CN106346100B - A kind of method of carbon nanotube enhancing three-dimensional structure middle layer assistant brazing - Google Patents
A kind of method of carbon nanotube enhancing three-dimensional structure middle layer assistant brazing Download PDFInfo
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- CN106346100B CN106346100B CN201611081818.6A CN201611081818A CN106346100B CN 106346100 B CN106346100 B CN 106346100B CN 201611081818 A CN201611081818 A CN 201611081818A CN 106346100 B CN106346100 B CN 106346100B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 63
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 63
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 33
- 238000005219 brazing Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 78
- 239000002184 metal Substances 0.000 claims abstract description 78
- 239000006260 foam Substances 0.000 claims abstract description 48
- 239000000919 ceramic Substances 0.000 claims abstract description 43
- 239000012535 impurity Substances 0.000 claims abstract description 32
- 229910000679 solder Inorganic materials 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000007654 immersion Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 241000196324 Embryophyta Species 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000000151 deposition Methods 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 229960004756 ethanol Drugs 0.000 claims description 9
- 238000005086 pumping Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 244000137852 Petrea volubilis Species 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 4
- 238000005476 soldering Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 19
- 239000010410 layer Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002905 metal composite material Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910017693 AgCuTi Inorganic materials 0.000 description 1
- 229910017985 Cu—Zr Inorganic materials 0.000 description 1
- 101000666657 Homo sapiens Rho-related GTP-binding protein RhoQ Proteins 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 102100038339 Rho-related GTP-binding protein RhoQ Human genes 0.000 description 1
- 229910004353 Ti-Cu Inorganic materials 0.000 description 1
- 229910004337 Ti-Ni Inorganic materials 0.000 description 1
- 229910010038 TiAl Inorganic materials 0.000 description 1
- 229910011209 Ti—Ni Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- -1 arc discharge method Chemical compound 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000011204 carbon fibre-reinforced silicon carbide Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- 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
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
- B23K1/206—Cleaning
-
- 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
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/008—Soldering within a furnace
-
- 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
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
Abstract
A kind of method of carbon nanotube enhancing three-dimensional structure middle layer assistant brazing, it is related to the method for ceramic soldering and metal.The invention solves existing ceramic materials to connect with solder bonding metal, the problem that residual stress is larger and high-temperature behavior is insufficient.Method: the one, foam metal after preparation is impregnated；Two, the foam metal after immersion is placed in plasma enhanced chemical vapor deposition vacuum plant, and heated up under certain pressure intensity and hydrogen atmosphere；Three, the foam metal of preparation carbon nanotube enhancing；Four, the ceramics of the metal of preparation removal surface impurity, the solder paillon and removal surface impurity that remove surface impurity；Five, the ceramics of foam metal, the solder paillon and removal surface impurity that remove surface impurity that the metal to be welded for removing surface impurity, carbon nanotube enhance successively are stacked, obtains part to be welded, part to be welded is brazed, then cools to room temperature.Method of the present invention for a kind of carbon nanotube enhancing three-dimensional structure middle layer assistant brazing.
Description
Technical field
The present invention relates to the methods of ceramic soldering and metal.
Background technique
Ceramic material is that rigidity is best in current engineering material, the highest material of hardness, while the linear expansion coefficient of ceramics
Lower than metal, when the temperature varies, ceramics have good dimensional stability；Ceramic material generally has high fusing point
(mostly at 2000 DEG C or more), it is not oxidizable at high temperature, and there is good resistance to corrosion to acid, alkali, salt, have and stablizes
Corrosion resistance, and its thermal conductivity is lower than metal material, is good heat-barrier material, and ceramics possess many excellent high temperatures
Energy.Ceramics can be widely used in aerospace, energy traffic, electricity there are many function ceramics according to its production method
Power electronics, biomedicine, chemical industry, the optically and mechanically fields such as engineering.
Although ceramics have the above excellent performance, its plasticity, toughness are lower, and mouldability is bad, it is difficult to be processed into multiple
Miscellaneous structure, therefore mostly use and connect with metal, is realized with metal in the complementary of aspect of performance, with obtain have ceramics with metal respectively
The ceramic-metal composite members of excellent properties.Ceramic-metal composite members are mostly in high temperature load applied by the fields such as space flight and aviation
It works under environment, selected ceramics and the tolerable hot environment of metal, and ceramics are often used method for welding with metal and are attached,
This undoubtedly causes huge challenge to soldered fitting, and the obtained soldered fitting of conventional method can occur molten under high temperature load
The phenomenon that changing, cracking.The soldering connection problem encountered of ceramic-metal composite members is as follows: on the one hand, the two chemical bond is not
Together, crystal structure is different, and physical and chemical composition difference is big, and it is big welding residual stress usually occur, reacts insufficient, brittlement phase mistake
The problems such as more, causes the decline of strength of joint；On the other hand, common method for welding high temperature resistance is poor, is unable to satisfy high temperature work
Make demand.Therefore a kind of guarantee Ceramic and metal joining intensity need to be developed, and the method for being able to satisfy hot operation demand.
Carbon nanotube is hollow tubular structure made of being wound as one or more layers graphene layer by certain spiral angle,
According to theoretical calculation and experiment measurement discovery, the Young's modulus of single-layer carbon nano-tube is worked as, about steel up to 1TPa with diamond phase
5 times of material；Its tensile strength is in the range of 11~63GPa, about 1000 times of steel, has high rigidity and intensity；
And it can reduce soldered fitting stress with lower linear expansion coefficient；Carbon nanotube fusing point with higher, can promote pricker
Expect fusion temperature, therefore it is widely used in reinforcement material.The advantages of carbon nanotube, is that the one-dimension of its structure, reunion
The performance of carbon nanotube performance is influenced, therefore the evenly dispersed of carbon nanotube has vital effect to the performance that it is acted on.
Traditional preparation method of carbon nano-tube such as arc discharge method, laser ablation method, solid-phase pyrolysis, electric glow discharge method, polymerization is anti-
Answer synthetic method etc., the unsetting carbon of generation that all can be different degrees of, reunion carbon nanotube, it is difficult to be used for reinforcement material.
Summary of the invention
The invention solves existing ceramic materials to connect with solder bonding metal, and residual stress is larger and high-temperature behavior is insufficient
The problem of, and a kind of method of carbon nanotube enhancing three-dimensional structure middle layer assistant brazing is provided.
A kind of method of carbon nanotube enhancing three-dimensional structure middle layer assistant brazing follows the steps below:
One, hydrochloric acid, acetone, dehydrated alcohol and the deionized water for being successively 1mol/L~3mol/L with concentration by foam metal
It is respectively washed 10min, then naturally dry, obtains pretreated foam metal, catalyst is added in dehydrated alcohol, obtain
To the ethanol solution for the catalyst that concentration is 0.001mol/L~1mol/L, pretreated foam metal is immersed in dense
Degree is 1h to be stood, then naturally dry, after obtaining immersion in the ethanol solution of the catalyst of 0.001mol/L~1mol/L
Foam metal；
Two, the foam metal after immersion is placed in plasma enhanced chemical vapor deposition vacuum plant, is evacuated to
Pressure is 20Pa~100Pa hereinafter, being passed through hydrogen, and adjusting hydrogen gas flow is 20sccm~60sccm, and adjusting vacuumizes speed
Pressure in plasma enhanced chemical vapor deposition vacuum plant control as 100Pa~300Pa by degree, and is 100Pa in pressure
Under~300Pa and hydrogen atmosphere, temperature is heated up most 300 DEG C~800 DEG C in 30min；
Three, it is passed through carbon-source gas, adjusting carbon-source gas gas flow is 10sccm~100sccm, adjusts hydrogen gas stream
Amount is 1sccm~40sccm, adjusts vacuum pumping rate and controls pressure in plasma enhanced chemical vapor deposition vacuum plant
For 100Pa~1000Pa, then depositing system radio-frequency power is 50W~200W, pressure is 100Pa~1000Pa, carbon source gas
Body gas flow is 10sccm~100sccm, hydrogen gas flow is 1sccm~40sccm and temperature is 300 DEG C~800 DEG C items
It is deposited under part, sedimentation time is 1min~60min, after deposition, closes radio-frequency power supply and heating power supply, stops being passed through
Carbon-source gas and hydrogen, are cooled to room temperature, and obtain the foam metal of carbon nanotube enhancing；
Four, 200 mesh, 400 mesh, 600 mesh and 800 mesh sand paper are successively used to polish metal to be welded, ceramics and solder paillon, so
10min~20min is pre-processed with acetone ultrasound afterwards, the metal to be welded of removal surface impurity is obtained, removes the ceramics of surface impurity
With the solder paillon of removal surface impurity；
Five, the solder of the metal to be welded of surface impurity, the foam metal of carbon nanotube enhancing, removal surface impurity will be removed
The ceramics of paillon and removal surface impurity successively stack, and obtain part to be welded, part to be welded is placed in vacuum brazing furnace, be in pressure
1×10-4Pa~5 × 10-3Under conditions of Pa and brazing temperature are 700 DEG C~1200 DEG C, 1min~20min is kept the temperature, then with drop
Warm speed is 2 DEG C/min~10 DEG C/min, and temperature is cooled to room temperature by 700 DEG C~1200 DEG C, i.e. the enhancing of completion carbon nanotube
The method of three-dimensional structure middle layer assistant brazing.
The basic principle of carbon nanotube enhancing three-dimensional structure middle layer assistant brazing of the present invention: existed using chemical vapor deposition
In-situ preparation carbon nanotube introduces carbon nanotube into weld seam as middle layer on foamed material, uniform due to carbon nanotube
Distribution plays one's part to the full, and dispersion-strengtherning slows down residual stress to improve strength of joint, reduces continuous brittlement phase and generates, and
It is good to form plasticity according to the good plasticity of selected foamed material for the high-temperature behavior for improving connector using the high-temperature behavior of itself
Solid solution, intermetallic compound, to alleviate biggish residual stress between ceramics and metal.
Beneficial effects of the present invention:
1, carbon nanotube high-intensitive in weld seam is uniformly distributed, and plays the effect of dispersion-strengtherning.
2, carbon nanotube thermal expansion coefficient is low, the thermal expansion coefficient of solder is adjusted, selected foamed material plasticity is preferably
Plastic property of weld bead can be improved, to reduce the residual stress of ceramics with metal joint.
3, carbon nanotube is reacted with active element, product Dispersed precipitate, does not form continuous brittlement phase, adjusts conversion zone
Thickness, to improve strength of joint.
4, the good high-temperature behavior of carbon nanotube can improve the high-temperature behavior of soldered fitting significantly.
5, the carbon nanotube of plasma enhanced chemical vapor deposition method synthesis introduces weld seam by middle layer, is not required to pair
Base material is handled, and is not influenced on base material structure, property.
Method of the present invention for a kind of carbon nanotube enhancing three-dimensional structure middle layer assistant brazing.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the foam metal of the carbon nanotube enhancing of one step 3 of embodiment preparation.
Specific embodiment
Technical solution of the present invention is not limited to the specific embodiment of act set forth below, further include each specific embodiment it
Between any combination.
Specific embodiment 1: a kind of carbon nanotube enhancing three-dimensional structure middle layer assistant brazing described in present embodiment
Method follow the steps below:
One, hydrochloric acid, acetone, dehydrated alcohol and the deionized water for being successively 1mol/L~3mol/L with concentration by foam metal
It is respectively washed 10min, then naturally dry, obtains pretreated foam metal, catalyst is added in dehydrated alcohol, obtain
To the ethanol solution for the catalyst that concentration is 0.001mol/L~1mol/L, pretreated foam metal is immersed in dense
Degree is 1h to be stood, then naturally dry, after obtaining immersion in the ethanol solution of the catalyst of 0.001mol/L~1mol/L
Foam metal；
Two, the foam metal after immersion is placed in plasma enhanced chemical vapor deposition vacuum plant, is evacuated to
Pressure is 20Pa~100Pa hereinafter, being passed through hydrogen, and adjusting hydrogen gas flow is 20sccm~60sccm, and adjusting vacuumizes speed
Pressure in plasma enhanced chemical vapor deposition vacuum plant control as 100Pa~300Pa by degree, and is 100Pa in pressure
Under~300Pa and hydrogen atmosphere, temperature is heated up most 300 DEG C~800 DEG C in 30min；
Three, it is passed through carbon-source gas, adjusting carbon-source gas gas flow is 10sccm~100sccm, adjusts hydrogen gas stream
Amount is 1sccm~40sccm, adjusts vacuum pumping rate and controls pressure in plasma enhanced chemical vapor deposition vacuum plant
For 100Pa~1000Pa, then depositing system radio-frequency power is 50W~200W, pressure is 100Pa~1000Pa, carbon source gas
Body gas flow is 10sccm~100sccm, hydrogen gas flow is 1sccm~40sccm and temperature is 300 DEG C~800 DEG C items
It is deposited under part, sedimentation time is 1min~60min, after deposition, closes radio-frequency power supply and heating power supply, stops being passed through
Carbon-source gas and hydrogen, are cooled to room temperature, and obtain the foam metal of carbon nanotube enhancing；
Four, 200 mesh, 400 mesh, 600 mesh and 800 mesh sand paper are successively used to polish metal to be welded, ceramics and solder paillon, so
10min~20min is pre-processed with acetone ultrasound afterwards, the metal to be welded of removal surface impurity is obtained, removes the ceramics of surface impurity
With the solder paillon of removal surface impurity；
Five, the solder of the metal to be welded of surface impurity, the foam metal of carbon nanotube enhancing, removal surface impurity will be removed
The ceramics of paillon and removal surface impurity successively stack, and obtain part to be welded, part to be welded is placed in vacuum brazing furnace, be in pressure
1×10-4Pa~5 × 10-3Under conditions of Pa and brazing temperature are 700 DEG C~1200 DEG C, 1min~20min is kept the temperature, then with drop
Warm speed is 2 DEG C/min~10 DEG C/min, and temperature is cooled to room temperature by 700 DEG C~1200 DEG C, i.e. the enhancing of completion carbon nanotube
The method of three-dimensional structure middle layer assistant brazing.
It is not only grown uniformly by plasma enhanced chemical vapor deposition method carbon nanotube generated, not the group of generation
It is poly-, it might even be possible to directive growth；Plasma enhanced chemical vapor deposition method, can without handling base material simultaneously
Directly can be introduced carbon nanotube among weld seam using foam metal as middle layer, property, the structure of base material are not produced
It is raw to influence, so that base material is more stable under high temperature environment.
The basic principle of present embodiment carbon nanotube enhancing three-dimensional structure middle layer assistant brazing: chemical gas is utilized
It is mutually deposited on in-situ preparation carbon nanotube on foamed material and introduces carbon nanotube into weld seam as middle layer, due to carbon nanometer
Being uniformly distributed for pipe plays one's part to the full, and dispersion-strengtherning slows down residual stress to improve strength of joint, reduces continuous brittlement phase
It generates, and improves the high-temperature behavior of connector using the high-temperature behavior of itself, according to the good plasticity of selected foamed material, form modeling
Property good solid solution, intermetallic compound, to alleviate biggish residual stress between ceramics and metal.
Present embodiment the utility model has the advantages that
1, carbon nanotube high-intensitive in weld seam is uniformly distributed, and plays the effect of dispersion-strengtherning.
2, carbon nanotube thermal expansion coefficient is low, the thermal expansion coefficient of solder is adjusted, selected foamed material plasticity is preferably
Plastic property of weld bead can be improved, to reduce the residual stress of ceramics with metal joint.
3, carbon nanotube is reacted with active element, product Dispersed precipitate, does not form continuous brittlement phase, adjusts conversion zone
Thickness, to improve strength of joint.
4, the good high-temperature behavior of carbon nanotube can improve the high-temperature behavior of soldered fitting significantly.
5, the carbon nanotube of plasma enhanced chemical vapor deposition method synthesis introduces weld seam by middle layer, is not required to pair
Base material is handled, and is not influenced on base material structure, property.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: foam described in step 1
Metal is foam copper or nickel foam.It is other same as the specific embodiment one.
Specific embodiment 3: unlike one of present embodiment and specific embodiment one or two: institute in step 1
The catalyst stated is six water nickel nitrates, ferric nitrate, cobalt nitrate, nickel sulfate, ferric sulfate or cobaltous sulfate.Other and specific embodiment
One or two is identical.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three: institute in step 3
The carbon-source gas stated is methane, acetylene or ethyl alcohol.It is other identical as specific embodiment one to three.
Specific embodiment 5: unlike one of present embodiment and specific embodiment one to four: institute in step 4
The metal to be welded stated is TC4 titanium alloy, TC10 titanium alloy, TiAl alloy, stainless steel or GH99 alloy.Other and specific embodiment party
Formula one to four is identical.
Specific embodiment 6: unlike one of present embodiment and specific embodiment one to five: institute in step 4
The ceramics stated are Cf/ C composite ceramics, C/SiC ceramics, SiO2- BN composite ceramics, SiO2Ceramics or SiO2f/SiO2Ceramics.It is other
It is identical as specific embodiment one to five.
Specific embodiment 7: unlike one of present embodiment and specific embodiment one to six: institute in step 4
The solder paillon stated is TiZrNiCu solder paillon, Ti-Cu solder paillon, Ti-Ni solder paillon, Cu-Zr solder paillon, AgCu
Solder paillon or AgCuTi solder paillon.It is other identical as specific embodiment one to six.
Specific embodiment 8: unlike one of present embodiment and specific embodiment one to seven: will in step 2
Foam metal after immersion is placed in plasma enhanced chemical vapor deposition vacuum plant, be evacuated to pressure be 30Pa with
Under, it is passed through hydrogen, adjusting hydrogen gas flow is 40sccm, adjusts vacuum pumping rate for plasma enhanced chemical vapor deposition
Pressure control is 200Pa in vacuum plant, and in the case where pressure is 200Pa and hydrogen atmosphere, in 30min most by temperature heating
570℃.It is other identical as specific embodiment one to seven.
Specific embodiment 9: unlike one of present embodiment and specific embodiment one to eight: leading in step 3
Enter carbon-source gas, adjusting carbon-source gas gas flow is 40sccm, and adjusting hydrogen gas flow is 10sccm, and adjusting vacuumizes speed
Degree controls pressure in plasma enhanced chemical vapor deposition vacuum plant for 700Pa, then in depositing system radio-frequency power
For 175W, pressure 700Pa, carbon-source gas gas flow be 40sccm, hydrogen gas flow is 10sccm and temperature is 570 DEG C
Under the conditions of deposited, sedimentation time 30min after deposition, closes radio-frequency power supply and heating power supply, and stopping is passed through carbon source
Gas and hydrogen, are cooled to room temperature, and obtain the foam metal of carbon nanotube enhancing.It is other with one to eight phase of specific embodiment
Together.
Specific embodiment 10: unlike one of present embodiment and specific embodiment one to nine: will in step 5
Remove the metal to be welded of surface impurity, the foam metal of carbon nanotube enhancing, the solder paillon and removal table for removing surface impurity
The ceramics of face impurity successively stack, and obtain part to be welded, part to be welded is placed in vacuum brazing furnace, are 3 × 10 in pressure-3Pa and pricker
Under conditions of weldering temperature is 930 DEG C, 10min is kept the temperature, temperature is then cooled to by 930 DEG C for 5 DEG C/min by room with cooling rate
Temperature.It is other identical as specific embodiment one to nine.
Specific embodiment 11: unlike one of present embodiment and specific embodiment one to ten: in step 2
Being evacuated to pressure is 25Pa~70Pa or less.It is other identical as specific embodiment one to ten.
Specific embodiment 12: present embodiment is unlike specific embodiment one to one of 11: step 2
Middle adjusting hydrogen gas flow is 30sccm~50sccm.It is other identical as specific embodiment one to 11.
Specific embodiment 13: present embodiment is unlike specific embodiment one to one of 12: step 2
Middle adjusting vacuum pumping rate controls pressure in plasma enhanced chemical vapor deposition vacuum plant for 150Pa~270Pa.Its
It is identical as specific embodiment one to 12.
Specific embodiment 14: present embodiment is unlike specific embodiment one to one of 13: step 2
In and pressure be 100Pa~300Pa and hydrogen atmosphere under, in 30min by temperature heat up most 400 DEG C~700 DEG C.It is other
It is identical as specific embodiment one to 13.
Specific embodiment 15: present embodiment is unlike specific embodiment one to one of 14: step 3
In be passed through carbon-source gas, adjusting carbon-source gas gas flow is 20sccm~80sccm.Other and specific embodiment one to ten
Four is identical.
Specific embodiment 16: present embodiment is unlike specific embodiment one to one of 15: step 3
Middle adjusting hydrogen gas flow is 5sccm~30sccm.It is other identical as specific embodiment one to 15.
Specific embodiment 17: present embodiment is unlike specific embodiment one to one of 16: step 3
Middle adjusting vacuum pumping rate controls pressure in plasma enhanced chemical vapor deposition vacuum plant for 270Pa~850Pa.Its
It is identical as specific embodiment one to 16.
Specific embodiment 18: present embodiment is unlike specific embodiment one to one of 17: step 3
In then depositing system radio-frequency power is 125W~190W, pressure is 100Pa~1000Pa, carbon-source gas gas flow is
10sccm~100sccm, hydrogen gas flow be 1sccm~40sccm and temperature be 300 DEG C~800 DEG C under the conditions of sunk
Product, sedimentation time are 1min~60min.It is other identical as specific embodiment one to 17.
Specific embodiment 19: present embodiment is unlike specific embodiment one to one of 18: step 3
In then depositing system radio-frequency power is 50W~200W, pressure is 100Pa~1000Pa, carbon-source gas gas flow is
10sccm~100sccm, hydrogen gas flow be 1sccm~40sccm and temperature be 300 DEG C~800 DEG C under the conditions of sunk
Product, sedimentation time are 1min~40min.It is other identical as specific embodiment one to 18.
Specific embodiment 20: present embodiment is unlike specific embodiment one to one of 19: step 5
It is middle that part to be welded is placed in vacuum brazing furnace, it is 1 × 10 in pressure-4Pa~5 × 10-3Pa and brazing temperature are 800 DEG C~1000
Under conditions of DEG C, 1min~20min is kept the temperature.It is other identical as specific embodiment one to 19.
Specific embodiment 21: present embodiment is unlike specific embodiment one to one of 20: step
Part to be welded is placed in vacuum brazing furnace in five, is 1 × 10 in pressure-4Pa~5 × 10-3Pa and brazing temperature be 700 DEG C~
Under conditions of 1200 DEG C, 5min~15min is kept the temperature.It is other identical as specific embodiment one to 20.
Specific embodiment 22: present embodiment is unlike specific embodiment one to one of 21: step
Then with cooling rate for 4 DEG C/min~8 DEG C/min in rapid five, temperature is cooled to room temperature by 700 DEG C~1200 DEG C.It is other with
Specific embodiment one to 21 is identical.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one:
A kind of method of the enhancing three-dimensional structure middle layer assistant brazing of carbon nanotube described in the present embodiment is according to following
What step carried out:
One, hydrochloric acid, acetone, dehydrated alcohol and deionized water that foam metal is successively 2mol/L with concentration are respectively washed
10min, then naturally dry, obtains pretreated foam metal, catalyst is added in dehydrated alcohol, obtains concentration and is
Pretreated foam metal is immersed in the catalysis that concentration is 0.1mol/L by the ethanol solution of the catalyst of 0.1mol/L
In the ethanol solution of agent, 1h is stood, then naturally dry, the foam metal after being impregnated；
Two, the foam metal after immersion is placed in plasma enhanced chemical vapor deposition vacuum plant, is evacuated to
Pressure is 30Pa hereinafter, being passed through hydrogen, and adjusting hydrogen gas flow is 40sccm, adjusts vacuum pumping rate for plasma enhancing
Pressure control is 200Pa in chemical vapor deposition vacuum plant, and in the case where pressure is 200Pa and hydrogen atmosphere, will in 30min
Temperature heats up most 570 DEG C；
Three, it is passed through carbon-source gas, adjusting carbon-source gas gas flow is 40sccm, adjusts hydrogen gas flow and is
10sccm adjusts vacuum pumping rate and controls pressure in plasma enhanced chemical vapor deposition vacuum plant for 700Pa, then
Depositing system radio-frequency power is 175W, pressure 700Pa, carbon-source gas gas flow are 40sccm, hydrogen gas flow is
10sccm and temperature are deposited under the conditions of being 570 DEG C, sedimentation time 30min, after deposition, are closed radio-frequency power supply and are added
Thermoelectric generator, stopping are passed through carbon-source gas and hydrogen, are cooled to room temperature, and obtain the foam metal of carbon nanotube enhancing；
Four, 200 mesh, 400 mesh, 600 mesh and 800 mesh sand paper are successively used to polish metal to be welded, ceramics and solder paillon, so
15min is pre-processed with acetone ultrasound afterwards, the metal to be welded of removal surface impurity is obtained, removes the ceramics and removal table of surface impurity
The solder paillon of face impurity；
Five, the solder of the metal to be welded of surface impurity, the foam metal of carbon nanotube enhancing, removal surface impurity will be removed
The ceramics of paillon and removal surface impurity successively stack, and obtain part to be welded, part to be welded is placed in vacuum brazing furnace, be in pressure
3×10-3Under conditions of Pa and brazing temperature are 930 DEG C, keep the temperature 10min, then with cooling rate for 5 DEG C/min, by temperature by
930 DEG C are cooled to room temperature, i.e. the method for completion carbon nanotube enhancing three-dimensional structure middle layer assistant brazing；
Foam metal described in step 1 is foam copper；
Catalyst described in step 1 is six water nickel nitrates；
Carbon-source gas described in step 3 is methane；
Metal to be welded described in step 4 is TC4 titanium alloy；
Ceramics described in step 4 are Cf/ C composite ceramics；
Solder paillon described in step 4 is TiZrNiCu solder paillon.
The foam metal of the carbon nanotube enhancing of step 3 preparation is measured by weight difference assay it is found that carbon nanotube enhances
Foam metal in carbon nanotube volume fraction be 4%.
The ceramics that present embodiment obtains are good with titanium alloy strength of joint, and high-temperature behavior is good, is not evident that
The defects of crackle, shear strength is up to 58MPa, and at 600 DEG C, elevated temperature strength can reach 24MPa.
Fig. 1 is the scanning electron microscope (SEM) photograph of the foam metal of the carbon nanotube enhancing of one step 3 of embodiment preparation.As seen from the figure,
The length of carbon nanotube of generation is longer, is evenly distributed, medium density, using dispersion of the carbon nanotube in solder connector, therefore can
Its effect is given full play to, solution Ceramic and metal joining center tap intensity is not high, the problem of high-temperature behavior deficiency.
Claims (1)
1. a kind of method of carbon nanotube enhancing three-dimensional structure middle layer assistant brazing, it is characterised in that a kind of carbon nanotube enhancing
The method of three-dimensional structure middle layer assistant brazing follows the steps below:
One, hydrochloric acid, acetone, dehydrated alcohol and deionized water that foam metal is successively 2mol/L with concentration are respectively washed
10min, then naturally dry, obtains pretreated foam metal, catalyst is added in dehydrated alcohol, obtains concentration and is
Pretreated foam metal is immersed in the catalysis that concentration is 0.1mol/L by the ethanol solution of the catalyst of 0.1mol/L
In the ethanol solution of agent, 1h is stood, then naturally dry, the foam metal after being impregnated；
Two, the foam metal after immersion is placed in plasma enhanced chemical vapor deposition vacuum plant, is evacuated to pressure
For 30Pa hereinafter, being passed through hydrogen, adjusting hydrogen gas flow is 40sccm, adjusts vacuum pumping rate for plasma enhanced chemical
The pressure control in vacuum plant that is vapor-deposited is 200Pa, and in the case where pressure is 200Pa and hydrogen atmosphere, by temperature in 30min
Most 570 DEG C of heating；
Three, it is passed through carbon-source gas, adjusting carbon-source gas gas flow is 40sccm, and adjusting hydrogen gas flow is 10sccm, is adjusted
Pressure in plasma enhanced chemical vapor deposition vacuum plant control as 700Pa by section vacuum pumping rate, is then depositing system
System radio-frequency power be 175W, pressure 700Pa, carbon-source gas gas flow are 40sccm, hydrogen gas flow be 10sccm and
Temperature is deposited under the conditions of being 570 DEG C, sedimentation time 30min, after deposition, closes radio-frequency power supply and heating power supply,
Stopping is passed through carbon-source gas and hydrogen, is cooled to room temperature, and obtains the foam metal of carbon nanotube enhancing；
Four, it successively uses 200 mesh, 400 mesh, 600 mesh and 800 mesh sand paper to polish metal to be welded, ceramics and solder paillon, then uses
Acetone ultrasound pre-processes 15min, and it is miscellaneous to obtain the metal to be welded of removal surface impurity, the ceramics for removing surface impurity and removal surface
The solder paillon of matter；
Five, the solder paillon of the metal to be welded of surface impurity, the foam metal of carbon nanotube enhancing, removal surface impurity will be removed
And removal surface impurity ceramics successively stack, obtain part to be welded, part to be welded be placed in vacuum brazing furnace, pressure be 3 ×
10-3Under conditions of Pa and brazing temperature are 930 DEG C, 10min is kept the temperature, then with cooling rate for 5 DEG C/min, by temperature by 930
It DEG C is cooled to room temperature, i.e. the method for completion carbon nanotube enhancing three-dimensional structure middle layer assistant brazing；
Foam metal described in step 1 is foam copper；
Catalyst described in step 1 is six water nickel nitrates；
Carbon-source gas described in step 3 is methane；
Metal to be welded described in step 4 is TC4 titanium alloy；
Ceramics described in step 4 are Cf/ C composite ceramics；
Solder paillon described in step 4 is TiZrNiCu solder paillon；
The volume fraction of carbon nanotube is 4% in the foam metal of the carbon nanotube enhancing of step 3 preparation.
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| CN107570830B (en) * | 2017-10-17 | 2022-03-01 | 哈尔滨工业大学 | Method for auxiliary brazing of foam copper intermediate layer enhanced by CuO nano structure |
| CN110153591A (en) * | 2019-05-29 | 2019-08-23 | 安徽工程大学 | A kind of amorphous composite soldering for ceramic soldering and alloy |
| CN110508892B (en) * | 2019-09-12 | 2021-06-18 | 中山大学 | Method for connecting ZrC-SiC composite ceramic and austenitic stainless steel |
| CN112404631B (en) * | 2020-10-27 | 2022-06-07 | 哈尔滨工业大学 | Method for soldering dissimilar materials with assistance of carbon nanotube sponge intermediate layer |
| CN112894047A (en) * | 2021-01-15 | 2021-06-04 | 华中科技大学 | Method for improving dissimilar metal fusion soldering joint performance through carbon nano tube |
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| CN104868134B (en) * | 2015-04-17 | 2017-04-19 | 华南理工大学 | Foam metal-carbon nanotube composite material, and preparation method and application thereof |
| CN105441711B (en) * | 2015-12-28 | 2017-07-28 | 哈尔滨工业大学 | A kind of preparation method of three-dimensional structure CNTs Reinforced Cu-Base Composites |
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| CN109851388B (en) * | 2019-03-19 | 2022-03-01 | 哈尔滨工业大学 | Surface modified auxiliary brazing SiO2Method of alloying of-BN with Invar |
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