CN116713326A - Method for preparing multilayer copper-molybdenum graphene lamination by cumulative hot-pressing and laminating - Google Patents
Method for preparing multilayer copper-molybdenum graphene lamination by cumulative hot-pressing and laminating Download PDFInfo
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- CN116713326A CN116713326A CN202310718170.2A CN202310718170A CN116713326A CN 116713326 A CN116713326 A CN 116713326A CN 202310718170 A CN202310718170 A CN 202310718170A CN 116713326 A CN116713326 A CN 116713326A
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- 238000007731 hot pressing Methods 0.000 title claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000001186 cumulative effect Effects 0.000 title claims abstract description 24
- 238000010030 laminating Methods 0.000 title claims abstract description 22
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 title claims abstract 14
- 238000003475 lamination Methods 0.000 title claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 91
- 229910052802 copper Inorganic materials 0.000 claims abstract description 52
- 239000010949 copper Substances 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 44
- 238000005096 rolling process Methods 0.000 claims abstract description 31
- 238000005097 cold rolling Methods 0.000 claims abstract description 30
- 238000000137 annealing Methods 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 49
- 229910052750 molybdenum Inorganic materials 0.000 claims description 49
- 239000011733 molybdenum Substances 0.000 claims description 49
- 239000011889 copper foil Substances 0.000 claims description 38
- 238000011282 treatment Methods 0.000 claims description 23
- 239000011888 foil Substances 0.000 claims description 17
- 108010022355 Fibroins Proteins 0.000 claims description 16
- 238000013329 compounding Methods 0.000 claims description 13
- 238000012360 testing method Methods 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 10
- 239000002648 laminated material Substances 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 9
- 230000003014 reinforcing effect Effects 0.000 claims description 8
- 238000004528 spin coating Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 238000011534 incubation Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 12
- 239000004020 conductor Substances 0.000 abstract description 6
- 229910001182 Mo alloy Inorganic materials 0.000 abstract description 4
- 238000009825 accumulation Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 45
- BLNMQJJBQZSYTO-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu][Mo][Cu] BLNMQJJBQZSYTO-UHFFFAOYSA-N 0.000 description 33
- 230000007547 defect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000005728 strengthening Methods 0.000 description 4
- 238000005056 compaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005098 hot rolling Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 2
- 229910039444 MoC Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- ZTXONRUJVYXVTJ-UHFFFAOYSA-N chromium copper Chemical compound [Cr][Cu][Cr] ZTXONRUJVYXVTJ-UHFFFAOYSA-N 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- -1 comprises annealing Chemical class 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/38—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling sheets of limited length, e.g. folded sheets, superimposed sheets, pack rolling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B47/00—Auxiliary arrangements, devices or methods in connection with rolling of multi-layer sheets of metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C51/00—Measuring, gauging, indicating, counting, or marking devices specially adapted for use in the production or manipulation of material in accordance with subclasses B21B - B21F
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/38—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling sheets of limited length, e.g. folded sheets, superimposed sheets, pack rolling
- B21B2001/386—Plates
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a method for preparing a multi-layer copper-molybdenum graphene laminate by accumulating hot-pressing and laminating, which realizes dislocation accumulation in a metal layer by repeatedly carrying out cold rolling and hot-pressing annealing on the copper-molybdenum graphene laminate, thereby achieving the purpose of grain refinement. The method for preparing the multi-layer copper-molybdenum graphene laminate by the cumulative hot-pressing and rolling can be used for preparing high-performance copper-based conductor materials, has the characteristics of simple preparation process, high controllability, obvious performance improvement and high success rate, and provides new possibility for the preparation method of copper-molybdenum alloy.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to a method for preparing a multi-layer copper-molybdenum graphene laminate by accumulating hot-pressing and rolling.
Background
Along with the development of modern power systems, the requirements of conductor materials are more and more strict, and the materials not only need good conductive properties but also have higher mechanical properties. The copper-based material has excellent conductivity and good mechanical property, is the conductor material most widely used in nature, but the single copper-based material has limited performance, and the tensile strength of the pure copper-based material is only 200-400MPa, so that the requirement of a modern power system on the conductor material can not be met. The existing method for improving the performance of the copper-based material mainly comprises the steps of adding a reinforcing phase material into the copper-based material, improving the mechanical performance, solid solution strengthening, second phase strengthening and the like through plastic deformation, such as preparing chromium-copper alloy through adding high-mechanical metal particles such as chromium, zirconium and the like into copper powder, or obtaining the high-performance alloy by taking a high-performance metal plate as an intermediate layer of the copper-based material through a cumulative rolling method, or adding a carbon material with excellent performance in electric heating into the copper-based material as strengthening and the like.
The improvement of mechanical properties of metals mainly comprises annealing, cold work hardening, shaping deformation and the like, and basically, the methods are all implemented by refining grains, and the more the grain boundaries are, the more the accumulated dislocation density is, the more the slip transmission is blocked, so that the mechanical properties of materials are improved. In practice, in order to refine the crystal grains into ultrafine crystals (100 nm < d <1 μm), most of the modes adopted are rapid solidification, vapor deposition, mechanical alloying, low-temperature metal forming, severe plastic deformation and the like, wherein the severe plastic deformation is most suitable for industrial operation, and the operation is simple and convenient. The processing modes of the severe shaping deformation of the workpieces with different shapes are different, and the most practical mode for the plates/foils is the accumulating and rolling technology. The accumulating rolling is to roll two metal sheet materials with the same size after degreasing, work hardening and other treatments on the surfaces at a certain temperature, automatically weld the two metal sheet materials, and repeatedly roll and weld the two metal sheet materials by repeating the same process, so that the structure of the material is thinned, the distribution of inclusions is uniform, and the mechanical property of the material is greatly improved. The key to influencing the performance of the sample after the accumulated rolling is the optimal deformation amount, deformation speed and annealing temperature of the sample, wherein the deformation amount directly influences the distribution of intermediate layer substances in the sample, the deformation speed influences the defect amount of the sample introduced by stress, and the annealing temperature directly influences whether the sample can successfully accumulate the performance improvement caused by rolling. The maximum boost is obtained by finding the optimal balance condition.
The preparation of copper/molybdenum composite sheets is also mentioned in the literature and in the patents. The rolling crimping process is taught in the U.S. patent documents (US 4957823, US4950554, US 4988392) for the preparation of copper/molybdenum/copper composite panels; in the patent with the publication number of CN102529217B, a method for preparing a molybdenum fiber copper/molybdenum composite plate is proposed, copper-molybdenum copper plates are directly hot-rolled at 750-850 degrees after being overlapped, and after repeated accumulated and laminated rolling for 4-7 times, the mechanical property of a final sample can reach 390-620 MPa, but due to the poor interface structure between a molybdenum layer and a copper layer in the finally prepared sample, the molybdenum layer is in a molybdenum fiber mode and is not beneficial to current transmission, so that the overall electrical property of the sample is reduced; in the patent of publication No. CN102941441B, a method for obtaining a copper-molybdenum laminate with high bonding precision is proposed, in which a diffusion welding method is adopted to obtain a tightly bonded copper/molybdenum/copper laminate, and then a laminate sample with interlayer interface bonding strength of 190MPa is obtained by a plurality of cold rolling methods, but stress is inevitably introduced in subsequent cold rolling to crack the molybdenum layer. The method improves the performance through rolling, reduces the electrical performance due to the defect introduced by rolling the copper/molybdenum bonding interface singly, and has cavities between the layers after rolling, and potential safety hazards exist for the materials for a long time.
Disclosure of Invention
The invention aims to provide a method for preparing a multi-layer copper-molybdenum graphene laminate by accumulating hot-pressing and rolling, which can be used for preparing a high-performance copper-based conductor material, has the characteristics of simple preparation process, high controllability, obvious performance improvement and high success rate, and provides new possibility for a preparation method of copper-molybdenum alloy.
In order to achieve the above purpose, the invention provides a method for preparing a multi-layer copper-molybdenum graphene laminate by cumulative hot-pressing and laminating, which comprises the following steps:
s1, pretreatment of materials
S11, material precutting: selecting copper foil and molybdenum foil according to the thickness ratio, cutting the copper foil and the molybdenum foil into preset shapes, sequentially carrying out ultrasonic treatment on the cut foil in acetone, alcohol and water, and primarily cleaning surface impurities;
s12, polishing copper foil: the copper foil treated in the step S11 is subjected to electrochemical polishing treatment, the polished copper foil is firstly subjected to alkali washing, then is washed by alcohol and deionized water, and is dried, and the dried copper foil is subjected to annealing reduction treatment to remove a surface oxide layer;
s2, silk fibroin spin coating
Placing the copper foil treated in the step S1 on a spin coater, dripping silk fibroin solution on the surface of the copper foil, coating uniformly, rotating at a high speed to throw off redundant silk fibroin solution, spin-coating uniformly, and drying the copper foil subjected to spin-coating of silk fibroin, so that a silk fibroin dry film is attached to the surface of the copper foil, and thus a film-attached copper foil is obtained;
s3, preliminary compounding
Sequentially and circularly stacking the foil materials together according to the sequence of the film-attached copper foil and the molybdenum foil to form a lamination taking copper/molybdenum/graphene as a basic circulation unit, placing the lamination in a hot-pressing die, heating and pressurizing the lamination when the set vacuum degree is reached, and applying pressure to the lamination after heat preservation for a period of time to thoroughly compound each layer into a whole, thereby obtaining the copper/molybdenum/graphene composite structural material;
s4, cold rolling treatment
Performing cold rolling treatment on the laminated layer prepared in the step S3, and then dividing the laminated layer subjected to the cold rolling treatment into two parts with the same size through linear cutting, and respectively performing grinding and polishing treatment on the two parts to remove an oxide layer and impurity on the surface of a material;
s5, re-compounding, namely re-compounding the two parts of samples processed in the step S4 into a new lamination under the condition of vacuum hot pressing after overlapping;
s6, repeating the treatment, namely performing one-pass accumulated hot-pressing and laminating operation on the laminated material, wherein the operation of performing one-pass accumulated hot-pressing and laminating operation on the laminated material is called performing multi-pass accumulated hot-pressing and laminating operation on the laminated material, so that a copper-molybdenum laminated sample with uniformly distributed reinforcing phases can be obtained;
s7, testing the sample, namely cutting the copper-molybdenum laminated sample with uniformly distributed reinforcing phases into a sample meeting the test standard, and then testing the performance and the structure of the sample.
Preferably, in step S3, the vacuum degree is 8×10 -3 Pa, the incubation time is 90min, the incubation temperature is 850 ℃, and the pressure applied to the sample is 45MPa.
Preferably, in step S4, the reduction of each pass of cold rolling operation is controlled to be 60% -65% in the cold rolling process, and the cold rolling process is uniform cold rolling.
Preferably, in step S5, the processing temperature for the re-compounding is selected in accordance with the recovery temperature during the recrystallization of the monolith.
Preferably, in step S1, the thickness of copper is greater than the thickness of molybdenum.
Preferably, in step S6, the passes of the compaction are related to the desired tensile strength, electrical properties, and thickness ratio of copper to molybdenum.
Therefore, the method for preparing the multilayer copper-molybdenum graphene lamination by adopting the cumulative hot-pressing and laminating method has the following technical effects:
(1) Samples with better performance can be obtained by regulating the thickness ratio of the copper-molybdenum graphene and the recombination temperature again, and the method has the characteristics of strong controllability and simple manufacturing process and can be used for mass production.
(2) The original insoluble metallic copper and metallic molybdenum form a mutually coated false alloy structure through repeated cold rolling and hot pressing, and meanwhile, the defects between two metallic interfaces introduced by cold rolling are overcome through hot pressing, so that interface combination is more stable.
(3) During cold rolling, the distance between two rollers is continuously adjusted downwards in a uniform speed cold rolling mode, so that a sample is uniformly stressed, and the defect and sudden increase of a metal layer caused by overlarge stress due to rapid cold rolling are prevented, and the performance of the sample is reduced.
(4) According to the invention, a cumulative hot-pressing and laminating process is adopted, meanwhile, graphene is introduced as a reinforcing item material, the graphene in the middle layer is uniformly distributed in copper and molybdenum at two sides after rolling, the thickness of the copper and molybdenum layer is continuously reduced along with repeated rolling, and the distribution of the graphene in the copper and molybdenum layer is deeper, so that the graphene provides good conductive paths for the upper layer metal and the lower layer metal, and the electrical property of the whole material is improved.
(5) The temperature in the compounding of the step S5 is selected to be near the recrystallization recovery temperature of the metallic molybdenum, and the copper layer can be well regrown at the temperature, so that the interlayer combination of the regrown copper layer and the molybdenum layer is tighter under the action of high pressure, the interface is further improved, and the gap and the fracture introduced in the rolling process are greatly reduced.
(6) With the increase of rolling passes, graphene and molybdenum carbide are refined and then are more uniformly distributed in the metal matrix, the metal matrix is coated with a reinforcing material under the action of hot press annealing, the reinforcing material in mechanical aspect is reinforced by dispersion strengthening, and the graphene which is uniformly distributed in electrical aspect provides a high conductive path for the material, so that the electrical property of the material is improved.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a multi-layered copper-molybdenum graphene stack by cumulative hot-pressing;
FIG. 2 is an SEM and mapping image of the surface of a sample after the cumulative hot rolling process;
FIG. 3 is a cross-sectional view of a sample of stacked different cumulative hot rolling passes;
FIG. 4 is a cross-sectional view of a nine pass cumulative hot-rolled sample;
FIG. 5 is a graph of sample performance for different cumulative hot rolling passes.
Detailed Description
The technical scheme of the invention is further described below through the attached drawings and the embodiments.
Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art. Such other embodiments are also within the scope of the present invention.
It should also be understood that the above-mentioned embodiments are only for explaining the present invention, the protection scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the protection scope of the present invention by equally replacing or changing the technical scheme and the inventive concept thereof within the scope of the present invention.
Techniques, methods, and apparatus known to one of ordinary skill in the relevant art may not be discussed in detail, but are intended to be considered part of the specification where appropriate.
The disclosures of the prior art documents cited in the present specification are incorporated by reference in their entirety into the present invention and are therefore part of the present disclosure.
Example 1
The invention provides a method for preparing a multi-layer copper-molybdenum graphene laminate by accumulating hot-pressing and laminating, which comprises the following steps:
s1, pretreatment of materials
S11, material precutting: selecting copper foil and molybdenum foil according to the thickness ratio, cutting the copper foil and the molybdenum foil into preset shapes, sequentially performing ultrasonic treatment on the cut foil in acetone, alcohol and water for 30 minutes, and primarily cleaning surface impurities;
s12, polishing copper foil: in order to obtain a smooth copper foil, placing the copper foil processed in the step S11 into polishing solution with main component phosphoric acid, performing electrochemical polishing treatment for 60S, washing the polished copper foil with alkali, washing with alcohol and deionized water, drying, and annealing and reducing the polished copper foil and molybdenum foil in hydrogen+nitrogen atmosphere to remove surface oxides and other impurities;
s2, silk fibroin spin coating
And (2) placing the copper foil treated in the step (S1) on a spin coater, dripping a silk fibroin solution on the surface of the copper foil, uniformly coating, throwing away the excessive silk fibroin solution at 4000-6000 rpm, spin-coating uniformly, and then drying the spin-coated copper foil in a 60-DEG drying box for 60min to enable a silk fibroin dry film to be attached to the surface of the copper foil, wherein the silk fibroin film is tightly attached to the surface of the copper foil, and thus the film-attached copper foil is obtained. The thickness of the SF protein film which is spin-coated and dried is preferably as thin as 20 mu m.
S3, preliminary compounding
The foil materials are sequentially and circularly stacked together according to the sequence of the film-attached copper foil and the molybdenum foil, thus forming a lamination taking copper/molybdenum/graphene as a basic circulation unit, and the lamination is placed in a hot-pressing die, and then when the set vacuum degree is 8 multiplied by 10 -3 Heating and pressurizing at Pa, and hot pressing to convert silk fibroin into graphene, primarily combining laminated layers into an integral material, preserving heat at 850 ℃ for 90min, and applying 45MPa pressure to the sample to thoroughly compound the layers into an integral, so as to obtain a primary sample, namely the copper/molybdenum/graphene composite structural material;
s4, cold rolling treatment
And (3) carrying out cold rolling treatment on the laminated layer prepared in the step (S3), wherein the reduction of each pass of cold rolling operation is controlled to be 60% -65% in the cold rolling process, and a uniform cold rolling mode is needed. The experiment shows that the mechanical property of the copper-molybdenum graphene laminated system prepared by the step S3 is greatly improved when the cold rolling reduction is 60% -65%, defects introduced by rolling are fewer, and the situation that the laminated layer is not annealed and recovered due to transitional rolling is prevented, so that the reduction is controlled to be 60% -65%. The rotating speed of the roller is controlled to be uniform, so that the laminated layers uniformly pass through a cold rolling mill, and the rolling is repeated for a plurality of times under each gradient rolling reduction until the thickness of the laminated layers is uniform. The rapid cold rolling method can prevent the defect and sudden increase of the metal layer caused by the overlarge local stress, thereby reducing the sample performance.
Then dividing the rolled lamination into two parts with the same size through linear cutting, and respectively polishing the two parts to remove an oxide layer and impurity on the surface of the material;
s5, re-compounding, namely re-compounding the two parts of samples processed in the step S4 into a new lamination under the condition of vacuum hot pressing after superposition, wherein the re-compounding treatment temperature is selected according to the recovery temperature in the recrystallization process of the integral material;
s6, repeating the treatment, namely performing one-pass accumulated hot-pressing and laminating operation on the laminated material, wherein the operation of performing one-pass accumulated hot-pressing and laminating operation on the laminated material is called performing multi-pass accumulated hot-pressing and laminating operation on the laminated material, so that a copper-molybdenum laminated sample with uniformly distributed reinforcing phases can be obtained;
s7, testing the sample, namely cutting the copper-molybdenum laminated sample with uniformly distributed reinforcing phases into a sample meeting the test standard, and then testing the performance and the structure of the sample.
The thickness of copper is greater than that of molybdenum, so that breakage caused by brittleness of molybdenum is prevented, and the thickness of copper can be increased according to the requirement of the copper on electrical properties.
The number of passes of the compaction is related to the required tensile strength, electrical properties and the thickness ratio of copper to molybdenum, and the more passes of the compaction before reaching the limit pass, the better the tensile strength.
Example two
The thickness ratio of copper to molybdenum is 2:1 copper molybdenum graphene laminate preparation
The steps and processes in the first embodiment are performed in this embodiment, since the recrystallization temperature in step S5 needs to be selected according to the recovery temperature during the recrystallization of the bulk material;
in the embodiment, the melting point of copper and the recrystallization temperature of molybdenum are comprehensively considered, the recrystallization temperature of molybdenum and copper is larger, the melting point of copper is lower, the composite temperature is 800 ℃ after the pre-test, the heat preservation time is 40min, and the treatment pressure is 40MPa.
Repeating the operations of step S4 and step S5 on the laminated sample in step S6, and repeating the cumulative hot-press-laminating operation of 0, 3, 5, 7 and 9 passes to obtain copper-molybdenum graphene laminated composite materials with different properties, as shown in table 1:
table 1 copper-molybdenum thickness ratio is 2:1, performance parameters of different stacking passes of the copper-molybdenum graphene laminate
From the above table, the copper-molybdenum laminated composite material with the tensile strength of 856MPa can be obtained by repeating the cumulative hot-pressing and rolling operation for 9 times, as the cumulative hot-pressing and rolling operation for 5 is increased, the tensile strength of the final laminated sample is continuously increased until reaching the maximum tensile strength, and the 9-time treatment is not the limit pass of the cumulative hot-pressing and rolling operation.
And cutting the sample obtained by multiple times of accumulated hot-pressing and laminating into a mechanical test shape conforming to the national test standard for testing the tensile strength and the resistivity, as shown in a fifth graph.
Example III
The thickness ratio of copper to molybdenum is 3:1 copper molybdenum graphene laminate preparation
In the first embodiment, the steps and the process in the first embodiment are performed, and since the copper ratio in the first embodiment is higher, the recrystallization temperature is selected to be 750 ℃ in S5, the corresponding composite pressure is reduced to be about 35MPa, and then the cumulative hot-pressing and laminating operation of 0 pass and 7 pass is repeated to obtain copper-molybdenum graphene laminated composite materials with different performances, as shown in table 2:
table 2 copper-molybdenum thickness ratio is 3:1, performance parameters of different stacking passes of the copper-molybdenum graphene laminate
| 0 pass | 7 passes of | |
| Resistivity (. Times.10) -8 Ω·m) | 2.27 | 2.72 |
| Tensile strength (MPa) | 308 | 510 |
In this embodiment, the ratio of copper in the laminated sample is larger than that of molybdenum in the sample, and when the copper layer and the molybdenum layer are subjected to rolling, deformation is generated at the same time, but the ductility of the copper layer is strong, so that the copper layer is more influenced by rolling, and gradually coats the molybdenum layer to form a cross-section structure with a wavy curved surface, and the staggered and stepwise combination of the copper layer and the molybdenum layer is close as shown in fig. 2-3 when the top of the sample is seen. The copper layer and the molybdenum layer regrow after being affected by high temperature and high pressure after hot pressing treatment, defects between copper and molybdenum interfaces gradually disappear, and the reinforced graphene and molybdenum carbide between the molybdenum layer and the copper layer are more uniformly distributed in the sample along with the increase of accumulated hot pressing rolling passes, so that the electrical property and the mechanical property of the sample are improved, as shown in fig. 4. Final test implementationThe tensile strength of the example nine-pass accumulated hot-pressing rolled sample can reach 800MPa-856MPa, and the resistivity can reach 2.75-2.9 (multiplied by 10) -8 Omega.m), the tensile strength of the two-seven passes of the embodiment can reach 510MPa, and the resistivity is 2.72 (multiplied by 10) -8 Ω·m), as in fig. 5. Higher performance laminates are obtained by finer tuning of experimental influencing factors.
Example IV
The thickness ratio of copper to molybdenum is 2:1 copper molybdenum laminate preparation
The difference between the present embodiment and the second embodiment is the presence or absence of graphene, and the second step in the first embodiment is deleted from the steps, and the rest of the operation steps are completely the same as those in the first embodiment. In the embodiment, 0-pass and 7-pass cumulative hot-pressing and laminating rolling operations are performed, and copper-molybdenum graphene laminated composite materials with different performances are obtained, as shown in table 3:
table 3 copper-molybdenum thickness ratio of 2:1, performance parameters of different stacking passes of the copper-molybdenum stack
| 0 pass | 7 passes of | |
| Resistivity (. Times.10) -8 Ω·m) | 2.55 | 3.10 |
| Tensile strength (MPa) | 355 | 605 |
The tensile strength of the final laminate was605MPa, resistivity of 3.10 (. Times.10) -8 Omega. M), example II had a tensile strength of 667MPa and a resistivity of 2.82 (. Times.10) at seven pass cumulative hot-press -8 Omega.m), the comparative analysis shows that the introduction of the graphene can improve the mechanical and electrical properties of the copper-molybdenum laminate, and the cumulative hot-pressing and laminating technology is proved to be a feasible method for preparing the copper-molybdenum alloy.
Therefore, the method for preparing the multi-layer copper-molybdenum graphene laminate by the cumulative hot-pressing and rolling can be used for preparing high-performance copper-based conductor materials, has the characteristics of simple preparation process, high controllability, obvious performance improvement and high success rate, and provides new possibility for the preparation method of copper-molybdenum alloy.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (6)
1. The method for preparing the multilayer copper-molybdenum graphene lamination by cumulative hot-pressing and laminating is characterized by comprising the following steps of:
s1, pretreatment of materials
S11, material precutting: selecting copper foil and molybdenum foil according to the thickness ratio, cutting the copper foil and the molybdenum foil into preset shapes, sequentially carrying out ultrasonic treatment on the cut foil in acetone, alcohol and water, and primarily cleaning surface impurities;
s12, polishing copper foil: the copper foil treated in the step S11 is subjected to electrochemical polishing treatment, the polished copper foil is firstly subjected to alkali washing, then is washed by alcohol and deionized water, and is dried, and the dried copper foil is subjected to annealing reduction treatment to remove a surface oxide layer;
s2, silk fibroin spin coating
Placing the copper foil treated in the step S1 on a spin coater, dripping silk fibroin solution on the surface of the copper foil, coating uniformly, rotating at a high speed to throw off redundant silk fibroin solution, spin-coating uniformly, and drying the copper foil subjected to spin-coating of silk fibroin, so that a silk fibroin dry film is attached to the surface of the copper foil, and thus a film-attached copper foil is obtained;
s3, preliminary compounding
Sequentially and circularly stacking the foil materials together according to the sequence of the film-attached copper foil and the molybdenum foil to form a lamination taking copper/molybdenum/graphene as a basic circulation unit, placing the lamination in a hot-pressing die, heating and pressurizing the lamination when the set vacuum degree is reached, and applying pressure to the lamination after heat preservation for a period of time to thoroughly compound each layer into a whole, thereby obtaining the copper/molybdenum/graphene composite structural material;
s4, cold rolling treatment
Performing cold rolling treatment on the laminated layer prepared in the step S3, and then dividing the laminated layer subjected to the cold rolling treatment into two parts with the same size through linear cutting, and respectively performing grinding and polishing treatment on the two parts to remove an oxide layer and impurity on the surface of a material;
s5, re-compounding, namely re-compounding the two parts of samples processed in the step S4 into a new lamination under the condition of vacuum hot pressing after overlapping;
s6, repeating the treatment, namely performing one-pass accumulated hot-pressing and laminating operation on the laminated material, wherein the operation of performing one-pass accumulated hot-pressing and laminating operation on the laminated material is called performing multi-pass accumulated hot-pressing and laminating operation on the laminated material, so that a copper-molybdenum laminated sample with uniformly distributed reinforcing phases can be obtained;
s7, testing the sample, namely cutting the copper-molybdenum laminated sample with uniformly distributed reinforcing phases into a sample meeting the test standard, and then testing the performance and the structure of the sample.
2. The method for preparing a multi-layered copper-molybdenum graphene laminate by cumulative hot-pressing and rolling according to claim 1, wherein in step S3, the vacuum degree is 8×10 -3 Pa, the incubation time is 90min, the incubation temperature is 850 ℃, and the pressure applied to the sample is 45MPa.
3. The method for preparing a multi-layered copper-molybdenum graphene laminate by cumulative hot-pressing according to claim 1, wherein in step S4, the reduction of each pass of cold rolling operation is controlled to be 60% -65% in the cold rolling process, and the cold rolling process is uniform cold rolling.
4. A method for producing a multilayer copper molybdenum graphene stack according to claim 1, characterized in that in step S5 the process temperature for re-compounding is selected according to the recovery temperature during the recrystallization of the monolith.
5. The method for preparing a multi-layered copper-molybdenum graphene laminate according to claim 1, wherein in step S1, the thickness of copper is greater than the thickness of molybdenum.
6. The method of producing a multi-layered copper-molybdenum graphene laminate according to claim 1, wherein in step S6, the rolling passes are related to the required tensile strength, electrical properties and thickness ratio of copper-molybdenum.
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