CN113664063B - Preparation method of copper-molybdenum-copper layered composite material - Google Patents
Preparation method of copper-molybdenum-copper layered composite material Download PDFInfo
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- CN113664063B CN113664063B CN202110987278.2A CN202110987278A CN113664063B CN 113664063 B CN113664063 B CN 113664063B CN 202110987278 A CN202110987278 A CN 202110987278A CN 113664063 B CN113664063 B CN 113664063B
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- 239000002131 composite material Substances 0.000 title claims abstract description 131
- BLNMQJJBQZSYTO-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu][Mo][Cu] BLNMQJJBQZSYTO-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 142
- 239000011733 molybdenum Substances 0.000 claims abstract description 142
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 141
- 229910052802 copper Inorganic materials 0.000 claims abstract description 134
- 239000010949 copper Substances 0.000 claims abstract description 134
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 124
- AHGIVYNZKJCSBA-UHFFFAOYSA-N [Ti].[Ag].[Cu] Chemical compound [Ti].[Ag].[Cu] AHGIVYNZKJCSBA-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000011888 foil Substances 0.000 claims abstract description 77
- 238000011282 treatment Methods 0.000 claims abstract description 77
- 238000005096 rolling process Methods 0.000 claims abstract description 55
- 238000007731 hot pressing Methods 0.000 claims abstract description 43
- 230000007704 transition Effects 0.000 claims abstract description 43
- 238000004140 cleaning Methods 0.000 claims abstract description 36
- 238000000137 annealing Methods 0.000 claims abstract description 30
- 238000005098 hot rolling Methods 0.000 claims abstract description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 52
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 229910002804 graphite Inorganic materials 0.000 claims description 23
- 239000010439 graphite Substances 0.000 claims description 23
- 238000005520 cutting process Methods 0.000 claims description 21
- 230000009467 reduction Effects 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 19
- 229910052786 argon Inorganic materials 0.000 claims description 17
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000005498 polishing Methods 0.000 claims description 12
- 238000013329 compounding Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000005266 casting Methods 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000004381 surface treatment Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 12
- 239000006104 solid solution Substances 0.000 description 8
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000011049 filling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005253 cladding Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000004100 electronic packaging Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002751 molybdenum Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 common rolling Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- GVLHKKPMWMGGOD-UHFFFAOYSA-N copper molybdenum Chemical compound [Mo][Cu][Mo] GVLHKKPMWMGGOD-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ZPZCREMGFMRIRR-UHFFFAOYSA-N molybdenum titanium Chemical compound [Ti].[Mo] ZPZCREMGFMRIRR-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/02—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of sheets
-
- 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
- B21B1/02—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 heavy work, e.g. ingots, slabs, blooms, or billets, in which the cross-sectional form is unimportant ; Rolling combined with forging or pressing
- B21B1/026—Rolling
-
- 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
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
-
- 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
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
- B23K26/3568—Modifying rugosity
- B23K26/3584—Increasing rugosity, e.g. roughening
-
- 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
- B21B1/02—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 heavy work, e.g. ingots, slabs, blooms, or billets, in which the cross-sectional form is unimportant ; Rolling combined with forging or pressing
- B21B2001/028—Slabs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B2003/005—Copper or its alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B2201/00—Special rolling modes
- B21B2201/06—Thermomechanical rolling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/18—Sheet panels
Abstract
The invention discloses a preparation method of a copper-molybdenum-copper layered composite material, which comprises the following steps: 1. preparing a copper plate, a copper silver titanium foil and a molybdenum plate respectively; 2. carrying out laser texturing treatment on the molybdenum plate; 3. respectively cleaning the treated molybdenum plate, copper plate and copper silver titanium foil; 4. respectively taking the cleaned molybdenum plate, copper plate and copper silver titanium foil as an intermediate layer, a copper layer and a transition layer, stacking, and performing hot pressing treatment to obtain a copper-molybdenum-copper composite blank; 5. carrying out hot rolling treatment and annealing to obtain a copper-molybdenum-copper composite material belt; 6. and cleaning, rolling and annealing to obtain the copper-molybdenum-copper layered composite material. According to the invention, the micro-level uniformly distributed uneven morphology is formed on the surface of the molybdenum plate through laser texturing, and the copper-silver-titanium foil is used as a transition layer for hot pressing treatment, so that the transition layer copper-silver-titanium foil and the molybdenum plate form good interface combination under the combined action of metallurgical combination and concave-convex occlusion, the separation phenomenon of the molybdenum plate and the copper plate is avoided, and the integral combination property of the copper-molybdenum-copper layered composite material is ensured.
Description
Technical Field
The invention belongs to the technical field of preparation of electronic packaging composite materials, and particularly relates to a preparation method of a copper-molybdenum-copper layered composite material.
Background
The copper-molybdenum-copper layered composite material has the advantages of molybdenum and copper, has high electric conduction and heat conduction, low thermal expansion coefficient and excellent high temperature resistance, has no compactness problem and is widely applied to the field of electronic packaging materials. The materials require planar layered composite, generally 3 to 5 layers, and the specific structure is that the outermost layer is a copper layer with stronger conductivity, the middle layer is a molybdenum layer with lower expansion coefficient, or molybdenum-copper-molybdenum alternating layers. However, as the physical properties of copper and molybdenum are greatly different and are not dissolved with each other, the existing preparation methods of copper-molybdenum-copper layered composite materials, such as common rolling, explosive cladding, electroplating cladding, casting cladding and the like, have the problems of insufficient interface bonding strength, uneven macroscopic interface, interface oxidation pollution and the like, and seriously cause the separation of molybdenum-copper two-layer materials or the separation phenomenon in the use process; there are studies to produce solid solutions at interfaces by adding low conductivity transition layers to achieve interfacial metallurgical bonding, but to produce a large amount of continuous solid solution phase which in turn affects the conductivity of the product; these seriously affect the yield, performance and stability in use of the product. The cost of the molybdenum surface copper ion implantation technology developed in recent years is too high to produce energy; the nano-treatment of the molybdenum surface is adopted to achieve the nano-size effect to promote the diffusion of silver or copper ions, but the silver and copper are not diffused in the molybdenum in practice.
Therefore, how to prepare the molybdenum-copper layered composite material which has firm interface bonding, low cost and high yield and can be produced in mass in production is a technical problem which needs to be solved by the technicians in the field.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a copper-molybdenum-copper layered composite material aiming at the defects of the prior art. According to the method, the surface of the molybdenum plate is formed into uneven shapes with micron-sized uniform distribution through laser texturing, copper plates are compounded on two sides of the molybdenum plate, and hot pressing treatment is carried out by combining copper silver titanium foil with the copper silver titanium foil serving as a transition layer, so that the transition layer copper silver titanium foil and the molybdenum plate form good interface combination under the combined action of metallurgical bonding and concave-convex occlusion, firm bonding is formed between the molybdenum plate and the copper plate, separation or using separation phenomenon of the molybdenum plate and the copper plate is avoided, and the integral bonding performance of the copper-molybdenum-copper layered composite material is ensured.
In order to solve the technical problems, the invention adopts the following technical scheme: the preparation method of the copper-molybdenum-copper layered composite material is characterized by comprising the following steps of:
step one, material preparation: rolling and annealing the red copper blank plate, cutting, and performing surface treatment to obtain a copper plate; casting by adopting a vacuum smelting method to obtain a copper-silver-titanium plate, rolling, and cutting to obtain copper-silver-titanium foil; rolling and annealing the molybdenum plate, cutting, and performing surface treatment to obtain a molybdenum plate; the lengths and the widths of the copper plate, the copper silver titanium foil and the molybdenum plate are the same;
step two, surface laser texturing treatment: carrying out laser texturing treatment on the front and back surfaces of the molybdenum plate obtained in the step one to obtain a treated molybdenum plate;
step three, surface cleaning: sequentially carrying out acid washing, desalted water washing and ultrasonic cleaning on the molybdenum plate treated in the second step to obtain a cleaned molybdenum plate, and respectively carrying out ultrasonic cleaning on the copper plate and the copper-silver-titanium foil obtained in the first step to obtain a cleaned copper plate and a cleaned copper-silver-titanium foil;
step four, hot pressing and compounding: the cleaned molybdenum plate obtained in the third step is used as an intermediate layer, the cleaned copper plate is used as a copper layer, the cleaned copper silver titanium foil is used as a transition layer, the copper silver titanium foil is stacked in a graphite mold according to a preset structure of a target product copper molybdenum copper layered composite material, then the graphite mold is placed in a vacuum hot-pressing furnace, the vacuum is pumped and the flowing high-purity argon is filled after three times of gas washing, so that the atmosphere in the furnace is kept at micro positive pressure, and then hot-pressing treatment is carried out, so that a copper molybdenum copper composite blank is obtained;
step five, rolling and thinning: taking out the copper-molybdenum-copper composite blank obtained in the step four, and then placing the blank into a hot rolling mill to carry out hot rolling treatment and annealing to obtain a copper-molybdenum-copper composite material belt;
step six, rolling for the final time: and D, cleaning the surface oxide of the copper-molybdenum-copper composite material belt obtained in the step five, and then rolling for more than one pass, and annealing to obtain the copper-molybdenum-copper layered composite material.
According to the invention, laser texturing treatment is carried out on the molybdenum plate, so that the surface of the molybdenum plate forms uneven shapes which are uniformly distributed in a micron level, copper plates are compounded on two sides of the molybdenum plate, copper silver titanium foil is adopted as a transition layer between the copper plates and a template in a combined mode for carrying out hot pressing treatment, the transition layer copper silver titanium foil and the molybdenum plate form good interface combination under the combined action of metallurgical bonding and concave-convex occlusion in a relatively low temperature and a relatively short time, and good metallurgical bonding is formed between the transition layer copper silver titanium foil and the copper plates through the solid solution effect of the same matrix material, so that firm bonding is formed between the molybdenum plate and the copper plates; and then rolling and thinning the copper-molybdenum-copper composite blank obtained by the hot-pressing treatment to obtain the copper-molybdenum-copper layered composite material, so that the bonding performance between laminate materials in the copper-molybdenum-copper layered composite material is greatly improved, and interface problems caused by interface pollution, oxidation and the like of direct hot rolling and compounding or multi-step rolling and compounding are avoided by combining the hot-pressing treatment with rolling, and the quality of the copper-molybdenum-copper layered composite material is improved.
The preparation method of the copper-molybdenum-copper layered composite material is characterized in that the thickness of the copper plate in the first step is 0.1-1.5 mm, the thickness of the copper-silver-titanium foil is 0.05-0.1 mm, the thickness of the molybdenum plate is 0.5-2.5 mm, the lengths of the copper plate, the copper-silver-titanium foil and the molybdenum plate are 150-200 mm, and the widths of the copper plate, the copper-silver-titanium foil and the molybdenum plate are 20-50 mm. The thicknesses of the copper plate, the copper silver titanium foil and the molybdenum plate are convenient for the operation of the surface treatment process, and the thicknesses of target products are easy to realize through combination, so that the times of subsequent rolling procedures are effectively reduced, and the workload is reduced; meanwhile, the thickness of the copper-silver-titanium foil is well combined with the thickness of the molybdenum plate and the thickness of the copper plate, uniformity of overall performance of the composite material is not affected, the copper-silver-titanium foil is suitable for common thickness combination collocation of the molybdenum plate and the copper plate, operation of subsequent processing equipment is facilitated, rejection rate of the prepared copper-molybdenum-copper layered composite material is reduced, and the selective inspection process of quality stability of the composite material is facilitated.
The preparation method of the copper-molybdenum-copper layered composite material is characterized in that in the first step, the mass ratio of copper element, silver element and titanium element in the copper-silver-titanium plate is 6-9: 0.8 to 3.5:0.2 to 0.5. According to the invention, the copper-silver-titanium foil is used as the transition layer, the component proportion of the copper-silver-titanium foil is controlled, the melting point of the copper-silver-titanium foil is reduced, and the fluidity of the copper-silver-titanium foil is enhanced, so that a proper amount of evenly distributed solid solution is formed at the interface between the copper-silver-titanium foil and the molybdenum plate and between the copper plate, the interface metallurgical bonding between adjacent layers in the copper-molybdenum-copper layered composite is further enhanced, and the performance and the use stability of the copper-molybdenum-copper layered composite are ensured.
The preparation method of the copper-molybdenum-copper layered composite material is characterized in that the surface treatment in the first step is as follows: and removing the surface oxide layer by mechanical polishing, and ultrasonically cleaning by adopting acetone.
The preparation method of the copper-molybdenum-copper layered composite material is characterized in that the diameter of a focusing light spot adopted by the laser texturing treatment in the second step is 5-25 mu m, the distance between the light spots is 5-25 mu m, the scanning track is a grid type, and the protective atmosphere is argon. Preferably, a grating scanning trace is adopted, so that each laser texturing pit on the molybdenum plate is not communicated and uniformly distributed, the plane direction isotropy of the copper-molybdenum-copper layered composite material prepared by taking the molybdenum plate after laser texturing as an intermediate layer is ensured, and the mechanical property of the copper-molybdenum-copper layered composite material is improved; meanwhile, the diameter of the focusing light spots and the distance between the light spots are adjusted according to the thickness of the molybdenum plate, so that the interface between the molybdenum plate and the adjacent layer is macroscopically combined smoothly, the microcosmic combination is good, and the thickness and the performance of the copper-molybdenum-copper layered composite material are accurately controlled.
The preparation method of the copper-molybdenum-copper layered composite material is characterized in that the cleaning process of the molybdenum plate in the third step is as follows: soaking a molybdenum plate in dilute sulfuric acid solution with the mass concentration of 5% -15% at 40 ℃ for 10min, taking out, placing the molybdenum plate in flowing desalted water for washing for 5min, then placing the molybdenum plate in acetone for ultrasonic cleaning for 15min, taking out, and drying by cold air; the cleaning process of the copper plate and the copper silver titanium foil comprises the following steps: and respectively ultrasonically cleaning the copper plate and the copper silver titanium foil by using acetone for 15min, taking out, and drying by using cold air. The optimized cleaning process completely removes the oxide on the surface of the molybdenum plate, and the organic matters and inorganic matter impurities physically attached to the surfaces of the molybdenum plate, the copper plate and the copper silver titanium foil, and has good removing effect, simple cleaning medium and equipment, easy operation, rapid process and easy realization of mass production.
The preparation method of the copper-molybdenum-copper layered composite material is characterized in that the vacuum degree of vacuumizing and gas washing in the fourth step is 10 -3 Pa, the mass purity of the high-purity argon is more than 99.95%, the pressure of the hot pressing treatment is 5-15 MPa, the temperature is 680-780 ℃, and the time of heat preservation and pressure maintaining is 10-30 min. The preferred vacuumizing and gas washing vacuum degree ensures that only trace air exists in the hot pressing furnace, and the preferred high-purity argon is combined, so that each layer of plate is prevented from being oxidized, carbonized and nitrided in the hot pressing treatment process, the quality of the copper-molybdenum-copper composite blank is ensured, and the method has low cost and high safety compared with hydrogen, helium and the like; the temperature of the optimized hot pressing treatment ensures that the transition layer is close to or in a molten state, the optimized pressure is matched to enable the transition layer to be fully filled in the surface roughened pits of the molybdenum plate and fully contact with the molybdenum plate and the copper plate at the two sides of the transition layer, the element is fully diffused and well dissolved, and finally good interface combination is achieved.
The preparation method of the copper-molybdenum-copper layered composite material is characterized in that in the fourth step, the preset structure is a unit structure of a copper layer-a transition layer-an intermediate layer-a transition layer-a copper layer, or a combined structure of the transition layer-the intermediate layer-the transition layer-the copper layer which is continuously stacked on the copper layer of the unit structure. The preferable preset structure of the invention not only comprises a basic unit structure, but also can continuously stack the copper plate and the middle layer molybdenum plate on the basis of the unit structure, thereby effectively adjusting the combination quantity of the copper plate and the molybdenum plate, and further adjusting the thickness of the copper-molybdenum-copper layered composite material on the premise of ensuring good interface combination.
The preparation method of the copper-molybdenum-copper layered composite material is characterized in that in the fourth step, a plurality of groups of preset structures are overlapped in the graphite mold along the height direction by adopting graphite paper as a space. According to the invention, the graphite paper is adopted as the interval overlapping of the multiple groups of preset structures and is simultaneously placed in the graphite mold for hot pressing treatment, so that the hot pressing efficiency is greatly improved.
The preparation method of the copper-molybdenum-copper layered composite material is characterized in that the reduction rate of each pass of the hot rolling treatment in the fifth step is 30% -60%, and the thickness of the copper-molybdenum-copper composite material belt is 10% -15% higher than that of a target product copper-molybdenum-copper layered composite material. The optimal reduction rate of each pass ensures the effective thinning of the copper-molybdenum-copper composite blank, and a proper allowance is reserved for the deformation of the finish rolling, namely the follow-up rolling, so that the finish rolling difficulty is reduced. More preferably, since the hot rolling treatment directly utilizes the temperature of the copper-molybdenum-copper composite blank after the hot rolling treatment, the first pass reduction rate of the hot rolling treatment generally adopts a higher value to ensure a larger effective deformation amount, so that the energy utilization rate and the hot rolling efficiency are improved, meanwhile, internal heat generated by rolling with a higher value provides enough deformation energy to be beneficial to hot rolling, the temperature of the copper-molybdenum-copper composite blank is reduced along with the progress of rolling, the deformation capability is weakened, the subsequent reduction rate per pass is gradually reduced, and the phenomenon that larger internal stress is formed in a composite interface due to the difference of molybdenum and copper performances, so that microcracks are generated in the composite interface due to the overlarge reduction rate per pass is avoided.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the surface of the molybdenum plate is formed into uneven shapes with micron-sized uniform distribution through laser texturing treatment, copper plates are compounded on two sides of the molybdenum plate, and hot pressing treatment is carried out by combining copper silver titanium foil with the copper silver titanium foil serving as a transition layer, so that the transition layer copper silver titanium foil and the molybdenum plate form good interface combination under the combined action of metallurgical bonding and concave-convex occlusion, thereby forming firm bonding between the molybdenum plate and the copper plate, avoiding the separation or using separation phenomenon of the molybdenum plate and the copper plate, and ensuring the integral bonding performance of the copper-molybdenum-copper layered composite material.
2. According to the invention, hot pressing treatment and rolling are combined, the copper-molybdenum-copper composite blank obtained by the hot pressing treatment is rolled and thinned, and on the premise of ensuring firm combination between a molybdenum plate and a copper plate, the interface problems possibly caused by direct hot rolling compounding or multi-working-mode rolling compounding interface pollution, oxidization and the like are avoided, and the quality of the copper-molybdenum-copper layered composite material is improved.
3. According to the invention, the component proportion of the copper-silver-titanium foil of the transition layer is controlled, the melting point of the copper-silver-titanium foil is reduced, and the fluidity of the copper-silver-titanium foil is enhanced, so that a proper amount of evenly distributed solid solution is formed at the interface between the copper-silver-titanium foil and the molybdenum plate and the copper plate, the metallurgical bonding of the interface between adjacent layers in the copper-molybdenum-copper layered composite material is further enhanced, and the performance and the use stability of the copper-molybdenum-copper layered composite material are ensured.
4. The copper-molybdenum-copper layered composite material provided by the invention is mainly made of copper-based materials, so that the material cost is effectively reduced, meanwhile, titanium in the copper-silver-titanium foil of the transition layer and molybdenum form a solid solution, so that the firm combination of a molybdenum plate and a copper plate is realized, and the silver with strong thermal conductivity in the copper-silver-titanium foil counteracts the adverse effect on the thermal conductivity of the product composite material due to poor thermal conductivity of titanium, so that the thermal conductivity complementation among components is realized.
5. The interfacial tensile strength of the copper-molybdenum-copper layered composite material reaches 250MPa, and fracture occurs at the copper parent metal.
6. The product prepared by the invention has stable performance, high yield, simple process and mature equipment application, and is suitable for batch production.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
Fig. 1a is a schematic diagram of the front structure of a molybdenum plate obtained by laser texturing according to the present invention.
FIG. 1b is a schematic view of the cut surface structure of a molybdenum plate obtained by laser texturing according to the present invention.
FIG. 2 is a schematic cross-sectional view of the copper-molybdenum-copper layered composite materials prepared in examples 1 to 4 of the present invention.
Fig. 3 is a metallographic image of the interface of each layer in the copper-molybdenum-copper layered composite material prepared in example 1 of the present invention.
Detailed Description
As shown in fig. 1a and 1b, after laser texturing treatment, laser texturing pits distributed in a grid form are formed on the surface of the molybdenum plate, so that the surface of the front surface and the surface of the back surface of the molybdenum plate are concave-convex.
As shown in fig. 2, the copper-molybdenum-copper layered composite materials prepared in examples 1 to 4 of the present invention contain a unit structure of copper layer-transition layer copper-silver-titanium layer-intermediate layer molybdenum layer-transition layer copper-silver-titanium layer-copper layer, and the front and back surfaces of the transition layer copper-silver-titanium layer and the intermediate layer molybdenum layer form metallurgical bonding and concave-convex occlusion.
Example 1
The embodiment comprises the following steps:
step one, material preparation: rolling and annealing a red copper blank plate, cutting, mechanically polishing to remove a surface oxide layer, and ultrasonically cleaning by using acetone to obtain a copper plate with the thickness of 0.1 mm; casting by adopting a vacuum smelting method to obtain a copper-silver-titanium plate, rolling, and cutting to obtain copper-silver-titanium foil with the thickness of 0.05 mm; cutting after rolling and annealing the molybdenum plate, mechanically polishing to remove a surface oxide layer, and ultrasonically cleaning by adopting acetone to obtain a molybdenum plate with the thickness of 0.5 mm; the lengths and the widths of the copper plate, the copper silver titanium foil and the molybdenum plate are the same, the lengths are 200mm, and the widths are 20mm;
the mass ratio of copper element, silver element and titanium element in the copper-silver-titanium plate is 9:0.8:0.2;
step two, surface laser texturing treatment: carrying out laser texturing treatment on the front and back surfaces of the molybdenum plate obtained in the step one to obtain a treated molybdenum plate; the diameter of a focusing light spot adopted by the laser texturing treatment is 5 mu m, the distance between the light spots is 5 mu m, a scanning track is a grid type, and the protective atmosphere is argon;
step three, surface cleaning: soaking the molybdenum plate treated in the second step in a dilute sulfuric acid solution with the mass concentration of 5% at 40 ℃ for 10min, taking out, then placing the molybdenum plate in flowing desalted water for washing for 5min, then placing the molybdenum plate in acetone for ultrasonic cleaning for 15min, taking out, drying by cold air to obtain a cleaned molybdenum plate, respectively carrying out ultrasonic cleaning on the copper plate and the copper-silver-titanium foil obtained in the first step by using acetone for 15min, taking out, drying by cold air, and obtaining a cleaned copper plate and a cleaned copper-silver-titanium foil;
step four, hot pressing and compounding: taking the cleaned molybdenum plate obtained in the third step as an intermediate layer, taking the cleaned copper plate as a copper layer, taking the cleaned copper silver titanium foil as a transition layer, and forming a unit junction according to the copper layer-transition layer-intermediate layer-transition layer-copper layerStacking 10 unit structures in a graphite mould along the height direction by adopting graphite paper as a space, then placing the unit structures in a vacuum hot pressing furnace, vacuumizing and flushing three times until the vacuum degree is 10 -3 Filling high-purity argon with the flowing mass purity of 99.99% after Pa, keeping the furnace atmosphere at micro positive pressure, and performing hot pressing treatment to obtain a copper-molybdenum-copper composite blank; the pressure of the hot pressing treatment is 15MPa, the temperature is 780 ℃, and the heat preservation and pressure maintaining time is 10min;
step five, rolling and thinning: taking out the copper-molybdenum-copper composite blank obtained in the step four, and then placing the blank into a hot rolling mill to carry out hot rolling treatment and annealing to obtain a copper-molybdenum-copper composite material belt; the reduction rate of the first pass of the hot rolling treatment is 45%, the reduction rate of each pass is gradually reduced, and the reduction rate of the last pass is 30%; the thickness of the copper-molybdenum-copper composite material belt is 10% higher than that of the target product copper-molybdenum-copper layered composite material;
step six, rolling for the final time: and D, cleaning the surface oxide of the copper-molybdenum-copper composite material belt obtained in the step five, then rolling for more than one pass, annealing to obtain the copper-molybdenum-copper layered composite material, and counting the thickness of the transition layer in the copper layer of the copper-molybdenum-copper layered composite material, wherein the thickness ratio of each layer of copper to molybdenum-copper in the obtained copper-molybdenum-copper layered composite material is 1:5:1.
And carrying out local corrosion on the joint interface of each layer in the copper-molybdenum-copper layered composite material prepared in the embodiment, and observing the metallographic structure of the corrosion part. Fig. 3 is a metallographic image of each layer interface in the copper-molybdenum-copper layered composite material prepared in this embodiment, and as can be seen from fig. 3, the copper-silver-titanium transition layer and the molybdenum layer in the copper-molybdenum-copper layered composite material form a concave-convex occlusion-shaped combination, the combination position is tight and seamless, a molybdenum-titanium solid solution thin layer with deep color and discontinuous distribution exists, a fuzzy area without obvious boundary layer is presented between the copper-silver-titanium transition layer and the copper layer due to mutual solid solution, and large crystal grains after corrosion appear on one side of the copper layer.
Comparative example 1
This comparative example differs from example 1 in that: the second step is not included, namely, the molybdenum plate is not subjected to laser texturing treatment; and step four, adopting the cleaned titanium foil as a transition layer.
Example 2
The embodiment comprises the following steps:
step one, material preparation: rolling and annealing a red copper blank plate, cutting, mechanically polishing to remove a surface oxide layer, and ultrasonically cleaning by using acetone to obtain a copper plate with the thickness of 0.45 mm; casting by adopting a vacuum smelting method to obtain a copper-silver-titanium plate, rolling, and cutting to obtain copper-silver-titanium foil with the thickness of 0.08 mm; cutting after rolling and annealing the molybdenum plate, mechanically polishing to remove a surface oxide layer, and ultrasonically cleaning by adopting acetone to obtain a molybdenum plate with the thickness of 1.4 mm; the lengths and the widths of the copper plate, the copper silver titanium foil and the molybdenum plate are the same, the lengths are 150mm, and the widths are 30mm;
the mass ratio of copper element, silver element and titanium element in the copper-silver-titanium plate is 7:2.6:0.4;
step two, surface laser texturing treatment: carrying out laser texturing treatment on the front and back surfaces of the molybdenum plate obtained in the step one to obtain a treated molybdenum plate; the diameter of a focusing light spot adopted by the laser texturing treatment is 15 mu m, the distance between the light spots is 15 mu m, a scanning track is a grid type, and the protective atmosphere is argon;
step three, surface cleaning: soaking the molybdenum plate treated in the second step in a dilute sulfuric acid solution with the mass concentration of 10% at 40 ℃ for 10min, taking out, then placing the molybdenum plate in flowing desalted water for washing for 5min, then placing the molybdenum plate in acetone for ultrasonic cleaning for 15min, taking out, drying by cold air to obtain a cleaned molybdenum plate, respectively carrying out ultrasonic cleaning on the copper plate and the copper-silver-titanium foil obtained in the first step by using acetone for 15min, taking out, drying by cold air, and obtaining a cleaned copper plate and a cleaned copper-silver-titanium foil;
step four, hot pressing and compounding: taking the cleaned molybdenum plate obtained in the third step as an intermediate layer, taking the cleaned copper plate as a copper layer, taking the cleaned copper silver titanium foil as a transition layer, stacking 4 unit structures in a graphite mold along the height direction by taking graphite paper as an interval according to the unit structure of the copper layer-transition layer-intermediate layer-transition layer-copper layer, then placing the graphite mold in a vacuum hot pressing furnace, vacuumizing and flushing three times until the vacuum degree is 10 -3 Filling high-purity argon with the flowing mass purity of 99.99% after Pa, keeping the furnace atmosphere at micro positive pressure, and performing hot pressing treatment to obtain a copper-molybdenum-copper composite blank; the pressure of the hot pressing treatment is 12MPa, the temperature is 700 ℃, and the time of heat preservation and pressure maintaining is 25min;
step five, rolling and thinning: taking out the copper-molybdenum-copper composite blank obtained in the step four, and then placing the blank into a hot rolling mill to carry out hot rolling treatment and annealing to obtain a copper-molybdenum-copper composite material belt; the reduction rate of the first pass of the hot rolling treatment is 55%, the reduction rate of each pass is gradually reduced, and the reduction rate of the last pass is 30%; the thickness of the copper-molybdenum-copper composite material belt is 13% higher than that of the target product copper-molybdenum-copper layered composite material;
step six, rolling for the final time: and D, cleaning the surface oxide of the copper-molybdenum-copper composite material belt obtained in the step five, then rolling for more than one pass, annealing to obtain the copper-molybdenum-copper layered composite material, and counting the thickness of the transition layer in the copper layer of the copper-molybdenum-copper layered composite material, wherein the thickness ratio of each layer of copper to molybdenum-copper in the obtained copper-molybdenum-copper layered composite material is 1:4:1.
Comparative example 2
This comparative example differs from example 2 in that: the second step is not included, namely, the molybdenum plate is not subjected to laser texturing treatment; and step four, adopting the cleaned titanium foil as a transition layer.
Example 3
The embodiment comprises the following steps:
step one, material preparation: rolling and annealing a red copper blank plate, cutting, mechanically polishing to remove a surface oxide layer, and ultrasonically cleaning by using acetone to obtain a copper plate with the thickness of 1.15 mm; casting by adopting a vacuum smelting method to obtain a copper-silver-titanium plate, rolling, and cutting to obtain copper-silver-titanium foil with the thickness of 0.1 mm; cutting after rolling and annealing the molybdenum plate, mechanically polishing to remove a surface oxide layer, and ultrasonically cleaning by adopting acetone to obtain a molybdenum plate with the thickness of 2.5 mm; the lengths and the widths of the copper plate, the copper silver titanium foil and the molybdenum plate are the same, the lengths are 150mm, and the widths are 50mm;
the mass ratio of copper element, silver element and titanium element in the copper-silver-titanium plate is 6:3.5:0.5;
step two, surface laser texturing treatment: carrying out laser texturing treatment on the front and back surfaces of the molybdenum plate obtained in the step one to obtain a treated molybdenum plate; the diameter of a focusing light spot adopted in the laser texturing treatment is 25 mu m, the distance between the light spots is 25 mu m, a scanning track is a grid type, and the protective atmosphere is argon;
step three, surface cleaning: soaking the molybdenum plate treated in the second step in a dilute sulfuric acid solution with the mass concentration of 15% at 40 ℃ for 10min, taking out, then placing the molybdenum plate in flowing desalted water for washing for 5min, then placing the molybdenum plate in acetone for ultrasonic cleaning for 15min, taking out, drying by cold air to obtain a cleaned molybdenum plate, respectively carrying out ultrasonic cleaning on the copper plate and the copper-silver-titanium foil obtained in the first step by using acetone for 15min, taking out, drying by cold air, and obtaining a cleaned copper plate and a cleaned copper-silver-titanium foil;
step four, hot pressing and compounding: taking the cleaned molybdenum plate obtained in the third step as an intermediate layer, taking the cleaned copper plate as a copper layer, taking the cleaned copper silver titanium foil as a transition layer, stacking 2 unit structures in a graphite mold along the height direction by taking graphite paper as an interval according to the unit structure of the copper layer-transition layer-intermediate layer-transition layer-copper layer, then placing the graphite mold in a vacuum hot pressing furnace, vacuumizing and washing gas three times until the vacuum degree is 10 -3 Filling high-purity argon with the flowing mass purity of 99.99% after Pa, keeping the furnace atmosphere at micro positive pressure, and performing hot pressing treatment to obtain a copper-molybdenum-copper composite blank; the pressure of the hot pressing treatment is 5MPa, the temperature is 680 ℃, and the time of heat preservation and pressure maintaining is 30min;
step five, rolling and thinning: taking out the copper-molybdenum-copper composite blank obtained in the step four, and then placing the blank into a hot rolling mill to carry out hot rolling treatment and annealing to obtain a copper-molybdenum-copper composite material belt; the reduction rate of the first pass of the hot rolling treatment is 60%, the reduction rate of each pass is gradually reduced, and the reduction rate of the last pass is 30%; the thickness of the copper-molybdenum-copper composite material belt is 15% higher than that of the target product copper-molybdenum-copper layered composite material;
step six, rolling for the final time: and D, cleaning the surface oxide of the copper-molybdenum-copper composite material belt obtained in the step five, then rolling for more than one pass, annealing to obtain the copper-molybdenum-copper layered composite material, and counting the thickness of the transition layer in the copper layer of the copper-molybdenum-copper layered composite material, wherein the thickness ratio of each layer of copper to molybdenum-copper in the obtained copper-molybdenum-copper layered composite material is 1:3:1.
Comparative example 3
This comparative example differs from example 3 in that: the second step is not included, namely, the molybdenum plate is not subjected to laser texturing treatment; and step four, adopting the cleaned titanium foil as a transition layer.
Example 4
The embodiment comprises the following steps:
step one, material preparation: rolling and annealing a red copper blank plate, cutting, mechanically polishing to remove a surface oxide layer, and ultrasonically cleaning by using acetone to obtain a copper plate with the thickness of 1.5 mm; casting by adopting a vacuum smelting method to obtain a copper-silver-titanium plate, rolling, and cutting to obtain copper-silver-titanium foil with the thickness of 0.07 mm; rolling and annealing a molybdenum plate, cutting, mechanically polishing to remove a surface oxide layer, and ultrasonically cleaning by using acetone to obtain a molybdenum plate with the thickness of 1.05 mm; the lengths and the widths of the copper plate, the copper silver titanium foil and the molybdenum plate are the same, the lengths are 180mm, and the widths are 50mm;
the mass ratio of copper element, silver element and titanium element in the copper-silver-titanium plate is 8:1.7:0.3;
step two, surface laser texturing treatment: carrying out laser texturing treatment on the front and back surfaces of the molybdenum plate obtained in the step one to obtain a treated molybdenum plate; the diameter of a focusing light spot adopted in the laser texturing treatment is 10 mu m, the distance between the light spots is 10 mu m, a scanning track is a grid type, and the protective atmosphere is argon;
step three, surface cleaning: soaking the molybdenum plate treated in the second step in a dilute sulfuric acid solution with the mass concentration of 15% at 40 ℃ for 10min, taking out, then placing the molybdenum plate in flowing desalted water for washing for 5min, then placing the molybdenum plate in acetone for ultrasonic cleaning for 15min, taking out, drying by cold air to obtain a cleaned molybdenum plate, respectively carrying out ultrasonic cleaning on the copper plate and the copper-silver-titanium foil obtained in the first step by using acetone for 15min, taking out, drying by cold air, and obtaining a cleaned copper plate and a cleaned copper-silver-titanium foil;
step four, hot pressing and compounding: taking the cleaned molybdenum plate obtained in the third step as an intermediate layer, taking the cleaned copper plate as a copper layer, taking the cleaned copper silver titanium foil as a transition layer, stacking 3 unit structures in a graphite mold along the height direction by taking graphite paper as an interval according to the unit structure of the copper layer-transition layer-intermediate layer-transition layer-copper layer, then placing the graphite mold in a vacuum hot pressing furnace, vacuumizing and washing gas three times until the vacuum degree is 10 -3 Filling high-purity argon with the flowing mass purity of 99.99% after Pa, keeping the furnace atmosphere at micro positive pressure, and performing hot pressing treatment to obtain a copper-molybdenum-copper composite blank; the pressure of the hot pressing treatment is 10MPa, the temperature is 750 ℃, and the time of heat preservation and pressure maintaining is 15min;
step five, rolling and thinning: taking out the copper-molybdenum-copper composite blank obtained in the step four, and then placing the blank into a hot rolling mill to carry out hot rolling treatment and annealing to obtain a copper-molybdenum-copper composite material belt; the reduction rate of the first pass of the hot rolling treatment is 50%, the reduction rate of each pass is gradually reduced, and the reduction rate of the last pass is 30%; the thickness of the copper-molybdenum-copper composite material belt is 12% higher than that of the target product copper-molybdenum-copper layered composite material;
step six, rolling for the final time: and D, cleaning the surface oxide of the copper-molybdenum-copper composite material belt obtained in the step five, then rolling for more than one pass, annealing to obtain the copper-molybdenum-copper layered composite material, and counting the thickness of the transition layer in the copper layer of the copper-molybdenum-copper layered composite material, wherein the thickness ratio of each layer of copper to molybdenum-copper in the obtained copper-molybdenum-copper layered composite material is 1:1:1.
Comparative example 4
This comparative example differs from example 4 in that: the second step is not included, namely, the molybdenum plate is not subjected to laser texturing treatment; and step four, adopting the cleaned titanium foil as a transition layer.
Example 5
The embodiment comprises the following steps:
step one, material preparation: rolling and annealing a red copper blank plate, cutting, mechanically polishing to remove a surface oxide layer, and ultrasonically cleaning by using acetone to obtain a copper plate with the thickness of 1.5 mm; casting by adopting a vacuum smelting method to obtain a copper-silver-titanium plate, rolling, and cutting to obtain copper-silver-titanium foil with the thickness of 0.07 mm; rolling and annealing a molybdenum plate, cutting, mechanically polishing to remove a surface oxide layer, and ultrasonically cleaning by using acetone to obtain a molybdenum plate with the thickness of 1.05 mm; the lengths and the widths of the copper plate, the copper silver titanium foil and the molybdenum plate are the same, the lengths are 180mm, and the widths are 50mm;
the mass ratio of copper element, silver element and titanium element in the copper-silver-titanium plate is 8:1.7:0.3;
step two, surface laser texturing treatment: carrying out laser texturing treatment on the front and back surfaces of the molybdenum plate obtained in the step one to obtain a treated molybdenum plate; the diameter of a focusing light spot adopted in the laser texturing treatment is 10 mu m, the distance between the light spots is 10 mu m, a scanning track is a grid type, and the protective atmosphere is argon;
step three, surface cleaning: soaking the molybdenum plate treated in the second step in a dilute sulfuric acid solution with the mass concentration of 15% at 40 ℃ for 10min, taking out, then placing the molybdenum plate in flowing desalted water for washing for 5min, then placing the molybdenum plate in acetone for ultrasonic cleaning for 15min, taking out, drying by cold air to obtain a cleaned molybdenum plate, respectively carrying out ultrasonic cleaning on the copper plate and the copper-silver-titanium foil obtained in the first step by using acetone for 15min, taking out, drying by cold air, and obtaining a cleaned copper plate and a cleaned copper-silver-titanium foil;
step four, hot pressing and compounding: taking the cleaned molybdenum plate obtained in the third step as an intermediate layer, taking the cleaned copper plate as a copper layer, taking the cleaned copper silver titanium foil as a transition layer, stacking the combined structure in a graphite mold along the height direction according to the combined structure of the copper layer-transition layer-intermediate layer-transition layer-copper layer-transition layer-intermediate layer-transition layer-copper layer, then placing the graphite mold in a vacuum hot pressing furnace, vacuumizing and washing three times until the vacuum degree is 10 -3 Filling high-purity argon with the flowing mass purity of 99.99% after Pa, keeping the furnace atmosphere at micro positive pressure, and performing hot pressing treatment to obtain a copper-molybdenum-copper composite blank; the pressure of the hot pressing treatment is 10MPa, the temperature is 750 ℃, and the time of heat preservation and pressure maintaining is 15min;
step five, rolling and thinning: taking out the copper-molybdenum-copper composite blank obtained in the step four, and then placing the blank into a hot rolling mill to carry out hot rolling treatment and annealing to obtain a copper-molybdenum-copper composite material belt; the reduction rate of the first pass of the hot rolling treatment is 50%, the reduction rate of each pass is gradually reduced, and the reduction rate of the last pass is 30%; the thickness of the copper-molybdenum-copper composite material belt is 12% higher than that of the target product copper-molybdenum-copper layered composite material;
step six, rolling for the final time: and D, cleaning the surface oxide of the copper-molybdenum-copper composite material belt obtained in the step five, then rolling for more than one pass, annealing to obtain a copper-molybdenum-copper layered composite material, and counting the thickness of a transition layer in the copper layer of the copper-molybdenum-copper layered composite material, wherein the thickness ratio of each layer of copper, molybdenum, copper and molybdenum in the obtained copper-molybdenum-copper layered composite material is 1:1:1:1:1.
Comparative example 5
This comparative example differs from example 5 in that: the second step is not included, namely, the molybdenum plate is not subjected to laser texturing treatment; and step four, adopting the cleaned titanium foil as a transition layer.
The properties of the copper-molybdenum-copper layered composites prepared in examples 1 to 5 and comparative examples 1 to 5 according to the present invention were examined, and the results are shown in Table 1.
TABLE 1
As can be seen from table 1, comparing examples 1 and 1, 2 and 2, 3 and 3, 4 and 4, and 5, the copper-molybdenum-copper layered composite materials prepared in examples 1 to 5 have higher copper-molybdenum interface bonding strength, thermal conductivity and thermal expansion coefficient than the corresponding comparative examples under the same product parameter specifications, i.e., the respective layer thickness ratios, and demonstrate that the bonding capability between the molybdenum plate and the copper plate and the thermal performance of the copper-molybdenum-copper layered composite material are improved by performing laser texturing treatment on the molybdenum plate and performing hot pressing treatment by combining copper-silver-titanium foil as a transition layer.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (10)
1. The preparation method of the copper-molybdenum-copper layered composite material is characterized by comprising the following steps of:
step one, material preparation: rolling and annealing the red copper blank plate, cutting, and performing surface treatment to obtain a copper plate; casting by adopting a vacuum smelting method to obtain a copper-silver-titanium plate, rolling, and cutting to obtain copper-silver-titanium foil; rolling and annealing the molybdenum plate, cutting, and performing surface treatment to obtain a molybdenum plate; the lengths and the widths of the copper plate, the copper silver titanium foil and the molybdenum plate are the same;
step two, surface laser texturing treatment: carrying out laser texturing treatment on the front and back surfaces of the molybdenum plate obtained in the step one to obtain a treated molybdenum plate;
step three, surface cleaning: sequentially carrying out acid washing, desalted water washing and ultrasonic cleaning on the molybdenum plate treated in the second step to obtain a cleaned molybdenum plate, and respectively carrying out ultrasonic cleaning on the copper plate and the copper-silver-titanium foil obtained in the first step to obtain a cleaned copper plate and a cleaned copper-silver-titanium foil;
step four, hot pressing and compounding: the cleaned molybdenum plate obtained in the third step is used as an intermediate layer, the cleaned copper plate is used as a copper layer, the cleaned copper silver titanium foil is used as a transition layer, the copper silver titanium foil is stacked in a graphite mold according to a preset structure of a target product copper molybdenum copper layered composite material, then the graphite mold is placed in a vacuum hot-pressing furnace, the vacuum is pumped and the flowing high-purity argon is filled after three times of gas washing, so that the atmosphere in the furnace is kept at micro positive pressure, and then hot-pressing treatment is carried out, so that a copper molybdenum copper composite blank is obtained;
step five, rolling and thinning: taking out the copper-molybdenum-copper composite blank obtained in the step four, and then placing the blank into a hot rolling mill to carry out hot rolling treatment and annealing to obtain a copper-molybdenum-copper composite material belt;
step six, rolling for the final time: and D, cleaning the surface oxide of the copper-molybdenum-copper composite material belt obtained in the step five, and then rolling for more than one pass, and annealing to obtain the copper-molybdenum-copper layered composite material.
2. The method for preparing the copper-molybdenum-copper layered composite material according to claim 1, wherein in the first step, the thickness of the copper plate is 0.1 mm-1.5 mm, the thickness of the copper-silver-titanium foil is 0.05 mm-0.1 mm, the thickness of the molybdenum plate is 0.5 mm-2.5 mm, the lengths of the copper plate, the copper-silver-titanium foil and the molybdenum plate are 150 mm-200 mm, and the widths of the copper plate, the copper-silver-titanium foil and the molybdenum plate are 20 mm-50 mm.
3. The method for preparing the copper-molybdenum-copper layered composite material according to claim 1, wherein in the first step, the mass ratio of copper element, silver element and titanium element in the copper-silver-titanium plate is 6-9: 0.8 to 3.5:0.2 to 0.5.
4. The method for preparing a copper-molybdenum-copper layered composite material according to claim 1, wherein in the first step, the surface treatments are: and removing the surface oxide layer by mechanical polishing, and ultrasonically cleaning by adopting acetone.
5. The method for preparing a copper-molybdenum-copper layered composite material according to claim 1, wherein in the second step, the diameter of a focusing light spot used for the laser texturing treatment is 5-25 μm, the distance between the light spots is 5-25 μm, the scanning track is a grid type, and the protective atmosphere is argon.
6. The method for preparing a copper-molybdenum-copper layered composite material according to claim 1, wherein the process of cleaning the molybdenum plate in the third step is as follows: soaking a molybdenum plate in dilute sulfuric acid solution with the mass concentration of 5% -15% at 40 ℃ for 10min, taking out, placing the molybdenum plate in flowing desalted water for washing for 5min, then placing the molybdenum plate in acetone for ultrasonic cleaning for 15min, taking out, and drying by cold air; the cleaning process of the copper plate and the copper silver titanium foil comprises the following steps: and respectively ultrasonically cleaning the copper plate and the copper silver titanium foil by using acetone for 15min, taking out, and drying by using cold air.
7. The method for preparing a copper-molybdenum-copper layered composite material according to claim 1, wherein the vacuum degree of the evacuation and the gas washing in the fourth step is 10 -3 Pa, the mass purity of the high-purity argon is more than 99.95%, the pressure of the hot pressing treatment is 5-15 MPa, the temperature is 680-780 ℃, and the time of heat preservation and pressure maintaining is 10-30 min.
8. The method according to claim 1, wherein in the fourth step, the predetermined structure is a unit structure of copper layer-transition layer-intermediate layer-transition layer-copper layer, or a combined structure of transition layer-intermediate layer-transition layer-copper layer continuously stacked on the copper layer of the unit structure.
9. The method for preparing a copper-molybdenum-copper layered composite material according to claim 1, wherein in the fourth step, a plurality of groups of preset structures are overlapped in the height direction by using graphite paper as a space in a graphite mold.
10. The method for preparing a copper-molybdenum-copper layered composite material according to claim 1, wherein the reduction rate of each pass of the hot rolling treatment in the fifth step is 30% -60%, and the thickness of the copper-molybdenum-copper composite material belt is 10% -15% higher than that of the target product copper-molybdenum-copper layered composite material.
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