a smelting device to be melted at 1180 ℃; adding a first Cu-RE intermediate alloy, then heating to 1300 ℃, and adding Fe metal sheets and Co metal sheets to perform first alloying; cooling to 1250 ℃, and then adding Cu-10wt% of Ti intermediate alloy and a second Cu-RE intermediate alloy for second alloying to obtain a copper alloy melt; the melting process is assisted with a coating agent, which is crystalline flake graphite.
Example 13
The difference from example 1 is that in step (1), melting and alloying: putting the Cu metal sheet into a smelting device to be melted at 1220 ℃; adding a first Cu-RE intermediate alloy, then heating to 1330 ℃, and adding Fe metal sheets and Co metal sheets for first alloying; cooling to 1300 ℃, and then adding Cu-10wt% of Ti intermediate alloy and a second Cu-RE intermediate alloy for second alloying to obtain a copper alloy melt; the melting process is assisted with a coating agent, which is crystalline flake graphite.
Example 14
The difference from example 1 is that in step (2), casting: under the assistance of an externally applied magnetic field, casting the copper alloy melt with the components reaching the standards at 1250 ℃ and at the speed of 30mm/min to obtain a copper alloy casting blank.
Example 15
The difference from example 1 is that in step (2), casting: under the assistance of an externally applied magnetic field, casting the copper alloy melt with the components reaching the standards at the temperature of 1300 ℃ and the speed of 80mm/min to obtain a copper alloy casting blank.
Example 16
The difference from example 1 is that in step (3), hot rolling: and (3) heating the copper alloy casting blank, and then carrying out hot rolling to obtain a copper alloy hot rolled plate blank, wherein the heating temperature is 900 ℃, the heat preservation time is 8 hours, and the thermal deformation is 70%.
Example 17
The difference from example 1 is that in step (3), hot rolling: and (3) heating the copper alloy casting blank, and then carrying out hot rolling to obtain a copper alloy hot rolled plate blank, wherein the heating temperature is 980 ℃, the heat preservation time is 2h, and the thermal deformation is 95%.
Example 18
The difference from example 1 is that in step (4), cold rolling: and (3) milling and cold rolling the copper alloy hot-rolled plate blank, wherein the cold rolling deformation is 50%, and the copper alloy cold-rolled plate blank is obtained.
Example 19
The difference from example 1 is that in step (5), heat treatment: performing heat treatment on the copper alloy cold-rolled plate blank to obtain a copper alloy plate blank; the heat treatment temperature is 300 ℃ and the time is 6 hours.
Example 20
The difference from example 1 is that in step (5), heat treatment: performing heat treatment on the copper alloy cold-rolled plate blank to obtain a copper alloy plate blank; the heat treatment temperature is 600 ℃ and the time is 1h.
Example 21
The composition of the copper alloy sheet strip for electromagnetic shielding was the same as in example 1.
The rare earth RE raw material used a Cu-5wt% RE master alloy, where RE comprises 50wt% La,40 wt% Ce and 10wt% Pr, according to the first Cu-RE master alloy: the second Cu-RE master alloy weight ratio = 1:2 is split into two parts.
(1) Melting and alloying: putting the Cu metal sheet into a smelting device to be melted at 1200 ℃; adding a first Cu-RE intermediate alloy, then heating to 1330 ℃, and adding Fe metal sheets and Co metal sheets for first alloying; cooling to 1250 ℃, and then adding Cu-10wt% of Ti intermediate alloy and a second Cu-RE intermediate alloy for second alloying to obtain a copper alloy melt; the melting process is assisted by using a covering agent which is crystalline flake graphite;
(2) Casting: under the assistance of an externally applied magnetic field, casting copper alloy melt with the components reaching standards at the temperature of 1255 ℃ and the speed of 70mm/min to obtain a copper alloy casting blank;
(3) Hot forging: heating a copper alloy casting blank, and then carrying out hot forging to obtain a copper alloy hot-forging strip blank, wherein the heating temperature is 900 ℃, the heat preservation time is 6 hours, and the thermal deformation is 80%;
(4) Cold rolling: milling and cold rolling the copper alloy hot-forging strip blank, wherein the cold rolling deformation is 95%, and obtaining a copper alloy cold-rolling strip blank;
(5) And (3) heat treatment: performing heat treatment on the copper alloy cold-rolled strip blank to obtain a copper alloy strip blank; the heat treatment temperature is 350 ℃ and the time is 5 hours;
(6) And (3) a finished product: after 4 times of cold rolling and 3 times of heat treatment are alternately performed, the copper alloy strip for broadband electromagnetic shielding with the thickness of 0.12mm is obtained after the last time of cold rolling.
Comparative example 1
The composition is shown in Table 1.
(1) Melting and alloying: putting the Cu metal sheet into a smelting device to be melted at 1200 ℃; heating to over 1330 ℃, adding Fe metal sheet to melt to obtain copper alloy melt;
(2) Casting: under the assistance of an externally applied magnetic field, casting copper alloy melt with the components reaching standards at the temperature of 1255 ℃ and the speed of 70mm/min to obtain a copper alloy casting blank;
(3) And (3) hot rolling: heating a copper alloy casting blank, and then carrying out hot rolling to obtain a copper alloy hot rolled blank, wherein the heating temperature is 950 ℃, the heat preservation time is 3h, and the thermal deformation is 80%;
(4) Cold rolling: milling and cold rolling the copper alloy hot-rolled plate blank, wherein the cold rolling deformation is 85%, and the copper alloy cold-rolled plate blank is obtained;
(5) And (3) heat treatment: performing heat treatment on the copper alloy cold-rolled plate blank to obtain a copper alloy plate blank; the heat treatment temperature is 350 ℃ and the time is 5 hours;
(6) And (3) a finished product: after 4 times of cold rolling and 3 times of heat treatment are alternately performed, the copper alloy sheet with the thickness of 0.15mm is obtained after the last time of cold rolling.
Comparative example 2
The composition is shown in Table 1.
(1) Melting and alloying: putting the Cu metal sheet into a smelting device to be melted at 1200 ℃; heating to over 1330 ℃, adding Fe metal sheet to melt to obtain copper alloy melt;
(2) Casting: under the assistance of an externally applied magnetic field, casting a copper alloy melt with the components reaching standards at the temperature of 1300 ℃ and the speed of 45mm/min to obtain a copper alloy casting blank;
(3) And (3) hot rolling: heating a copper alloy casting blank, and then carrying out hot rolling to obtain a copper alloy hot rolled plate blank, wherein the heating temperature is 980 ℃, the heat preservation time is 2h, and the thermal deformation is 90%;
(4) Cold rolling: milling and cold rolling the copper alloy hot-rolled plate blank, wherein the cold rolling deformation is 85%, and the copper alloy cold-rolled plate blank is obtained;
(5) And (3) heat treatment: performing heat treatment on the copper alloy cold-rolled plate blank to obtain a copper alloy plate blank; the heat treatment temperature is 550 ℃ and the time is 1h;
(6) And (3) a finished product: after 4 times of cold rolling and 3 times of heat treatment are alternately performed, the copper alloy sheet with the thickness of 0.20mm is obtained after the last time of cold rolling.
Comparative examples 3 to 8
The difference from example 1 is that the composition of the copper alloy sheet and strip for electromagnetic shielding is different, and the details are shown in Table 1.
The SEM morphology (500×) of the cross-sectional structure of the copper alloy billet of example 1 is shown in fig. 2, the SEM morphology (5000×) of the cross-sectional structure of the copper alloy billet is shown in fig. 3, a in fig. 3 is an FeTi/CoTi compound, and b in fig. 3 is a rare earth-containing compound.
The main performance test results of the copper alloy strips of the above examples and comparative examples are shown in table 2.
The testing method comprises the following steps:
tensile strength: based on GB/T228.1-2010 section 1 of Metal Material tensile test: room temperature test methods, sample preparation and measurement.
Elongation percentage: based on GB/T228.1-2010 section 1 of Metal Material tensile test: room temperature test methods, sample preparation and measurement.
Vickers hardness: based on GB/T4340.1-2009 section 1 of Vickers hardness test of Metal materials: test methods.
Conductivity: based on GB/T32791-2016 test method for testing conductivity vortex of copper and copper alloy.
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As can be seen from fig. 2 and 3, the Ti and Co elements added in the embodiments of the present application are distributed between solidification fronts and dendrites of Fe elements by forming FeTi compounds and CoTi compounds, which helps to refine the size and uniformity of distribution of Fe phases in the alloy, and Co helps to precipitate Fe phases from the copper matrix, so as to promote optimal matching of material strength and conductivity.
Compared with the comparative examples, the embodiment of the application can effectively avoid air holes during preparation by controlling the content of Fe element in the copper alloy plate and strip material for electromagnetic shielding in a specific range, thereby homogenizing alloy structure and realizing optimal balance of conductivity and ferromagnetism of the material. Meanwhile, ti and Co with specific contents are added to form synergistic effect with a small amount of RE, so that Cu matrix and Fe phase in the copper alloy plate and strip material can be thinned, and the problems of partial aggregation and coarse components are effectively solved. In conclusion, the copper alloy plate strip with specific components does not need to be added with a large amount of rare earth elements, so that the material cost can be effectively reduced, good conductivity and mechanical properties can be simultaneously considered, and the broadband electromagnetic shielding effect of the copper alloy plate strip in high-frequency electric fields and low-frequency electromagnetic fields is improved.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (12)
1. The copper alloy plate strip for electromagnetic shielding is characterized by comprising, by weight, 5-10wt% of Fe, 0.05-0.4wt% of Ti, 0.02-0.2wt% of Co, 0.02-0.3wt% of RE and the balance of Cu and unavoidable impurities;
wherein RE is rare earth element, and the sum of Ti and Co is less than or equal to 0.5wt%.
2. The copper alloy strip for electromagnetic shielding according to claim 1, wherein the copper alloy strip comprises 7.5-9wt% of Fe, 0.05-0.3wt% of Ti, 0.02-0.1wt% of Co, 0.06-0.2wt% of RE, and the balance of Cu and unavoidable impurities;
wherein the weight ratio of Ti to Co is (0.5-7): 1.
3. The copper alloy sheet strip for electromagnetic shielding according to claim 1 or 2, wherein RE includes one or more of Y, la, ce, and Pr.
4. The copper alloy sheet strip for electromagnetic shielding according to claim 3, wherein the RE comprises, by weight, 45 to 55% La,35 to 45% Ce and 5 to 15% Pr, based on 100% RE.
5. The copper alloy sheet strip for electromagnetic shielding according to claim 1 or 2, wherein the tensile strength of the copper alloy sheet strip for electromagnetic shielding is 550 to 700mpa, the elongation is not less than 3%, and the electrical conductivity is 50 to 65% iacs.
6. The method for producing a copper alloy sheet strip for electromagnetic shielding according to any one of claims 1 to 5, comprising the steps of:
step S1, sequentially melting and alloying raw materials of a copper alloy plate strip for electromagnetic shielding to obtain a copper alloy melt;
step S2, casting the copper alloy melt to obtain a copper alloy casting blank;
step S3, carrying out hot rolling or hot forging on the copper alloy casting blank to obtain a copper alloy plate strip blank;
s4, cold rolling the copper alloy plate strip blank to obtain a copper alloy cold rolled blank;
and S5, performing heat treatment on the copper alloy cold-rolled blank to obtain the copper alloy plate strip for electromagnetic shielding.
7. The method according to claim 6, wherein the step S1 comprises: melting raw material Cu, adding raw material Fe and raw material Co for first alloying, and adding raw material Ti and raw material RE for second alloying to obtain copper alloy melt; and/or
The raw material Cu, the raw material Fe and the raw material Co are all added in the form of pure metal sheets, the raw material Ti is added in the form of Cu-Ti intermediate alloy, and the raw material RE is added in the form of Cu-RE intermediate alloy; and/or
The weight percentage of Ti in the Cu-Ti master alloy is 10wt%; and/or the weight percentage of RE in the Cu-RE master alloy is 5-15wt%; and/or
Dividing the Cu-RE intermediate alloy into two parts, namely a first Cu-RE intermediate alloy and a second Cu-RE intermediate alloy, wherein the weight ratio of the first Cu-RE intermediate alloy to the second Cu-RE intermediate alloy is 1:2, adding the first Cu-RE intermediate alloy before adding the raw material Fe, and adding the second Cu-RE intermediate alloy in the second alloying; and/or
The melting temperature is 1180-1220 ℃; and/or the temperature of the first alloying is 1300-1330 ℃; and/or the temperature of the second alloying is 1250-1300 ℃.
8. The method of claim 6, wherein in step S2, the casting comprises rapid solidification casting.
9. The method according to claim 8, wherein in the step S2, the rapid solidification casting is performed at a temperature of 1250-1300 ℃ and a speed of 30-80 mm/min.
10. The method according to claim 6, wherein in the step S3, the temperature of the hot rolling or hot forging is 900-980 ℃ for 2-8 hours; and/or
The deformation of the hot rolling is more than or equal to 70 percent.
11. The method according to claim 6, wherein in the step S4, the deformation amount of the cold rolling is 50 to 95%.
12. The method according to claim 6, wherein in the step S5, the heat treatment is performed at a temperature of 300 to 600 ℃ for a time of 1 to 6 hours.
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