CN110257795A - A kind of preparation method of three-dimensional structure graphene enhancing Cu-base composites - Google Patents
A kind of preparation method of three-dimensional structure graphene enhancing Cu-base composites Download PDFInfo
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- CN110257795A CN110257795A CN201910467441.5A CN201910467441A CN110257795A CN 110257795 A CN110257795 A CN 110257795A CN 201910467441 A CN201910467441 A CN 201910467441A CN 110257795 A CN110257795 A CN 110257795A
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- foam copper
- gas
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- base composites
- dimensional structure
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
Abstract
The invention discloses a kind of preparation methods of three-dimensional structure graphene enhancing Cu-base composites, it is to be cleaned by ultrasonic foam copper first, then the excessive dipping nickel of foam copper is carried out, then three-dimensional grapheme is prepared on foam Copper substrate enhances Cu-base composites to get to three-dimensional structure graphene；The present invention is by impregnating nickel on foam Copper substrate, some fine nickel are filled in the large aperture of foam copper can increase catalysis area, the graphene for growing CVD method, so that carbon atom is in foam copper surface migration and when internally spread, can have more perfect three-dimensional net structure, the mechanical strength for improving network is allowed to preferably enhance the intensity of metal-base composites.
Description
Technical field
The present invention relates to a kind of preparation methods of three-dimensional structure graphene enhancing Cu-base composites.
Background technique
Graphene is a kind of obform body that hexagonal lattice is arranged in by single layer of carbon atom, has carbon atom sp2Hydridization rail
Road is according to honeycomb crystal arrangement, and the thickness of only one carbon atom, it is the basic structural element of many other obform bodies of carbon,
Such as graphite, diamond, carbon, carbon nanotube and fullerene；The unique two-dimensional structure of graphene make it have excellent conductivity,
The performances such as thermal conductivity, electron mobility, mechanical strength, since being found, for graphene as semiconductor devices, crystal
The research of the new core material such as pipe, high sensor and energy storage electrode material has large-scale research and more good
Good research achievement；And macroscopical assembly of the three-dimensional grapheme as two-dimensional graphene, inheriting the same of graphene excellent properties
When, special three-dimensional porous network structure also assigns its higher specific surface area, big porosity, conductive network interconnected
With special microenvironment；Three-dimensional grapheme construct by the damping of the performance of graphene itself and porous material, absorption, catalysis,
The performances such as heat-insulated combine, and can greatly widen it in the application prospect of macroscopic arts；
Copper has good thermal conductivity, electric conductivity, corrosion resistance, ductility as very common metal material, wherein leading
Electrically, thermal conductivity is only second to silver, is widely used in electric power and electronics industry；But the intensity of fine copper is low, heat-resisting quantity is poor
Disadvantage receives its application range and greatly limits, and has been unable to satisfy current industrial requirement.Graphene is as a kind of
Novel enhanced body achieves certain progress in field of metal matrix composite；Chemical vapour deposition technique is to prepare height
The main method of quality three-dimensional graphene, the method generally uses foam transition metal to make catalyst and template at present, but prepares
Three-dimensional grapheme aperture be up to hundreds of microns, bulk density is lower, directly influences the mechanical strength of three-dimensional network.
Summary of the invention
The purpose of the present invention is to solve the above the deficiencies in the prior art, propose a kind of three-dimensional structure graphene enhancing
The preparation method of Cu-base composites, follows the steps below:
(1) foam copper is put into cleaning agent and is cleaned by ultrasonic 30-60min, obtain pretreated foam copper；
(2) pretreated foam copper is immersed in maceration extract and is excessively impregnated, dip time 12-24h takes out through dry
It is dry to be air-dried, progress dipping process 2-4 times is repeated, dry be placed at 600 DEG C -900 DEG C of last time roasts 4h-6h,
Obtain impregnated foam copper；The maceration extract includes: 30-65 parts of nickel sulfate, 40-60 parts of nickel acetate, nickelous carbonate 20- by weight
35 parts and water 100-150 parts；
(3) impregnated foam copper is placed in tube furnace, is passed through protective gas and reducibility gas, set heating curve,
It is warming up at 900~1000 DEG C and is made annealing treatment with the heating rate of 15-20 DEG C/min, soaking time 15-30min；It is described
Reducibility gas flow be 100-200sccm, the protective gas flow be 200-400sccm；
(4) reducibility gas is closed, carbon-source gas is passed through, the carbon-source gas and protective gas keep certain flow
Than carrying out the deposition of three-dimensional network graphene, growing and finish after reaction 30-60min, carbon-source gas is closed, in protective gas
Under atmosphere, it is cooled to 200-300 DEG C with the rate of temperature fall of 5-10 DEG C/min, room temperature is cooled to the furnace later and is tied to get to three-dimensional
Structure graphene enhances Cu-base composites.
Preferably, the cleaning agent is the mixed solution of ethyl alcohol and acetone, and the ethyl alcohol and acetone volume ratio are 1:
1.2-1.5。
Preferably, the maceration extract includes: 60 parts of nickel sulfate, 55 parts of nickel acetate, 25 parts of nickelous carbonate and water by weight
130 parts.
Preferably, the reducibility gas is hydrogen, and the protective gas is nitrogen or argon gas, the carbon source
Gas is methane.
Preferably, the volume ratio of the carbon-source gas and protective gas is 1: (10-25).
Beneficial effects of the present invention are as follows: the present invention is by impregnating nickel on foam Copper substrate, in the large aperture of foam copper
The interior some fine nickel of filling can increase catalysis area, the graphene for growing CVD method, so that carbon atom is on foam copper surface
Migration can have more perfect three-dimensional net structure, improve the mechanical strength of network, be allowed to when internally diffusion
Preferably enhance the intensity of metal-base composites；Meanwhile carbon atom is higher in nickel surface permeability, and carbon consolidating on copper foil
Solubility is lower, limits deposition of the carbon atom in copper foil, has good coordinative role between ambrose alloy, nickel can equably divide
It is dispersed in foam Copper substrate, ambrose alloy mutual cooperation can grow more perfect network structure, and three-dimensional grapheme has smaller
Aperture, higher bulk density and better connectivity, and then preferably improve the intensity of composite material.
Specific embodiment
In order to deepen the understanding of the present invention, the present invention will be described in further detail with reference to the examples below, the embodiment
For explaining only the invention, it is not intended to limit the scope of the present invention..
Embodiment 1
A kind of preparation method of three-dimensional structure graphene enhancing Cu-base composites, it is characterised in that it is according to following step
Suddenly it carries out:
(1) foam copper is put into cleaning agent and is cleaned by ultrasonic 40min, obtain pretreated foam copper；
(2) pretreated foam copper is immersed in maceration extract and is excessively impregnated, dip time 12h takes out through drying
It is air-dried, repeats progress dipping process 2 times, dry be placed at 800 DEG C of last time roasts 4h, obtain impregnated foam
Copper；The maceration extract includes: 60 parts of nickel sulfate, 55 parts of nickel acetate, 25 parts of nickelous carbonate and 130 parts of water by weight；
(3) impregnated foam copper is placed in tube furnace, is passed through nitrogen and hydrogen, heating curve is set, with 15 DEG C/min's
Heating rate is warming up at 900 DEG C and is made annealing treatment, soaking time 30min；Hydrogen flowing quantity is 100sccm, and nitrogen flow is
200sccm；
(4) hydrogen gas supply is closed, is passed through methane gas, the volume ratio of methane gas and nitrogen is 1: 20, carries out three dimensional network
The deposition of network graphene grow and finishes after reacting 40min, closes methane and supplies, under protective gas atmosphere, with 8 DEG C/min
Rate of temperature fall be cooled to 220 DEG C, cooling to room temperature with the furnace later to get to three-dimensional structure graphene enhances copper-based composite wood
Material.
Embodiment 2
A kind of preparation method of three-dimensional structure graphene enhancing Cu-base composites, it is characterised in that it is according to following step
Suddenly it carries out:
(1) foam copper is put into cleaning agent and is cleaned by ultrasonic 60min, obtain pretreated foam copper；
(2) pretreated foam copper is immersed in maceration extract and is excessively impregnated, dip time is for 24 hours, to take out through drying
It is air-dried, repeats progress dipping process 3 times, dry be placed at 900 DEG C of last time roasts 6h, obtain impregnated foam
Copper；The maceration extract includes: 45 parts of nickel sulfate, 45 parts of nickel acetate, 35 parts of nickelous carbonate and 130 parts of water by weight；
(3) impregnated foam copper is placed in tube furnace, is passed through helium and hydrogen, heating curve is set, with 20 DEG C/min's
Heating rate is warming up at 950 DEG C and is made annealing treatment, soaking time 20min；Hydrogen flowing quantity is 200sccm, and helium gas flow is
400sccm；
(4) hydrogen gas supply is closed, methane gas is passed through, methane and helium keep certain flow ratio, carry out three dimensional network trachelospermum jasminoide
The deposition of black alkene grow and finishes after reacting 30-60min, closes methane gas supply, fast with the cooling of 5 DEG C/min under helium atmosphere
Rate is cooled to 300 DEG C, and cooling to room temperature with the furnace later to get to three-dimensional structure graphene enhances Cu-base composites.
After tested, the three-dimensional structure graphene of Examples 1 and 2 enhances Cu-base composites performance testing index such as 1 institute of table
Show:
Table 1
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of preparation method of three-dimensional structure graphene enhancing Cu-base composites, which is characterized in that according to the following steps into
Capable:
(1) foam copper is put into cleaning agent and is cleaned by ultrasonic 30-60min, obtain pretreated foam copper；
(2) pretreated foam copper is immersed in maceration extract and is excessively impregnated, dip time 12-24h takes out through dry empty
Gas is dry, repeats progress dipping process 2-4 times, and dry be placed at 600 DEG C -900 DEG C of last time roasts 4h-6h, obtain
Impregnated foam copper；The maceration extract includes: 30-65 parts of nickel sulfate, 40-60 parts of nickel acetate, 20-35 parts of nickelous carbonate by weight
With 100-150 parts of water；
(3) impregnated foam copper is placed in tube furnace, is passed through protective gas and reducibility gas, heating curve is set, with 15-
The heating rate of 20 DEG C/min is warming up at 900~1000 DEG C and is made annealing treatment, soaking time 15-30min；The reduction
Property gas flow be 100-200sccm, the protective gas flow be 200-400sccm；
(4) reducibility gas to be closed, carbon-source gas is passed through, the carbon-source gas and protective gas keep certain flow ratio, into
The deposition of row three-dimensional network graphene grow and finishes after reacting 30-60min, closing carbon-source gas, in protective gas atmosphere
Under, it is cooled to 200-300 DEG C with the rate of temperature fall of 5-10 DEG C/min, cools to room temperature with the furnace later to get three-dimensional structure stone is arrived
Black alkene enhances Cu-base composites.
2. a kind of preparation method of three-dimensional structure graphene enhancing Cu-base composites according to claim 1, feature
It is, the cleaning agent is the mixed solution of ethyl alcohol and acetone, and the ethyl alcohol and acetone volume ratio are 1:1.2-1.5.
3. a kind of preparation method of three-dimensional structure graphene enhancing Cu-base composites according to claim 1, feature
It is, the maceration extract includes: 60 parts of nickel sulfate, 55 parts of nickel acetate, 25 parts of nickelous carbonate and 130 parts of water by weight.
4. a kind of preparation method of three-dimensional structure graphene enhancing Cu-base composites according to claim 1, feature
It is, the reducibility gas is hydrogen, and the protective gas is nitrogen or argon gas, and the carbon-source gas is first
Alkane.
5. a kind of preparation method of three-dimensional structure graphene enhancing Cu-base composites according to claim 1, feature
It is, the volume ratio of the carbon-source gas and protective gas is 1: (10-25).
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Cited By (3)
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| CN113173616A (en) * | 2021-04-25 | 2021-07-27 | 中国海洋大学 | Three-dimensional integrated photo-thermal conversion material and preparation method thereof |
| CN116516268A (en) * | 2023-04-14 | 2023-08-01 | 常熟市普华电工材料有限公司 | Alloy copper wire annealing process |
| CN117286364A (en) * | 2023-11-24 | 2023-12-26 | 中铝科学技术研究院有限公司 | Graphene reinforced metal matrix composite material with three-dimensional network structure and preparation method thereof |
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