CN108034984A - A kind of preparation method of carbon nanotubes copper-based laminated composite material - Google Patents
A kind of preparation method of carbon nanotubes copper-based laminated composite material Download PDFInfo
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- CN108034984A CN108034984A CN201711288623.3A CN201711288623A CN108034984A CN 108034984 A CN108034984 A CN 108034984A CN 201711288623 A CN201711288623 A CN 201711288623A CN 108034984 A CN108034984 A CN 108034984A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/02—Electrophoretic coating characterised by the process with inorganic material
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
- C22C2026/002—Carbon nanotubes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2204/00—End product comprising different layers, coatings or parts of cermet
Abstract
A kind of preparation method of carbon nanotubes copper-based laminated composite material, is related to a kind of preparation method of CNTs/Cu composite.The present invention is to solve the unmatched problem of CNTs/Cu composite obdurability prepared by existing method.Method：First, the cleaning of the acidification of carbon nanotubes and copper sheet；2nd, the preparation of composite sheet；3rd, the preparation of composite material.The present invention is using the method for electrophoretic deposition come dispersing Nano carbon tubes, make the surface for being dispersed in metallic plate of carbon nanotubes Direct Uniform, the degree of scatter of carbon nanotubes is improved, the method by hot pressed sintering and subsequently rolled, it is possible to achieve the structure of composite laminate constructions.Composite laminate constructions can change the fracture behaviour of material, increase the energy expenditure in fracture process, thus the intensity of composite material is obviously improved compared with matrix, while toughness also accordingly improves.The present invention is used to prepare CNTs/Cu composite.
Description
Technical field
The present invention relates to a kind of preparation method of CNTs/Cu composite.
Background technology
Metal-base composites due to itself excellent mechanical property and feature, aerospace, automobile and
The fields such as mobile communication are more and more widely used.It is more and more as emerging one-dimensional carbon material, carbon nanotubes
The reinforcement for being used as metal-base composites.But due to the nanoscale of itself, mutual serious model moral
Magnificent power effect so that carbon nanotubes and its easily mutually entanglement.Simultaneously because wetability poor between carbon nanotubes and metal,
Therefore it is extremely difficult realized in metallic matrix it is dispersed.
The existing method for preparing Cu-base composites is mainly powder metallurgy, in-situ authigenic etc., it is common the characteristics of be carbon
Nanotube is dispersed in material internal three dimensions, while the strength of materials is lifted, often causes plasticity and tough
The reduction of property, the elongation percentage of Cu-base composites are generally below 5%.And the elongation percentage of fine copper matrix generally about 30%, it is so strong
Toughness mismatches and often leads to that the deflection that material can be born is smaller, easily triggers sudden failure, limits such compound
The application range of material.
The content of the invention
The present invention is to solve CNTs/Cu composite prepared by existing method to ask there are obdurability is unmatched
A kind of topic, there is provided preparation method of carbon nanotubes copper-based laminated composite material.
The preparation method of carbon nanotubes copper-based laminated composite material of the present invention, comprises the following steps：
First, the cleaning of the acidification of carbon nanotubes and copper sheet：
Take carbon nanotubes to be placed in distilled water, be ultrasonically treated, remove remaining impurity in preparation process, take out carbon nanotubes
It is dried for standby；The carbon nanotubes of drying is placed in the mix acid liquor of sulfuric acid and nitric acid, carries out supersound process 2~3h, Zhi Hou
22~24h is soaked in the mix acid liquor of sulfuric acid and nitric acid, filtering, is cleaned with distilled water, until solution is changed into neutral, is taken out
Carbon nanotubes is dried, and obtains the carbon nanotubes that surface introduces active group；The body of sulfuric acid and nitric acid wherein in mix acid liquor
Product ratio is (1~3):(1~3)；
Copper sheet is put into the sulfuric acid solution that concentration expressed in percentage by volume is 9%~11% and is cleaned, afterwards in clear water and wine
Cleaned successively in essence, drying is spare；
2nd, the preparation of composite sheet：
Take nitric acid alumina particles and carbon nanotubes that step 1 obtains, be added in the mixed liquor of alcohol and acetone, surpassed
6~7h of sonication, the copper sheet that step 1 was cleaned do cathode, stainless steel substrates as anode, fixed plate spacing and deposition voltage,
The composite sheet of deposition of carbon nanotubes is obtained in cathode；
The length of sedimentation time finally influences the content of carbon nanotubes in composite material, when this method can be deposited by controlling
Between adjust composite inner difference reinforcement changes of contents.
3rd, the preparation of composite material
Stacked in multi-layers composite sheet, is sintered under vacuum, carries out rolling deformation, controlled material group to material afterwards
Knit, obtain the carbon nanotube reinforced copper-base composite material with layer structure；The technological parameter wherein rolled is temperature 400-450
DEG C, pass deformation 5%-20%, cumulative deformation 60%-90%.
Further, the length of carbon nanotubes is 2-5 μm in step 1, a diameter of 10-50nm.
Further, the temperature dried in step 1 is 100~105 DEG C.
Further, in step 1 in the mix acid liquor of sulfuric acid and nitric acid, sulfuric acid and nitric acid be the commercially available concentrated sulfuric acid and
Concentrated nitric acid.
Further, nitric acid alumina particles and the mass ratio of carbon nanotubes are 1 in step 2:1.
Further, plate spacing described in step 2 is 50~52mm.
Further, deposition voltage described in step 2 is 30~50V.
Further, the volume ratio of alcohol and acetone is 1 in the mixed liquor of alcohol and acetone in step 2:1；Alcohol and third
In the mixed liquor of ketone, mass concentration >=99.7 of alcohol, acetone is that analysis is pure.
Further, the pressure sintered in step 3 is 30~50MPa, and sintering temperature is 950~1050 DEG C, sintering time
For 4~6h.
Beneficial effects of the present invention：
For the present invention using the method for electrophoretic deposition come dispersing Nano carbon tubes, make carbon nanotubes Direct Uniform is dispersed in metal
The surface of plate, improves the degree of scatter of carbon nanotubes, passes through the method for hot pressed sintering, it is possible to achieve composite laminate constructions
Structure.Dispersed carbon nanotubes improves the effect of load transmission, stratiform knot to composite inner in the two-dimensional direction
Structure can change the fracture behaviour of material, increase the energy expenditure in fracture process, thus the intensity of composite material have compared with matrix it is bright
Aobvious lifting.
The method of the present invention is dispersed on a metal plate in advance by carbon nanotubes, afterwards carries out the composite plate being prepared
Hot pressed sintering, makes the carbon nanotubes that material internal is prepared be distributed in two-dimensional directional, composite material has obvious stratiform knot
Structure.By lifting the degree of scatter and structure stratiform biomimetic structure of carbon nanotubes, the Compound Material Engineering being prepared
Can have compared with matrix and be obviously improved.Dispersed carbon nanotubes shows high enhancing efficiency in the composite.
1st, carbon nanotubes is distributed in the two-dimensional direction, solves the problems, such as that carbon nanotubes is easily reunited entanglement, is conducive to carbon
Combination between nanotube and matrix.Only carbon nanotubes is distributed in the two-dimensional direction, can just build to obtain carbon nanotubes
Nanometer laminated structure, and the copper sheet of micron-scale are overlapped mutually, the common composite material for building layer structure.
2nd, the design of layer structure, it is therefore an objective to simulate biomaterial, utilize the property of structure effect, preferably lifting material
Energy.Carbon nanotubes is distributed in the two-dimensional direction, adds the contact range between matrix, can preferably realize load in base
Transmission between body and reinforcement carbon nanotubes；Meanwhile the material of layer structure is in loading procedure, it is possible to achieve different layers it
Between fracture mismatch, increase the deflection and kinking of crackle, that is, add the extensions path of crackle, so as to consume more
More energy.Both the carbon nanotubes of layer structure and Two dimensional Distribution collective effects, can make composite material tensile strength compared with
While lifting, toughness is lifted at the same time.
The Cu-base composites tensile strength with layer structure that this method is prepared is lifted about compared with matrix
20%, while the elongation percentage of material and matrix are maintained at phase same level, the elongation percentage of Cu-base composites of the present invention is about 32%
(elongation percentage of fine copper matrix about 30%), it is meant that the toughness of material gets a promotion compared with matrix.
3rd, this method has wider use scope, can extend to other metallic matrixes, while preparation process is simple,
Metal-base composites can efficiently be prepared.
Brief description of the drawings
Fig. 1 is distribution scanned picture of the carbon nanotubes on copper sheet in embodiment 1 after electrophoretic deposition；
Fig. 2 is the transmission microstructure figure of composite material in embodiment 1；
Fig. 3 is the tensile property result figure of fine copper and composite material in embodiment 1.
Embodiment
Technical solution of the present invention is not limited to act embodiment set forth below, further includes between each embodiment
Any combination.
Embodiment one：The preparation method of present embodiment carbon nanotubes copper-based laminated composite material, including it is following
Step：
First, the cleaning of the acidification of carbon nanotubes and copper sheet：
Take carbon nanotubes to be placed in distilled water, be ultrasonically treated, remove remaining impurity in preparation process, take out carbon nanotubes
It is dried for standby；The carbon nanotubes of drying is placed in the mix acid liquor of sulfuric acid and nitric acid, carries out supersound process 2~3h, Zhi Hou
22~24h is soaked in the mix acid liquor of sulfuric acid and nitric acid, filtering, is cleaned with distilled water, until solution is changed into neutral, is taken out
Carbon nanotubes is dried, and obtains the carbon nanotubes that surface introduces active group；The body of sulfuric acid and nitric acid wherein in mix acid liquor
Product ratio is (1~3):(1~3)；
Copper sheet is put into the sulfuric acid solution that concentration expressed in percentage by volume is 9%~11% and is cleaned, afterwards in clear water and wine
Cleaned successively in essence, drying is spare；
2nd, the preparation of composite sheet：
Take nitric acid alumina particles and carbon nanotubes that step 1 obtains, be added in the mixed liquor of alcohol and acetone, surpassed
6~7h of sonication, the copper sheet that step 1 was cleaned do cathode, stainless steel substrates as anode, fixed plate spacing and deposition voltage,
The composite sheet of deposition of carbon nanotubes is obtained in cathode；Wherein described plate spacing is 50~52mm, and deposition voltage is 30~50V；
3rd, the preparation of composite material
Stacked in multi-layers composite sheet, is sintered under vacuum, carries out rolling deformation to material afterwards, obtains with layer
The carbon nanotube reinforced copper-base composite material of shape structure；The technological parameter wherein rolled is 400-450 DEG C of temperature, pass deformation
5%-20%, cumulative deformation 60%-90%.
Embodiment two：The present embodiment is different from the first embodiment in that：Carbon nanotubes in step 1
Length is 2-5 μm, a diameter of 10-50nm.It is other identical with embodiment one.
Embodiment three：The present embodiment is different from the first and the second embodiment in that：Dried in step 1
Temperature is 100~105 DEG C.It is other the same as one or two specific embodiments.
Embodiment four：Unlike one of present embodiment and embodiment one to three：Mixed in step 1
It is 3 to close the volume ratio of sulfuric acid and nitric acid in acid solution:1.It is other identical with one of embodiment one to three.
Embodiment five：Unlike one of present embodiment and embodiment one to three：Mixed in step 1
It is 1 to close the volume ratio of sulfuric acid and nitric acid in acid solution:1.It is other identical with one of embodiment one to three.
Embodiment six：Unlike one of present embodiment and embodiment one to three：Mixed in step 1
It is 1 to close the volume ratio of sulfuric acid and nitric acid in acid solution:3.It is other identical with one of embodiment one to three.
Embodiment seven：Unlike one of present embodiment and embodiment one to six：Nitre in step 2
Sour alumina particles and the mass ratio of carbon nanotubes are 1:1.It is other identical with one of embodiment one to six.
Embodiment eight：Unlike one of present embodiment and embodiment one to seven：Wine in step 2
The volume ratio of alcohol and acetone is 1 in the mixed liquor of essence and acetone:1.It is other identical with one of embodiment one to seven.
Embodiment nine：Unlike one of present embodiment and embodiment one to eight：Described in step 2
Plate spacing is 51mm.It is other identical with one of embodiment one to eight.
Embodiment ten：Unlike one of present embodiment and embodiment one to nine：Described in step 2
Deposition voltage is 35~45V.It is other identical with one of embodiment one to nine.
Embodiment 11：Unlike one of present embodiment and embodiment one to ten：In step 3
The pressure of sintering is 30~50MPa, and sintering temperature is 950~1050 DEG C, and sintering time is 4~6h.Other and specific embodiment party
One of formula one to ten is identical.
Embodiment 12：Present embodiment is unlike embodiment one to one of 11：Step 3
The pressure of middle sintering is 40MPa, and sintering temperature is 1000 DEG C, sintering time 5h.Other and embodiment one to 11
One of it is identical.
Embodiment 13：Present embodiment is unlike embodiment one to one of 12：Step 3
The technological parameter of middle rolling is 450 DEG C of temperature, pass deformation 10%, cumulative deformation 80%.Other and specific embodiment party
Formula one to one of 12 is identical.
Elaborate below to the embodiment of the present invention, following embodiments under premised on technical solution of the present invention into
Row is implemented, and gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following realities
Apply example.
Embodiment 1：
It is 3 μm or so to take length, and the carbon nanotubes 0.2g of a diameter of 30nm or so, is placed in distilled water, is ultrasonically treated it
Afterwards by obtained carbon nanotubes in 105 DEG C of drying.The carbon nanotubes of drying is placed in the mix acid liquor of sulfuric acid and nitric acid (wherein
The volume ratio of sulfuric acid and nitric acid is 3 in mix acid liquor:1) supersound process 2h, is carried out, afterwards in sulfuric acid and the mix acid liquor of nitric acid
Middle immersion 24h, filtering, is cleaned with distilled water, until solution is changed into neutral, carbon nanotubes is in 105 DEG C of drying.Configuration
The sulfuric acid solution of 10vol%, copper sheet is put into wherein, 10s is cleaned, is cleaned, blown successively in clear water and alcohol afterwards
It is dry spare.Take 300 milliliters of alcohol and 300 milliliters of acetone to be mixed, take 0.05g nitric acid alumina particles and 0.05g acidifications
Carbon nanotubes, be added in mixed liquor, be ultrasonically treated, ultrasonic time is set as 6h, and the copper sheet cleaned is done cathode,
Stainless steel substrates set plate spacing as 50mm, deposition voltage 30V, you can obtain deposition of carbon nanotubes in cathode as anode
Composite sheet.Stacked in multi-layers composite sheet, is sintered under vacuum, pressure 30MPa, and sintering temperature is 950 DEG C, during sintering
Between be 4h, rolling deformation is carried out to material afterwards, wherein the technological parameter rolled be 450 DEG C of temperature, pass deformation 10% is tired
Product deflection is 80%, and the carbon nanotube reinforced copper-base composite material with layer structure is prepared.
The fine copper with layer structure is prepared using identical technique.Using Instron-5569 universal tensile testing machines pair
Fine copper and composite material carry out tensile test at room temperature, rate of extension 0.5mm/min.
After Fig. 1 is electrophoretic deposition, distribution scanned picture of the carbon nanotubes on copper sheet, can significantly find out, carbon is received
Mitron is dispersed on copper sheet, does not tangle between each other, this method can effective dispersing Nano carbon tubes, build at the same time
The composite laminate constructions primitive of well-formed.
Fig. 2 is the transmission microstructure of composite material, as can be seen that carbon nanotubes is adjacent from transmission results
It is distributed between copper sheet, sintering process makes carbon nanotubes be embedded at the same time among adjacent copper sheet, forms good combination.
Fig. 3 is that (stress strain curve a represents fine copper, stress strain curve b in Fig. 3 for the tensile property result figure of fine copper and composite material
Represent composite material), this it appears that the tensile strength of composite material reaches about 239MPa from figure, compared with fine copper, (tension is strong
Degree 200MPa) it is obviously improved, lifting about 20%, illustrate the dispersed of carbon nanotubes and build the structure of stratiform, can
With collective effect.While the strength of materials is lifted, the toughness of material is obviously improved compared with matrix.The extension of Cu-base composites
Rate is about 32% (elongation percentage of fine copper matrix about 30%).Toughness is the size below stress strain curve, so being carried in intensity
Rise, in the case that elongation percentage remains unchanged, the toughness of material is lifting compared with fine copper matrix.Simultaneously as composite inner
Content of carbon nanotubes is very low, and carbon nanotubes can be calculated has high enhancing efficiency in the composite inner.
Claims (10)
1. a kind of preparation method of carbon nanotubes copper-based laminated composite material, it is characterised in that this method comprises the following steps：
First, the cleaning of the acidification of carbon nanotubes and copper sheet：
Take carbon nanotubes to be placed in distilled water, be ultrasonically treated, remove remaining impurity in preparation process, take out carbon nanotubes drying
It is spare；The carbon nanotubes of drying is placed in the mix acid liquor of sulfuric acid and nitric acid, 2~3h of supersound process is carried out, afterwards in sulfuric acid
With 22~24h of immersion in the mix acid liquor of nitric acid, filtering, is cleaned with distilled water, until solution is changed into neutral, is taken out carbon and is received
Mitron is dried, and obtains the carbon nanotubes that surface introduces active group；The volume ratio of sulfuric acid and nitric acid wherein in mix acid liquor
For (1~3):(1~3)；
Copper sheet is put into the sulfuric acid solution that concentration expressed in percentage by volume is 9%~11% and is cleaned, afterwards in clear water and alcohol
Cleaned successively, drying is spare；
2nd, the preparation of composite sheet：
Take nitric acid alumina particles and carbon nanotubes that step 1 obtains, be added in the mixed liquor of alcohol and acetone, carry out at ultrasound
6~7h is managed, the copper sheet that step 1 was cleaned does cathode, stainless steel substrates exist as anode, fixed plate spacing and deposition voltage
Cathode obtains the composite sheet of deposition of carbon nanotubes；Wherein described plate spacing is 50~52mm, and deposition voltage is 30~50V；
3rd, the preparation of composite material
Stacked in multi-layers composite sheet, is sintered under vacuum, carries out rolling deformation to material afterwards, obtains with stratiform knot
The carbon nanotube reinforced copper-base composite material of structure；The technological parameter wherein rolled is 400-450 DEG C of temperature, pass deformation 5%-
20%, cumulative deformation 60%-90%.
A kind of 2. preparation method of carbon nanotubes copper-based laminated composite material according to claim 1, it is characterised in that step
The length of carbon nanotubes is 2-5 μm in rapid one, a diameter of 10-50nm.
A kind of 3. preparation method of carbon nanotubes copper-based laminated composite material according to claim 1 or 2, it is characterised in that
The temperature dried in step 1 is 100~105 DEG C.
A kind of 4. preparation method of carbon nanotubes copper-based laminated composite material according to claim 3, it is characterised in that step
The volume ratio of sulfuric acid and nitric acid is 3 in mix acid liquor in rapid one:1.
A kind of 5. preparation method of carbon nanotubes copper-based laminated composite material according to claim 3, it is characterised in that step
The volume ratio of sulfuric acid and nitric acid is 1 in mix acid liquor in rapid one:1.
A kind of 6. preparation method of carbon nanotubes copper-based laminated composite material according to claim 3, it is characterised in that step
The volume ratio of sulfuric acid and nitric acid is 1 in mix acid liquor in rapid one:3.
7. a kind of preparation method of carbon nanotubes copper-based laminated composite material according to claim 1,2 or 4, its feature exist
Nitric acid alumina particles and the mass ratio of carbon nanotubes are 1 in step 2:1.
A kind of 8. preparation method of carbon nanotubes copper-based laminated composite material according to claim 7, it is characterised in that step
The volume ratio of alcohol and acetone is 1 in the mixed liquor of alcohol and acetone in rapid two:1.
A kind of 9. preparation method of carbon nanotubes copper-based laminated composite material according to claim 8, it is characterised in that step
Rapid two deposition voltage is 35~45V.
A kind of 10. preparation method of carbon nanotubes copper-based laminated composite material according to claim 9, it is characterised in that step
The pressure sintered in rapid three is 30~50MPa, and sintering temperature is 950~1050 DEG C, and sintering time is 4~6h.
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| CN109354012A (en) * | 2018-11-22 | 2019-02-19 | 哈尔滨工业大学 | A kind of preparation method of low cost high-volume graphene |
| CN109609984A (en) * | 2018-12-20 | 2019-04-12 | 昆明理工大学 | A kind of preparation method of layered carbon nano pipe enhancing Cu-base composites |
| CN111379002A (en) * | 2020-03-31 | 2020-07-07 | 西安稀有金属材料研究院有限公司 | Method for rapidly preparing high-strength and high-toughness layered titanium-based composite material |
| CN112064077A (en) * | 2020-09-21 | 2020-12-11 | 江西理工大学 | Preparation method of copper foil/carbon nanotube/copper foil composite foil |
| CN113373493A (en) * | 2021-05-31 | 2021-09-10 | 南京理工大学 | Preparation method of carbon nanotube reinforced fiber metal laminate |
| CN114672865A (en) * | 2022-04-26 | 2022-06-28 | 昆明理工大学 | Preparation method of CNTs/Cu composite board |
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| CN113373493A (en) * | 2021-05-31 | 2021-09-10 | 南京理工大学 | Preparation method of carbon nanotube reinforced fiber metal laminate |
| CN114672865A (en) * | 2022-04-26 | 2022-06-28 | 昆明理工大学 | Preparation method of CNTs/Cu composite board |
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Application publication date: 20180515 |