CN102275022B - Connecting method of C/C composite material and copper or copper alloy - Google Patents

Connecting method of C/C composite material and copper or copper alloy Download PDF

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CN102275022B
CN102275022B CN 201110191054 CN201110191054A CN102275022B CN 102275022 B CN102275022 B CN 102275022B CN 201110191054 CN201110191054 CN 201110191054 CN 201110191054 A CN201110191054 A CN 201110191054A CN 102275022 B CN102275022 B CN 102275022B
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copper
composite
copper alloy
active
solder
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CN102275022A (en
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张劲松
沈元勋
李正林
郝传勇
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Institute of Metal Research of CAS
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Institute of Metal Research of CAS
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Abstract

The invention relates to a connection method of a C/C composite material and copper or copper alloy, belong to the field of heterogeneous material connection and solving the problems of complex preparation method of an active coating, overhigh heat treatment temperature, low joint strength, and the like in the prior art. According to the method, active elements Ti and Si undergo a physicochemical reaction on the surface of the CC composite material to form a laminated transitional reaction layer, therefore the wettability of brazing filler metal is improved, stronger interface combination is formed, and tight connection between the C/C composite material and the copper or copper alloy is realized. According to the invention, the connection between the C/C composite material and the copper or copper alloy is realized by adopting the active Cu-Si brazing filler metal, a transitional interface of CC/(TiC+SiC+Ti5Si3)/copper or copper alloy is formed through the physiochemical reaction of active elements Ti and Si on the interface, therefore the combination strength is high; and a welding joint after welding is of a pure copper structure which is beneficial to retarding the thermal stress of a joint through plastic deformation. The invention has the main technical effects that: compared with an active casting method, the connecting method disclosed by the invention has the advantages that: the prepared joint has high strength and excellent thermal shock stability, and the active element Ti and Si are introduced with a simple method.

Description

The method of attachment of a kind of C/C composite and copper or copper alloy
Technical field
The present invention relates to the method for attachment of a kind of C/C composite and copper or copper alloy, belong to the dissimilar materials connection area.
Background technology
Carbon fiber reinforced carbon matrix composite (C/C) has low-density, low-expansion coefficient, high heat conductance, anti-ablation, anti-thermal shock and thermal fatigue resistance and good mechanical behavior under high temperature, is applied to plasma facing the first wall material in the ITER nuclear fusion test plant.The first wall material need to bear high heat load and Ions Bombardment, and the C/C composite need to connect to form cooling system with heat sink CuCrZr alloy.Therefore, C/C composite and CuCrZr jointing require to have high strength, high heat conductance and high thermal shock stability.Yet, there is significant physical chemistry attribute difference between the two, metallurgical compatibility is poor, and traditional melting connects very difficult.Soldering is one of the most effective dissimilar materials method of attachment, but larger thermal expansion coefficient difference (the Δ α ≈ 16 * 10 of both existence -6/ k), the cooling procedure center tap produces larger residual stress with the severe exacerbation joint performance.Therefore, usually select the fine copper of high heat conduction, low yield strength to alleviate the joint thermal stress as the intermediate layer.Its key technology that is connected of C/C composite and CuCrZr alloy is being connected of C/C composite and copper intermediate layer.The money base active solder can be realized pottery and being connected of alloy, but silver can become cadmium under neutron irradiation, so silver-containing solder can not be applied to nuclear fusion device as facing the plasma parts.
at present, C/C composite and the copper method of attachment reported mainly contain: the reactive metal casting of Austrian Plansee SE technique center exploitation, in advance C/C surface employing laser roughening is processed, then by CVD or PVD deposition techniques one deck active element Ti [F.Rainer, et al.Patent EP 0663670.1995] or Ti+Si[B Schedler, et al.Physica Scripta, 2007, T128:200-203], higher than copper melting temperature (1100 ℃), under vacuum condition, fine copper extruding is cast in the C/C surface and realize that C/C is connected with the tight of Cu.Strength of joint 53.7~73.4MPa that this legal system is standby, but the active coating preparation method is too complicated and higher to equipment requirement.Italy announces a C/C process for modifying surface for the be connected [F.Rainer of C/C with fine copper, et al, patent EP 0663670,1995], group vib Cr, Mo, W element powders are coated in the C/C surface heat-treats, by solid-state reaction Formed compound layer, then fine copper is cast in C/C surface after modification and forms being connected of C/C and Cu, then adopt electron beam welding or etc. static pressure connection Cu and CuCrZr.This technology prepares strength of joint 33MPa, but C/C surface modification heat treatment temperature too high (>1300 ℃), and cost is higher, complex process.Adopt the CuGeNi solder brazing to connect C/C and Cu [M.Salvo, et al.Journal ofNuclear materials.2008,374:69-74], need to through the modification of chromium high-temperature heat treatment, there be above-mentioned shortcoming in strength of joint 34MPa equally but C/C is surperficial.Adopt the TiCuNi amorphous brazing filler metal to connect C/C and Cu[P.Appendino, et al.Fusion Engineering and Design, 2003,66-68:225-229], strength of joint is 24MPa only.Tan Mo wait by force the people adopt active casting connect C/C composite and copper [Tan Moqiang, etc. weld journal, 2006,27 (6): 61-66].The people such as Xie Fengchun adopt TiZrCuNi solder brazing graphite and copper [Xie Fengchun, Deng. welding journal, 2008,29:73-76], between the hard brittle metal that weld seam generates, compound can not effectively be alleviated the joint thermal stress, and strength of joint is low and far can not satisfy the requirement of thermal fatigue property.
In sum, at present mainly there is following problem in the C/C composite with the copper method of attachment: 1. the CC/Cu strength of joint for preparing take Ti+Si as active element of the active casting of the employing height of comparing, but CVD or PVD method complex process are adopted in the active coating preparation, higher to equipment requirement, production cost is higher; 2. the CC/Cu strength of joint for preparing after adopting the group vib metallic element to the C/C surface modification is lower, heat treatment temperature too high (>1300 ℃), and complex process, production cost is higher; 3. adopt the titanium based solder soldering to connect C/C and copper, strength of joint is low, and the fragile metal compound that weld seam generates can't be alleviated joint stress and poor heat conductivity, and thermal shock resistance is poor.At present the domestic C/C composite is connected with copper rarely have report, be badly in need of the exploitation preparation and have the interconnection technique of high strength, high thermal shock stability C/C composite and copper alloy.
Summary of the invention
The present invention is directed to the shortcoming of present C/C composite and copper or copper alloy interconnection technique, the method of attachment of a kind of C/C composite and copper or copper alloy is proposed, adopt copper-based active soldering connection method, solve the problems such as the active coating preparation method who exists in prior art is complicated, heat treatment temperature is too high, strength of joint is low.
Technical scheme of the present invention is:
The present invention forms the transient response layer by active element at the physical-chemical reaction of C/C composite material surface, improves the wetability of solder and forms stronger interface combination, realizes that the C/C composite is connected with the tight of copper or copper alloy.Wherein:
(1) C/C composite: adopt in advance laser technology or other micro-processing technology to the C-base composte material face of weld texturing of punching process, form the bellmouth that the evenly distributed degree of depth is 300~1000 μ m on the surface, the diameter on bellmouth surface is 100~1000 μ m.
(2) titanium processing: after machining, adopt and brush TiH 2Powder method, magnetron sputtering method, PVD or CVD method are carried out the titanium processing, titanium layer thickness 0.5~50 μ m to the C/C surface.
(3) Cu-Si solder: the composition of Cu-Si alloy is: Cu:90~99wt%; Si:1~10wt% uses state to be thin slice or powder, and sheet thickness is 100~500 μ m, and powder size is 50~200 μ m.
(4) welded metal: welded metal is the strong copper alloys of the heat such as anaerobic fine copper, CuCr, CuCrZr or CuCrZrNb.
(5) with C/C composite, Cu-Si solder and copper or copper alloy intermediate layer by the assembling of " C/C-solder-copper or copper alloy " sandwich structure, be placed in vacuum brazing furnace, be warming up to above 20~50 ℃ of welding temperatures of solder fusing point, insulation 5~30min completes soldering.
In the present invention, by active element Ti and the Si physical-chemical reaction at the interface, form CC (TiC+SiC+Ti 5Si 3)/Cu or CC/ (TiC+SiC+Ti 5Si 3The transition interface of)/Cu alloy.
In the present invention, the composition of CuCr copper alloy is as follows: by weight percentage, and Cr:0.3-1.2; All the other are Cu.
In the present invention, the composition of CuCrZr copper alloy is as follows: by weight percentage, Cr:0.25-0.65, Zr:0.08-0.20, all the other are Cu.
In the present invention, the composition of CuCrZrNb copper alloy is as follows: by weight percentage, and Cr:0.15-0.40; Zr:0.10-0.25; Nb:0.08-0.25; Ce:0.02-0.16; All the other are Cu.
Beneficial effect of the present invention:
The present invention adopts active Cu-Si solder to realize being connected of C/C composite and copper or copper alloy, at the physical-chemical reaction at interface, forms CC/ (TiC+SiC+Ti by active element Ti and Si 5Si 3The transition interface of)/copper or copper alloy, bond strength is high; The postwelding weld seam is the fine copper tissue, is conducive to slow down the joint thermal stress by plastic deformation.Major technique effect of the present invention is: compare with active casting, the strength of joint of the present invention's preparation is high, and thermal shock resistance is excellent, and active element Ti and Si introducing method are simple.
Description of drawings
Fig. 1 is C/C composite and the oxygen-free copper joint assembling schematic diagram of preparation in embodiment 1.In figure, 1, the anaerobic fine copper; 2, Cu-3.5Si solder; 3, laser hole; 4, C/C composite.
Fig. 2 is C/C composite and the oxygen-free copper joint weld interface scanning electron microscope (SEM) photograph of embodiment 1 preparation.
Fig. 3 is C/C and Cu-3.5Si solder interface microstructure scanning electron microscope (SEM) photograph in the C/C composite of embodiment 1 preparation and oxygen-free copper joint.
Fig. 4 is the C/C composite of embodiment 1 preparation and the XRD collection of illustrative plates of oxygen-free copper joint median surface conversion zone phase.
The specific embodiment
Embodiment 1
The present invention forms stratiform transient response layer by active element at the physical-chemical reaction of C/C composite material surface, improves the wetability of solder and forms stronger interface combination, realizes that the C/C composite is connected with the tight of copper.Wherein:
1.C/C composite is cut into 15mm * 10mm * 5mm, adopt laser technology to face of weld the texturing of punching process.After machining, use TiH 2Powder (powder size is<20 μ m) brushing C/C surface forms uniform TiH 2Coating, coating layer thickness are 40 μ m.Cu-3.5Si solder foil thickness 200 μ m are processed into 15mm * 10mm * 5mm with the anaerobic fine copper.
2. become sandwich to be placed in soldering oven with the anaerobic fine copper by " C/C-solder-copper " assembled in sequence C/C composite, Cu-3.5Si solder, when vacuum reaches 2 * 10 -3Pa~5 * 10 -3During Pa, be warming up to the welding temperature of 1050~1070 ℃, insulation 5~20min completes soldering.
As shown in Figure 1, have laser hole 3 on C/C composite 4, laser hole 3 is bellmouth evenly distributed in the 4 surface formation of C/C composite, the degree of depth 300~1000 μ m, the diameter on bellmouth surface is 300 μ m, and anaerobic fine copper 1, Cu-3.5Si solder 2 and C/C composite 4 form sandwich in order.
As shown in Figure 2, can find out from C/C composite and oxygen-free copper joint weld interface scanning electron microscope (SEM) photograph, the wetability of the C/C composite material surface of Cu-3.5Si solder after texturing is better, and in the laser roughening hole, solder is filled better, the defectives such as interface flawless, hole.In figure, Braze is solder, and Copper is the oxygen-free copper joint.
As shown in Figure 3, C/C and Cu-3.5Si solder interface microstructure scanning electron microscope (SEM) photograph can be found out from C/C composite and oxygen-free copper joint, solder and C/C composite and oxygen-free copper all form combines closely, and the interface is intact to be fallen into, interface formation significant reaction layer.In figure, Braze is solder, and Reaction layer is interfacial reaction layer.
As shown in Figure 4, can find out from the XRD collection of illustrative plates of C/C composite and oxygen-free copper joint median surface conversion zone phase, XRD analysis shows, the conversion zone phase is TiC, SiC and Ti 5Si 3
In embodiment 1, experimental result data is as follows:
The CC/CuCrZr connector is carried out performance test, and the room temperature shear strength reaches 75MPa, 450 ℃ of thermal shock tests (shrend) through 30 thermal cycles after joint interface remain intact, do not find Interface Crack and peel off obscission.
Embodiment 2
Difference from Example 1 is,
1.C/C composite is cut into 15mm * 10mm * 5mm, adopt laser technology to face of weld the texturing of punching process.After machining, adopt magnetron sputtering method to carry out the titanium processing to the C/C surface, the C/C surface forms uniform Ti coating, and thickness is 10 μ m.Cu-3.5Si solder foil thickness 200 μ m cut into 16mm * 11mm * 7mm size with the CuCrZr alloy, in the CuCrZr alloy, by weight percentage, and Cr:0.25-0.65, Zr:0.08-0.20, all the other are Cu.
2. become sandwich to be placed in soldering oven with the CuCrZr alloy by " C/C-solder-copper alloy " assembled in sequence C/C composite Cu-3.5Si solder, when vacuum reaches 2 * 10 -3Pa~5 * 10 -3During Pa, be warming up to the welding temperature of 1050~1070 ℃, insulation 5~20min completes soldering.After soldering was completed, with greater than the cooling velocity fast cooling to 475 of 1 ℃/s ℃, insulation 3h carried out Ageing Treatment, and after insulation finished, joint cooled to room temperature with the furnace.
In embodiment 2, experimental result data is as follows:
The CC/CuCrZr connector is carried out performance test, and the room temperature shear strength is up to 55MPa, 450 ℃ of thermal shock tests (shrend) through 30 thermal cycles after joint interface remain intact, do not find Interface Crack and peel off obscission.
Embodiment 3
Difference from Example 1 is,
On C/C composite that embodiment 1 obtains and oxygen-free copper joint (CC/Cu joint, Cu thickness 2mm) basis, adopt diffusion welding (DW) to connect CC/Cu joint and CuCrZr alloy, acquisition CC/Cu/CuCrZr connector.
The technological parameter that diffusion welding (DW) connects is as follows:
Diffusion welding (DW) connects 600~800 ℃ of temperature, Bonding pressure 5~10MPa, connect hours 10~60min, vacuum 2 * 10 -3Pa.
The CC/Cu/CuCrZr connector is carried out performance test, and the room temperature shear strength is up to 79MPa, 450 ℃ of thermal shock tests (shrend) through 50 thermal cycles after joint interface remain intact, do not find Interface Crack and peel off obscission, thermal shock resistance is excellent.

Claims (2)

1. the method for attachment of a C/C composite and copper or copper alloy, it is characterized in that: form the transient response layer by active element Ti and Si at the physical-chemical reaction of C/C composite material surface, improve the wetability of solder and form stronger interface combination, realizing that the C/C composite is connected with the tight of copper or copper alloy; Comprise the steps:
(1) C/C composite: adopt in advance laser technology or other micro-processing technology to the C-base composte material face of weld texturing of punching process, form the bellmouth that the evenly distributed degree of depth is 300~1000 μ m on the surface, the diameter on bellmouth surface is 100~1000 μ m;
(2) titanium processing: after machining, adopt and brush TiH 2Powder method, magnetron sputtering method, PVD method or CVD method are carried out the titanium processing, titanium layer thickness 0.5~50 μ m to the C/C surface;
(3) Cu-Si solder: the composition of Cu-Si alloy is Cu:90~99wt%; Si:1~10wt% uses state to be thin slice or powder, and sheet thickness is 100~500 μ m, and powder size is 50~200 μ m;
(4) welded metal: welded metal is anaerobic fine copper, CuCr, CuCrZr or the strong copper alloy of CuCrZrNb heat;
(5) with C/C composite, Cu-Si solder and copper or copper alloy intermediate layer by the assembling of " C/C-solder-copper or copper alloy " sandwich structure, be placed in vacuum brazing furnace, be warming up to above 20~50 ℃ of welding temperatures of solder fusing point, insulation 5~30min completes soldering.
2. according to the method for attachment of C/C composite claimed in claim 1 and copper or copper alloy, it is characterized in that, by active element Ti and the Si physical-chemical reaction at the interface, form CC/ (TiC+SiC+Ti 5Si 3The transition interface of)/copper or copper alloy.
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CN103990880B (en) * 2014-06-06 2015-12-02 哈尔滨工业大学 The nonmetallic materials of inierpeneirating network structure brazed seam and the method for welding of metal material can be formed
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CN104708161B (en) * 2015-02-12 2016-11-30 武汉工程大学 A kind of composite solder
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CN105174991B (en) * 2015-09-25 2017-07-07 浙江工业大学 A kind of laser cladding technology is used for the method for connecting ceramics and metal
CN106695043A (en) * 2016-12-22 2017-05-24 核工业西南物理研究院 Carbon base material and copper brazing connection method
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CN109175659B (en) * 2018-10-31 2020-09-25 天津重型装备工程研究有限公司 Method for positioning bonding interface of metal composite product
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