CN106269958A - One not solid solution metal system lamination metal complex method - Google Patents
One not solid solution metal system lamination metal complex method Download PDFInfo
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- CN106269958A CN106269958A CN201510259639.6A CN201510259639A CN106269958A CN 106269958 A CN106269958 A CN 106269958A CN 201510259639 A CN201510259639 A CN 201510259639A CN 106269958 A CN106269958 A CN 106269958A
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- 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
Abstract
The present invention relates to one not solid solution metal system lamination metal complex method, belong to laminated composite materials preparing technical field.The method includes that the surface of core processes；The surface modification of core and once cover copper；Vacuum electron beam welding with copper clad note copper core material；Secondary covers copper；Cold rolling finishing；And hydrogen shield annealing etc..Not solid solution metal system lamination metal composite prepared by the present invention has interface bond strength height, dimensional accuracy is high, plate shape is good, the sandwich layer quality advantage that layer thickness deviation is little and the depth of parallelism is good good, each, can be applied to electronic information technical field as a kind of electronic package material or heat sink material.
Description
Technical field
The not solid solution metal system lamination metal that the present invention relates to a kind of high interfacial bonding strength high dimensional accuracy is combined
Method, the method can make the immiscible bimetallic system of solid-state obtain high interfacial bonding strength, three layers of high dimensional accuracy
And above lamination metal is combined, particularly to copper/molybdenum/copper (CMC), copper/tungsten/copper (CWC), copper/molybdenum-copper/copper
(CPC), copper/tungsten-copper/copper, copper/molybdenum/copper/molybdenum/copper, copper/molybdenum/copper/molybdenum/... the laminations such as/copper (the total number of plies≤29)
The high interfacial bonding strength of composite, in high precision complex method, belong to laminated composite materials preparing technical field.
Background technology
Three layers and the above lamination metal composites, i.e. the metal ground plane composite wood of " sandwich " structure such as copper/molybdenum/copper
Material, this material had both had, at in-plane, the heat-conductivity conducting performance that copper is excellent, had had again the refractory metal such as tungsten, molybdenum
High intensity, low-expansion feature, and can be by changing each layer thickness ratio with some critical electronic materials such as
Silicon, GaAs, aluminium oxide, beryllium oxide, aluminium nitride etc. match, simultaneously this material air-tightness height, processing characteristics
Well, the favor of the industries such as electronics, microwave, communication, radio frequency, medical treatment, Aero-Space is therefore enjoyed.Particularly
Along with Electronic Encapsulating Technology miniaturization, lightweight, low cost, high-performance, the development trend of high reliability, copper/
The laminated composite materials such as molybdenum/copper are in field performances such as HB-LED, multi-chip group substrate material, heat sink heat radiation, radars
Go out increasingly extensive application prospect.
At present, the complex method of the laminated composite materials such as CMC has Rolling compund, Explosion composite, hot pressing compound, molten
Cover compound, electroplating deposition, Diffusion Welding, hot spray process etc..Wherein, blast, hot pressing, cladding, electroplate, expand
Dissipate the methods such as weldering, thermal spraying in surface quality, layers of copper quality, boundary strength, dimensional accuracy, sandwich layer quality, power
Learn that performance etc. is a certain or some aspects is the most not ideal enough；Roll-bonding method in the research of the laminated composite materials such as CMC and
Production is most widely used, but is because the immiscible bi-metal interface of solid-state such as molybdenum-copper, tungsten-copper at draught pressure
Under cannot realize metallurgical binding, it is difficult to obtain high interfacial bonding strength；Copper and the ductility of the refractory metal such as tungsten, molybdenum
Differ greatly with resistance of deformation, laminated composite materials layer thickness ratio and precision controlling difficulty can be caused；Meanwhile,
Cooperative transformation difficulty between the two, huge deflection during Rolling compund, easily causes bigger deformation processing in addition
Residual stress；And in the operation of rolling colded and heat succeed each other, it is easy that the greatest differences of thermal coefficient of expansion makes in material
Form thermal stress；These stress tend in organizational structure loosely, adhesion is more weak molybdenum/copper, tungsten/copper interface
The sandwich layer of, low thermal coefficient of expansion relatively poor with plasticity is concentrated, reduce interface bond strength, destroy interfacial structure and
Sandwich layer tissue, and ultimately result in laminated composite materials layering, foaming, peeling and sandwich layer layering, cracking.
In order to obtain high interfacial bonding strength, high dimensional accuracy, lamination composite material that sandwich layer is intact, research
Persons have attempted various method.The Chinese patent of publication number CN102995028A proposes a kind of based on irradiation damage expansion
Dissipate copper/molybdenum/carbon/carbon-copper composite material and the preparation method of alloying, it is desirable to by irradiation damage, molybdenum plate is diffused alloy
Changing, re-plating is covered copper and is aided with high annealing, and to reaching, molybdenum plate is penetrated in copper diffusion, copper-molybdenum interface forms metallurgy
In conjunction with, improve interface bond strength purpose.But, galvanoplastic resulting copper layer is equal at purity, compactness, thickness
The each side such as even property compare to rolling and differ greatly, it is difficult to meet the Electronic Packaging application performance requirement to material.
The patent of Publication No. CN102126112A proposes the plasticity difference unsuitable plastic deformation processing in view of core molybdenum, uses
Diffusion Welding direct combination prepares multilayer materials.But the Publication No. of identical first inventor's application
The patent of CN102941441A proposes only poor by Diffusion Welding combined strength bination, therefore uses Diffusion Welding+large deformation
The method of cold rolling (in embodiment deflection all more than 90%) measured is to obtaining high interfacial bonding strength, high-precision
Copper-molybdenum-copper laminated composite materials.But, as this inventor points out, aximal deformation value is cold rolling to molybdenum sandwich layer tissue
The destruction of structure and dimensional accuracy is difficult to avoid that, and copper and molybdenum ductility under aximal deformation value, resistance of deformation huge
The residual stress that big difference causes makes actual being difficult to of the method obtain high interfacial bonding strength.
Therefore, it is necessary to for a kind of high interfacial bonding strength of solid-state immiscible bimetallic system exploitation, high size essence
Degree, three layers and above (the total number of plies≤29) lamination metal complex method that sandwich layer is intact.
Summary of the invention
For above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of high interfacial bonding strength, high chi
Very little precision, plate shape are good, the sandwich layer quality not solid solution metal system that layer thickness deviation is little and the depth of parallelism is good good, each is folded
Layer metal composite method.The method uses the high energy copper ion implantation technology of nonequilibrium state to be modified core surfaces
And once cover copper formation transition layers of copper；The high temperature insostatic pressing (HIP) complex technique using nearly end form carries out secondary and covers copper, reduces each
Layer cooperative transformation amount, it is ensured that obtain the high strength bond at copper/molybdenum/copper interface；Use the cold rolling (deflection of small deformation amount
≤ 20%) composite board finishing is carried out, it is ensured that the thickness and precision of laminated composite materials and tolerance, plate shape, sandwich layer matter
Amount, surface roughness, each layer thickness deviation and the depth of parallelism.This group technology is not solid solution metal system lamination metal
The intact preparation of the high interfacial bonding strength of composite, high dimensional accuracy, sandwich layer provides strong technical support.
One not solid solution metal system lamination metal complex method, employing ion implanting interface modification+once cover copper+heat
Isostatic pressed secondary covers copper+cold rolling finishing makes not solid solution metal system lamination metal be combined.First, energetic ion is used
Injection technique carries out surface modification and once covers copper lamellar core, forms transition zone at core surfaces, will be the most not solid
Molten bi-metal interface is converted into copper/copper interface；Then, use high temperature insostatic pressing (HIP) method to carry out secondary and cover copper, and be aided with cold
Roll finishing, after through hydrogen shield anneal, obtain lamination composite material.
Above-mentioned not solid solution metal system lamination metal complex method, including step in detail below:
(1) surface of core processes
By core (molybdenum sheet, or tungsten, tungsten-copper, molybdenum-copper, molybdenum+copper sheet etc.) at polishing, defat and acid-wash activation
After reason, with deionized water, alcohol washes and be vacuum dried；
(2) surface modification of core and once cover copper
Based on oxygen-free copper negative electrode, use high energy copper ion implantation technology that core is carried out surface modification, and at plated surface
Copper film, forms transition zone, non-solid-solution bi-metal interface is converted into copper/copper interface；By adjusting arc voltage, acceleration
The parameter such as voltage and line to control the copper ion injection degree of depth, speed, distribution and copper film thickness in core, and
Injection and the plating dosage of copper ion, thus regulation and control molybdenum copper transition is controlled with injection charge integration value or injection length
The size of layer and composition；
(3) vacuum electron beam welding of oxygen-free copper stripe cladding note copper core material
Wrap up the core of the most two-sided note copper with anaerobic Copper Foil, copper strips or copper coin doubling, with copper bar or tungsten rod flatten Copper Foil,
Copper strips or copper coin weld seam also carry out vacuum electron beam welding, control weldquality by adjusting welding condition；
(4) secondary covers copper
The secondary using hot isostatic pressing technique to carry out core covers copper, obtains the copper/core/copper lamination composite wood of nearly end form
Material；
(5) cold rolling finishing
The laminated composite materials of the nearly end form obtained is carried out cold rolling finishing；
(6) hydrogen shield annealing
Under hydrogen atmosphere is protected, laminated composite materials is made annealing treatment.
In step (1), described core material be molybdenum, tungsten, tungsten-copper, molybdenum-copper, or molybdenum and copper interval many
Layer molybdenum-steel structure, the total number of plies≤27 of sandwich layer, it is shaped as lamellar；In tungsten-copper or molybdenum-copper, copper content is≤50w%；Institute
The thickness of the core stated is 0.05～10.0mm.
In step (2), during using high energy copper ion implantation, copper ion implantation technological parameter is: arc voltage is
50～300V, accelerating potential is 1～100KeV, and line is 1～20mA；The injection degree of depth of copper ion be 0～
2000nm, preferably 50～2000nm, the implantation dosage of copper ion is 1015～1020Individual/cm2, preferably 1015~
1018Individual/cm2, copper film thickness is 1～10 μm.
In step (3), the thickness of described anaerobic Copper Foil, copper strips or copper coin is 0.05～10.0mm；Described
The technological parameter of vacuum electron beam welding is: welding current is 1～50mA, and voltage is 30～100kV.
In step (4), in hot isostatic pressing, high temperature insostatic pressing (HIP) secondary covers process for copper parameter and is: temperature be 500～
1000 DEG C, pressure is 50～200MPa, and the time is 0.1～5h.
In step (5), described cold rolling finishing is the cold rolling finishing process of low total deformation rate, total deformation rate≤20%；
Nearly to carry out low total deformation rate cold rolling for the laminated composite materials of end form, uses the hard alloy roll of high rigidity, passes through
Adjust the rolling technological parameters such as draught pressure, mill speed and roll gap, stablize, accurately control laminated composite materials
Plate shape, thickness and tolerance thereof, surface roughness and flatness.
In described cold-rolled process, cold rolling finishing process parameter is: draught pressure is 20～100t, and mill speed is
0～10m/min, preferably 0.5～10m/min, roll gap is 0～8mm, preferably 0.1～8mm.
In step (6), the temperature of described annealing is 500～1000 DEG C, and temperature retention time is 0.5～4 little
Time.
The present invention compared with prior art has the advantage that
(1) the high energy copper ion implantation technology of nonequilibrium state is used core surfaces to be modified and once covers copper shape
Transition layers of copper, utilization and matrix is become to have the transition zone of the strongest adhesion, by the molybdenum/copper interface transform of not solid solution originally
For copper/copper interface, thus obtain high interfacial bonding strength；
(2) the high temperature insostatic pressing (HIP) complex technique using nearly end form carries out secondary and covers copper, reduces each layer cooperative transformation amount,
Prevent molybdenum layer layering, cracking, it is ensured that obtain the high strength bond at copper/molybdenum/copper interface；
(3) use small deformation amount High Precision Cold (deflection≤20%) to carry out composite board finishing, reduce each layer
Cooperative transformation amount, it is ensured that the thickness and precision of laminated composite materials and tolerance, plate shape, sandwich layer quality, rough surface
Degree, each layer thickness deviation and the depth of parallelism.
Not solid solution metal system lamination metal composite prepared by the present invention has interface bond strength height, size
Precision is high, plate shape is good, the sandwich layer quality advantage that layer thickness deviation is little and the depth of parallelism is good good, each, can be as one
Electronic package material or heat sink material are applied to electronic information technical field.
Accompanying drawing explanation
The photo in kind of the CMC laminated composite materials that Fig. 1 is obtained by the embodiment of the present invention 1.
Fig. 2 is that the tensile sample assembly of molybdenum in the present invention/copper laminated composite materials interface bond strength test is (with reference to row
Industry standard SJ/T-3326-2001).
Fig. 3-1 and Fig. 3-2 is that the CMC laminated composite materials cross-sectional metallographic obtained in the embodiment of the present invention 2 shines
Sheet.
Fig. 4-1 and Fig. 4-2 is the copper-tungsten copper obtained in the embodiment of the present invention 7-copper laminated composite materials cross section gold
Phase photo.
Detailed description of the invention
The not solid solution metal system lamination metal complex method of the high interfacial bonding strength high dimensional accuracy of the present invention, bag
Include following steps:
(1) surface of core processes
By the core molybdenum sheet of thickness 0.05～10.0mm (or tungsten, tungsten-copper, molybdenum-copper, molybdenum+copper sheet, molybdenum+copper+molybdenum
+ ...+molybdenum (the sandwich layer number of plies≤27), tungsten-copper, molybdenum-copper sheet copper content is 0～50%, the most all using molybdenum sheet as generation
Watch core material) after fine sandpaper polishing, defat and acid-wash activation process, do by deionized water, alcohol washes vacuum
Dry.
(2) surface modification of core and once cover copper
Based on oxygen-free copper negative electrode, use high energy copper ion implantation technology that core is carried out surface modification, and at plated surface
Copper film, forms transition zone, non-solid-solution bi-metal interface is converted into copper/copper interface.By adjust arc voltage (50～
300V), accelerating potential (1～100KeV) and line (1～20mA) are to control copper ion note in molybdenum sheet
Enter the degree of depth (0～2000nm), speed, distribution and copper film thickness (1～10 μm), and to inject charge integration
Value or injection length control injection and the plating dosage (10 of copper ion15～1020Individual/cm2), thus regulation and control molybdenum copper
The size of transition zone and composition, cover copper for follow-up secondary, realize good interface cohesion and lay the foundation.
(3) vacuum electron beam welding of oxygen-free copper stripe cladding note copper core material
Right with the anaerobic Copper Foil of thickness 0.05～10.0mm, copper strips or copper coin (following all using copper strips as representing)
Folding wraps up the molybdenum sheet of the most two-sided note copper, flattens copper strips weld seam with copper bar or tungsten rod and carries out electron beam vacuum welding, logical
Cross adjustment welding current (1～50mA), voltage (30～100kV) controls weldquality.
(4) secondary covers copper
Use hot isostatic pressing technique, under the conditions of 500～1000 DEG C, 50～200MPa, 0.1～5h, carry out core
The secondary of molybdenum sheet covers copper, obtains the CMC laminated composite materials of nearly end form.
(5) cold rolling finishing
Above-mentioned nearly end form CMC laminated composite materials is carried out low total deformation rate cold rolling, use the hard of high rigidity to close
Gold roll, by adjusting draught pressure (20～100t), mill speed (0～10m/min) and roll gap (0～8mm)
Deng rolling technological parameter, stable, accurately control the thickness of CMC laminated composite materials and tolerance thereof, plate shape,
Sandwich layer quality, surface roughness and flatness.
(6) hydrogen shield annealing
Under hydrogen atmosphere is protected, laminated composite materials is annealed in 500～1000 DEG C of insulations for 0.5～4 hour
Process.
The following is the specific embodiment of the present invention, but the invention is not restricted to following embodiment.
Embodiment 1
Choose the core molybdenum sheet of 0.1mm thickness after fine sandpaper polishing, defat and acid-wash activation process, use deionization
Water, alcohol washes are also vacuum dried；Based on oxygen-free copper negative electrode, at arc voltage 100V, accelerating potential 50KeV, bundle
Molybdenum core after under stream 5mA processing surface carries out ion implanting interface modification and once covers copper；The note of copper ion
Entering the degree of depth is 50nm, and the implantation dosage of copper ion is 3 × 1015Individual/cm2, copper film thickness is 1 μm；With thickness it is
The core molybdenum sheet of double-sided copper-clad is wrapped up in the anaerobic Copper Foil doubling of 0.1mm, is lined with copper sheet between edge two-layer Copper Foil,
And flatten copper strips weld seam with copper bar, under welding current 5mA, voltage 30kV, carry out electron beam vacuum welding, for
Next step high temperature insostatic pressing (HIP) covers copper prepares；600 DEG C, the high temperature insostatic pressing (HIP) secondary that carries out molybdenum sheet under 50MPa cover copper
0.1h, obtains the laminated composite materials of nearly end form；Use the hard alloy roll of high rigidity, draught pressure 20t,
Under mill speed 6m/min, roll gap 0.1mm, above-mentioned nearly end form laminated composite materials is cold-rolled to 0.25mm thickness,
Total deformation rate 16.7%；Under nitrogen atmosphere is protected, laminated composite materials is annealed in 600 DEG C of insulations for 0.5 hour
Process, it is thus achieved that the CMC laminated composite materials of 0.25mm thickness.
The photo in kind of CMC laminated composite materials is as shown in Figure 1.This composite panel shape is smooth, each stacked parallel
Degree is good.Its thickness is 0.25mm, deviation≤± 3 μm；Stack thickness deviation layer by layer≤± 3 μm, surface roughness
Ra≤0.1μm.After testing, this method the CMC laminated composite materials molybdenum/copper interface bond strength prepared is
150MPa；The test of its interface bond strength is with reference to industry standard SJ/T-3326-2001, and related tension sample assembly is such as
Shown in Fig. 2.
Embodiment 2
Choose the core molybdenum sheet of 0.21mm thickness after fine sandpaper polishing, defat and acid-wash activation process, spend from
Sub-water, alcohol washes are also vacuum dried；Based on oxygen-free copper negative electrode, arc voltage 180V, accelerating potential 70KeV,
Molybdenum core after under line 10mA processing surface carries out ion implanting interface modification and once covers copper；Copper ion
The injection degree of depth is 200nm, and the implantation dosage of copper ion is 6 × 1018Individual/cm2, copper film thickness is 6 μm；Use thickness
The core molybdenum sheet of double-sided copper-clad is wrapped up in anaerobic Copper Foil doubling for 0.06mm, flattens copper strips weld seam with copper bar,
Carry out electron beam vacuum welding under welding current 5mA, voltage 60kV, cover copper for next step high temperature insostatic pressing (HIP) and prepare；
700 DEG C, the high temperature insostatic pressing (HIP) secondary that carries out molybdenum sheet under 100MPa cover copper 0.5h, obtain the lamination composite wood of nearly end form
Material；Use hard alloy roll, be by upper under 0.1mm at draught pressure 60t, mill speed 1m/min, roll gap
State nearly end form laminated composite materials and be cold-rolled to 0.29mm thickness, total deformation rate 12.1%；Under nitrogen atmosphere is protected,
Laminated composite materials is made annealing treatment in 800 DEG C of insulations for 2 hours, it is thus achieved that the CMC lamination of 0.29mm thickness
Composite.
The cross-sectional metallographic photo of CMC laminated composite materials is as shown in Fig. 3-1 and Fig. 3-2, it can be seen that this is combined
Plate of material shape is smooth, and each lamination depth of parallelism is good.Its thickness is 0.29mm, deviation≤± 3 μm；Stack thickness layer by layer
Deviation≤± 3 μm, surface roughness Ra≤0.1 μm.After testing, this method the CMC laminated composite materials prepared
Molybdenum/copper interface bond strength is 147MPa.
Embodiment 3
Choose the core molybdenum sheet of 6.3mm thickness after fine sandpaper polishing, defat and acid-wash activation process, use deionization
Water, alcohol washes are also vacuum dried；Based on oxygen-free copper negative electrode, at arc voltage 200V, accelerating potential 100KeV, bundle
Molybdenum core after under stream 5mA processing surface carries out ion implanting interface modification and once covers copper；The note of copper ion
Entering the degree of depth is 800nm, and the implantation dosage of copper ion is 5 × 1017Individual/cm2, copper film thickness is 3 μm；With thickness it is
The core molybdenum sheet of double-sided copper-clad is wrapped up in the no-oxygen copper plate doubling of 2.1mm, flattens copper strips weld seam with copper bar, in welding
Carry out electron beam vacuum welding under electric current 10mA, voltage 80kV, cover copper for next step high temperature insostatic pressing (HIP) and prepare；?
900 DEG C, the high temperature insostatic pressing (HIP) secondary carrying out molybdenum sheet under 200MPa cover copper 5h, obtain the laminated composite materials of nearly end form；
Use hard alloy roll, be by above-mentioned under 6mm at draught pressure 100t, mill speed 0.5m/min, roll gap
Nearly end form laminated composite materials is cold-rolled to 10mm thickness, total deformation rate 4.8%；Under nitrogen atmosphere is protected, by lamination
Composite makes annealing treatment in 800 DEG C of insulations for 4 hours, it is thus achieved that the CMC lamination composite wood of 10mm thickness
Material.
This composite panel shape is smooth, and each lamination depth of parallelism is good.Its thickness is 10mm, deviation≤± 20 μm；Respectively
Lamination layer thickness deviation≤± 20 μm, surface roughness Ra≤0.1 μm.After testing, this method the CMC prepared
Laminated composite materials molybdenum/copper interface bond strength is 142MPa.
Embodiment 4
Choose the core molybdenum sheet 2 of 0.45mm thickness, oxygen-free copper stripe 1 (same size), polish through fine sandpaper,
After defat and acid-wash activation process, with deionized water, alcohol washes and be vacuum dried；Based on oxygen-free copper negative electrode,
2 molybdenum cores after under arc voltage 150V, accelerating potential 70KeV, line 20mA processing surface carry out ion
Inject interface modification and once cover copper；The injection degree of depth of copper ion is 200nm, and the implantation dosage of copper ion is 1020
Individual/cm2, copper film thickness is 8 μm；Molybdenum sheet (double-sided copper-clad), copper strips are arranged according to the order of molybdenum/copper/molybdenum；
With oxygen-free copper stripe doubling parcel molybdenum/copper/molybdenum sheet that thickness is 0.45mm, flatten copper strips weld seam with copper bar, at welding electricity
Carry out electron beam vacuum welding under stream 5mA, voltage 50kV, cover copper for next step high temperature insostatic pressing (HIP) and prepare；?
700 DEG C, carry out the high temperature insostatic pressing (HIP) secondary outside molybdenum/copper/molybdenum sheet under 100MPa and cover copper 1h, obtain the copper of nearly end form/
Molybdenum/copper/molybdenum/copper laminated composite materials；Use hard alloy roll, draught pressure 40t, mill speed 0.5m/min,
Under roll gap 1mm, above-mentioned nearly end form laminated composite materials is cold-rolled to 2mm thickness, total deformation rate 11.1%；At hydrogen
Under atmosphere protection, laminated composite materials is made annealing treatment in 700 DEG C of insulations for 1 hour, it is thus achieved that 2mm thickness
Copper/molybdenum/copper/molybdenum/copper laminated composite materials.
This composite panel shape is smooth, and each lamination depth of parallelism is good.Its thickness is 2mm, deviation≤± 10 μm；Respectively
Lamination layer thickness deviation≤± 10 μm, surface roughness Ra≤0.1 μm.After testing, this method the CMC prepared
Laminated composite materials molybdenum/copper interface bond strength is 156MPa.
Embodiment 5
Choose the core leaf of 0.21mm thickness after fine sandpaper polishing, defat and acid-wash activation process, spend from
Sub-water, alcohol washes are also vacuum dried；Based on oxygen-free copper negative electrode, arc voltage 300V, accelerating potential 70KeV,
Tungsten core after under line 10mA processing surface carries out ion implanting interface modification and once covers copper；Copper ion
The injection degree of depth is 1500nm, and the implantation dosage of copper ion is 6 × 1019Individual/cm2, copper film thickness is 7 μm；By thickness
The core leaf of double-sided copper-clad is wrapped up in the oxygen-free copper stripe doubling that degree is 0.21mm, flattens copper strips weld seam with copper bar,
Under welding current 5mA, voltage 60kV, carry out electron beam vacuum welding, cover copper for next step high temperature insostatic pressing (HIP) and do standard
Standby；700 DEG C, the high temperature insostatic pressing (HIP) secondary that carries out leaf under 100MPa cover copper 4h, the lamination obtaining nearly end form is multiple
Condensation material；Use hard alloy roll, be 0.2mm at draught pressure 80t, mill speed 0.5m/min, roll gap
Lower above-mentioned nearly end form laminated composite materials is cold-rolled to 0.6mm thickness, total deformation rate 4.8%；Protect in nitrogen atmosphere
Under, laminated composite materials is made annealing treatment in 900 DEG C of insulations for 2 hours, it is thus achieved that the copper/tungsten of 0.6mm thickness/
Copper laminated composite materials.After testing, this method the copper/tungsten prepared/copper laminated composite materials tungsten/copper interface cohesion is strong
Degree is 130MPa.
This composite panel shape is smooth, and each lamination depth of parallelism is good.Its thickness is 0.6mm, deviation≤± 10 μm；Respectively
Lamination layer thickness deviation≤± 10 μm, surface roughness Ra≤0.1 μm.After testing, this method the CMC prepared
Laminated composite materials tungsten/copper interface bond strength is 135MPa.Embodiment 6
Choose the core molybdenum-copper sheet (Mo85Cu15) of 2.2mm thickness, live through fine sandpaper polishing, defat and pickling
After change processes, with deionized water, alcohol washes and be vacuum dried；Based on oxygen-free copper negative electrode, at arc voltage 180V, add
Molybdenum-copper core material after under speed voltage 70KeV, line 10mA processing surface carries out ion implanting interface modification and
Secondary cover copper；The injection degree of depth of copper ion is 250nm, and the implantation dosage of copper ion is 7 × 1018Individual/cm2, copper film is thick
Degree is 6 μm；Molybdenum-copper core the material of double-sided copper-clad is wrapped up, with copper bar with the no-oxygen copper plate doubling that thickness is 2.2mm
Flatten copper strips weld seam, under welding current 5mA, voltage 60kV, carry out electron beam vacuum welding, for next step heat
Isostatic pressed covers copper prepares；700 DEG C, the high temperature insostatic pressing (HIP) secondary that carries out molybdenum copper sheet under 100MPa cover copper 0.6h,
Laminated composite materials to nearly end form；Use hard alloy roll, draught pressure 40t, mill speed 1m/min,
Roll gap is, under 2mm, above-mentioned nearly end form laminated composite materials is cold-rolled to 6mm thickness, total deformation rate 9.1%；At hydrogen
Under atmosphere protection, laminated composite materials is made annealing treatment in 700 DEG C of insulations for 1 hour, it is thus achieved that 6mm thickness
Copper/molybdenum-copper/copper laminated composite materials.After testing, this method the copper/molybdenum-copper/copper laminated composite materials molybdenum-copper prepared
/ copper interface bond strength is 180MPa.
This composite panel shape is smooth, and each lamination depth of parallelism is good.Its thickness is 6mm, deviation≤± 20 μm；Respectively
Lamination layer thickness deviation≤± 20 μm, surface roughness Ra≤0.1 μm.After testing, this method the CMC prepared
Laminated composite materials molybdenum/copper interface bond strength is 162MPa.
Embodiment 7
Choose core tungsten copper sheet (W87Cu13) of 0.21mm thickness, through fine sandpaper polishing, defat and acid-wash activation
After process, with deionized water, alcohol washes and be vacuum dried；Based on oxygen-free copper negative electrode, in arc voltage 180V, acceleration
Tungsten-copper core material after under voltage 70KeV, line 10mA processing surface carries out ion implanting interface modification and once
Cover copper；The injection degree of depth of copper ion is 250nm, and the implantation dosage of copper ion is 5 × 1018Individual/cm2, copper film thickness
It is 5 μm；Tungsten-copper core the material of double-sided copper-clad is wrapped up, with copper bar pressure with the anaerobic Copper Foil doubling that thickness is 0.07mm
Flat copper strips weld seam, carries out electron beam vacuum welding under welding current 5mA, voltage 50kV, for next step heat etc.
Static pressure covers copper prepares；700 DEG C, the high temperature insostatic pressing (HIP) secondary that carries out tungsten-copper sheet under 100MPa cover copper 0.8h,
Laminated composite materials to nearly end form；Use hard alloy roll, draught pressure 60t, mill speed 0.6m/min,
Roll gap is, under 0.2mm, above-mentioned nearly end form laminated composite materials is cold-rolled to 0.30mm thickness, total deformation rate 14.3%；
Under nitrogen atmosphere is protected, laminated composite materials is made annealing treatment in 700 DEG C of insulations for 1 hour, it is thus achieved that 0.30mm
Copper/tungsten-copper/copper the laminated composite materials of thickness.
The cross-sectional metallographic photo of copper/tungsten-copper/copper laminated composite materials is as shown in Fig. 4-1 and Fig. 4-2, it can be seen that
This composite panel shape is smooth, and each lamination depth of parallelism is good.Its thickness is 0.30mm, deviation≤± 5 μm；Each lamination
Layer thickness deviation≤± 5 μm, surface roughness Ra≤0.2 μm.After testing, this method the copper/tungsten-copper/copper prepared is folded
Layer composite tungsten-copper/copper interface bond strength is 160MPa.
The not solid solution metal system lamination metal complex method of the present invention, uses the high energy copper ion implantation of nonequilibrium state
Core surfaces is modified and once covers copper forming transition layers of copper by technology, by originally not solid solution molybdenum/copper interface turn
Turn to copper/copper interface, thus obtain high interfacial bonding strength；The high temperature insostatic pressing (HIP) complex technique using nearly end form carries out two
Secondary cover copper, carry out composite board finishing in conjunction with small deformation amount cold-rolling process (deflection≤20%), reduce each layer and work in coordination with
Deflection, it is ensured that the thickness and precision of laminated composite materials and tolerance, plate shape, sandwich layer quality, surface roughness,
Each layer thickness deviation and the depth of parallelism.Not solid solution metal system lamination metal composite prepared by the present invention, by horizontal stroke
Cross section metallograph is it will be seen that plate shape is smooth, and each lamination depth of parallelism is good, thickness and stack thickness deviation layer by layer
Little, surface roughness Ra≤0.1 μm.Interface bond strength test is carried out with reference to industry standard SJ/T-3326-2001,
After testing, this method laminated composite materials molybdenum (the tungsten)/copper interface bond strength prepared is 135～162MPa.
The above, only presently preferred embodiments of the present invention, not the present invention is done any restriction, every basis is sent out
Any simple modification made for any of the above embodiments, change and equivalent structure are changed by bright technical spirit, all still fall within
In the protection domain of technical solution of the present invention.
Claims (10)
1. a not solid solution metal system lamination metal complex method, including step in detail below:
(1) surface of core processes: by core after polishing, defat and acid-wash activation process, with deionized water, alcohol washes and be vacuum dried；
(2) surface modification of core and once cover copper: based on oxygen-free copper negative electrode, use high energy copper ion implantation technology that core carries out surface modification, and at plated surface copper film, form transition zone；
(3) with the vacuum electron beam welding of copper clad note copper core material: wrap up the core of the most two-sided note copper with anaerobic Copper Foil, copper strips or copper coin doubling, flatten Copper Foil, copper strips or copper coin weld seam with copper bar or tungsten rod and carry out vacuum electron beam welding, controlling weldquality by adjusting welding condition；
(4) secondary covers copper: the secondary using hot isostatic pressing technique to carry out core covers copper, obtains the copper/core/copper laminated composite materials of nearly end form；
(5) cold rolling finishing: the laminated composite materials of the nearly end form obtained is carried out cold rolling finishing；
(6) hydrogen shield annealing: under hydrogen atmosphere is protected, laminated composite materials is made annealing treatment.
Not solid solution metal system lamination metal complex method the most according to claim 1, it is characterised in that: described core material is molybdenum, tungsten, tungsten-copper, molybdenum-copper, or molybdenum and the multilamellar molybdenum-copper at copper interval, in the total number of plies≤27 of sandwich layer, tungsten-copper or molybdenum-copper, copper content is≤50w%.
Not solid solution metal system lamination metal complex method the most according to claim 2, it is characterised in that: the thickness of described core is 0.05～10.0mm.
Not solid solution metal system lamination metal complex method the most according to claim 1, it is characterised in that: during using high energy copper ion implantation, arc voltage is 50～300V, and accelerating potential is 1～100KeV, and line is 1～20mA.
Not solid solution metal system lamination metal complex method the most according to claim 4, it is characterised in that: the injection degree of depth of copper ion is 0～2000nm, and the implantation dosage of copper ion is 1015～1020Individual/cm2, copper film thickness is 1～10 μm.
Not solid solution metal system lamination metal complex method the most according to claim 1, it is characterised in that: the thickness of described anaerobic Copper Foil, copper strips or copper coin is 0.05～10.0mm.
Not solid solution metal system lamination metal complex method the most according to claim 1, it is characterised in that: the welding current of described vacuum electron beam welding is 1～50mA, and voltage is 30～100kV.
Not solid solution metal system lamination metal complex method the most according to claim 1, it is characterised in that: the temperature of high temperature insostatic pressing (HIP) is 500～1000 DEG C, and pressure is 50～200MPa, and the time is 0.1～5h.
Not solid solution metal system lamination metal complex method the most according to claim 1, it is characterised in that: in cold-rolled process, draught pressure is 20～100t, and mill speed is 0～10m/min, and roll gap is 0～8mm；Total deformation rate≤20% of described cold rolling finishing.
Not solid solution metal system lamination metal complex method the most according to claim 1, it is characterised in that: the temperature of described annealing is 500～1000 DEG C, and temperature retention time is 0.5～4 hour.
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| CN110125407A (en) * | 2019-06-25 | 2019-08-16 | 上海交通大学 | The stratiform copper electrode and its increasing material manufacturing device and method of tungstenic copper alloy layer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5858557A (en) * | 1997-10-14 | 1999-01-12 | Yoon; Sunghee | Nickel/gold plating of a copper-refractory metal material |
| CN103698271A (en) * | 2013-11-22 | 2014-04-02 | 天津大学 | Method for detecting bonding strength of interlayer interfaces of immiscible metal laminated composite material |
| CN103911634A (en) * | 2014-03-06 | 2014-07-09 | 中国电子科技集团公司第五十五研究所 | Surface nickel plating method for molybdenum-based composite material |
| CN106584976A (en) * | 2016-08-10 | 2017-04-26 | 上海交通大学 | High-conductivity graphene/copper-based layered composite material and preparation method thereof |
-
2015
- 2015-05-20 CN CN201510259639.6A patent/CN106269958B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5858557A (en) * | 1997-10-14 | 1999-01-12 | Yoon; Sunghee | Nickel/gold plating of a copper-refractory metal material |
| CN103698271A (en) * | 2013-11-22 | 2014-04-02 | 天津大学 | Method for detecting bonding strength of interlayer interfaces of immiscible metal laminated composite material |
| CN103911634A (en) * | 2014-03-06 | 2014-07-09 | 中国电子科技集团公司第五十五研究所 | Surface nickel plating method for molybdenum-based composite material |
| CN106584976A (en) * | 2016-08-10 | 2017-04-26 | 上海交通大学 | High-conductivity graphene/copper-based layered composite material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110125407A (en) * | 2019-06-25 | 2019-08-16 | 上海交通大学 | The stratiform copper electrode and its increasing material manufacturing device and method of tungstenic copper alloy layer |
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Effective date of registration: 20190117 Address after: 101407 No. 11 Xingke East Street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: Research Institute of engineering and Technology Co., Ltd. Address before: No. 2, Xinjie street, Xicheng District, Beijing, Beijing Patentee before: General Research Institute for Nonferrous Metals |