CN108716114A - A kind of preparation method of new copper/graphene/polymer composite fibrous - Google Patents

A kind of preparation method of new copper/graphene/polymer composite fibrous Download PDF

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CN108716114A
CN108716114A CN201810581263.4A CN201810581263A CN108716114A CN 108716114 A CN108716114 A CN 108716114A CN 201810581263 A CN201810581263 A CN 201810581263A CN 108716114 A CN108716114 A CN 108716114A
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graphene
copper
polymer
composite
composite fibre
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郑坚
张晓�
熊超
支建庄
于贵波
苏续军
殷军辉
崔凯波
康小勇
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Army Engineering University of PLA
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Abstract

The invention discloses a kind of preparation methods of new copper/graphene/polymer composite fibrous, include the following steps:The first step handles high purity copper fiber surface using polishing method, prepares the copper fiber of low surface roughness;High-purity copper fiber is placed in chemical vapor deposition tube furnace by second step, by chemical vapor deposition method, graphene is grown on copper fiber surface, to obtain copper/graphene composite fibre;Third walks, and prepares copper/graphene/polymer multi-layer composite fibre;New copper/graphene of the present invention/polymer composite fibrous preparation method, process conditions are simple, and flow is easy to control, and gained composite conducting fiber material is evenly distributed, and is tightly combined, and composite fibre quality is higher, high yield rate.

Description

A kind of preparation method of new copper/graphene/polymer composite fibrous
Technical field
The present invention relates to a kind of preparation methods of new copper/graphene/polymer composite fibrous, belong to conductive material preparation Technical field.
Background technology
Copper and its alloy conductive and thermal conductivity are preferable, but hardness and strength are relatively low, poor heat resistance, and easily softening becomes under high temperature Shape, therefore application range is very restricted;To obtain high-strength material, the method generally used is to be added to increase into Copper substrate Strong body forms composite material, and common reinforcement type has particle, fiber, graphite etc., novel reinforcement also have carbon nanotubes, Graphene etc.;Electric conductivity is to weigh the important indicator of Cu-base composites, when developing high-strength copper based composites, the head that faces It is that the electric conductivity of material and intensity are difficult to take into account to want problem, i.e. the raising of intensity is using the loss of conductivity as cost, intensity Gao Ze Conductivity is low;Therefore, when improving the intensity of Cu-base composites, ensure that its conductivity is still maintained at higher level, become mesh One of the hot spot of preceding Cu-base composites research;Copper fiber electric conductivity is fine, is largely used to manufacture electric wire, cable, brush etc.;For The comprehensive performance of copper fiber is promoted, many researchs make it have good for manufacturing regeneration copper fiber and compound copper fiber Electric conductivity and mechanical property;With the development of science and technology, it develops multiple by the various new type functionals of matrix of copper fiber Copper fiber is closed, application field and the market of copper fiber have been further expanded.
Graphene has perfect two dimensional crystal structure, its lattice is the hexagon surrounded by six carbon atoms, thickness For an atomic layer;It is keyed with σ between carbon atom, combination sp2Hydridization, it is extremely excellent that these σ keys assign graphene Mechanical property and structural rigidity;Its feature is frivolous, high-strength, electric conductivity is excellent, is once called " king of new material ", these Special physical property makes it in numerous necks such as semi-conducting material, energy storage material, polymer composite, electronic device and sensor Domain has a wide range of applications;Graphene is as a kind of New Two Dimensional material of monoatomic layer thickness, compared with other carbon materials, tool There are more excellent physical and chemical properties;Graphene theoretical specific surface area is 2630 m2g-1, Young's modulus reaches 1000 GPa, tensile strength are 130 GPa, are more than 100 times of steel;The carrier mobility of graphene at room temperature is about 15000cm2/ (V s), this numeric ratio have exceeded 10 times of silicon materials;Meanwhile graphene has superelevation thermal conductivity(~5000 Wm-1K-1), play an important roll for the transmission of energy;There is graphene quantum hall effect, ambipolar field to imitate in terms of electricity Properties should be waited, therefore the fields such as scene effect transistor, ultracapacitor have a good application prospect;In various graphenes In preparation method, for chemical vapour deposition technique because it can realize large-scale production, the number of plies is controllable, suitable growth high quality, big face The advantages that long-pending graphene, increasingly favored by researcher;In chemical vapour deposition technique preparation process, the choosing of base material It selects particularly important;The result shows that, copper is selected to be obtained extensively as the base material of chemical vapor deposition method by years of researches Approve.
Copper is both growth substrate during the CVD growth of graphene, while being also used as catalyst, has certain catalysis Activity;The graphene that CVD method obtains is utilized on Cu foils surface, due to its special growth mechanism, i.e. surface self termination effect Absolute monolayer growth may be implemented, simultaneously because the Van der Waals interaction of interlayer can lead to the growth of bilayer graphene;Cause This, the graphene grown on Cu foils has become the important materials in related Fundamental Aspects research;In the base of this technology On plinth, by graphene growth in the surface of copper fiber, copper/graphene composite material of high-quality graphene cladding is also can get, However such research is less at present;Method that at present can be by graphene coated in copper fiber mainly has:CVD method, hydro-thermal method, spray Coating etc., however graphene and copper fiber interface obtained by hydro-thermal method are loose, generate larger gap, interface connection is insecure, spraying Method is simple for process, but is difficult to coat uniformly;CVD method obtains the best in quality and very high with copper surface compatability of graphene, can Give full play to the advantage and performance of composite construction.
Insulating material of polymer not only has many advantages, such as light weight, easy processing, at low cost, also has environment wide adaptation range The characteristics of, it has been widely used in electrical, electronics industry;Currently, power equipment and electronic device etc. are just towards high-power, small-sized Change and the directions such as lightweight are developed, requirements at the higher level are proposed to Insulation Problems;Conductive fiber surfaces coated polymer can rise To insulating effect, simultaneously as the mechanical property that polymer is excellent, can effectively promote the flexibility of fiber, avoid internal junction Structure is destroyed;Polymer for conductive fiber insulation usually has excellent electric property and mechanical property, simultaneously also Should have good high temperature resistance, such as polyethylene, modified polypropene.The present invention by graphene and is gathered using copper as base material It closes object and is wrapped in copper material surface successively and copper/graphene/polymer composite fibrous is made so that the electric conductivity and power of composite fibre It learns performance to improve a lot compared with copper/graphene composite material, and infiltrating can be further in the polymeric layer of fiber surface The flexibility and fatigue resistance of composite fibre are improved, while assigning the insulating properties of fiber surface, and internal structure can be protected Do not corroded by the external world, improve corrosion resistance, extends working life.
Invention content
To solve the above problems, the present invention proposes a kind of preparation side of new copper/graphene/polymer composite fibrous Method, composite conducting fiber material made from this method are evenly distributed, are tightly combined.
New copper/graphene of the present invention/polymer composite fibrous preparation method, includes the following steps:
The first step prepares the copper fiber of low surface roughness, handles high purity copper fiber surface using polishing method, prepares low surface The copper fiber of roughness;
Second step prepares copper/graphene composite fibre, high-purity copper fiber is placed in chemical vapor deposition tube furnace, is passed through Chemical vapor deposition grows graphene, to obtain copper/graphene composite fibre on copper fiber surface;
Third walks, and prepares copper/graphene/polymer multi-layer composite fibre, takes infiltrated with molten metal method, utilizes traction machine travel second Copper/graphene bundle of composite fibers obtained makes composite fibre by the mold of the thermoplastic polymer materials containing melting in step Beam is extracted out after obtaining good infiltration, prepares copper/graphene/polymer multi-layer composite fibre.
Further, for high-purity copper fiber in the first step after the polishing treatment of surface, surface roughness reduces by 10 Times or more.
Still further, the polishing method in the first step is electrochemical polishing method.
As preferred embodiment, graphene is grown on copper fiber surface using chemical vapor deposition in the second step During, using methane gas as carbon source, hydrogen is during which passed through into tube furnace;And in copper/graphene composite fibre cooling When, argon gas and hydrogen are passed through into tube furnace.
Further, the graphene growth time in the second step is 40min, growth pressure 80Pa.
Further, the high polymer is polypropylene, polyethylene, polystyrene, makrolon, acrylonitrile-styrene-fourth Diene copolymers, polyamide, polybutylene terephthalate, polyethylene terephthalate, polyphenylene oxide, polyphenylene sulfide, hard are poly- Vinyl chloride, polymethyl methacrylate, polyformaldehyde, polysulfones, polyimides, polytetrafluoroethylene (PTFE), polytrifluorochloroethylene, perfluoroethylene The modified product of propylene, polybutylene terephthalate, chlorinated polyether or above-mentioned high polymer.
Further, the bundle of composite fibers for the package high polymer extracted out after infiltration is immersed in the third step cold in sink But, composite fibre after cooling is at the uniform velocity wound on reel;By 60 ~ 120 DEG C in an oven of the composite fibre of winding after coiling Dry 8 hours or more, it is put into the dry container of guarantor and preserves.
The present invention compared with prior art, the preparation side of new copper/graphene of the invention/polymer composite fibrous Method, process conditions are simple, and flow is easy to control, and gained composite fibre quality is higher, high yield rate;Graphene is on copper fiber surface Be not in the agglomeration of graphene, therefore graphene is evenly distributed on copper fiber surface during growth;It is coated on copper The graphene number of plies of fiber surface is few, and defect is few, can give full play to graphene excellent electricity and mechanical property, therefore compound The electric conductivity and mechanical property of fiber improve a lot, including conductivity, intensity, elasticity, fatigue resistance, the property such as corrosion-resistant Energy;Infiltration can further increase the flexibility and fatigue resistance of composite fibre in the polymeric layer of fiber surface, assign simultaneously The insulating properties of fiber surface is given, and not corroded by the external world for internal structure can be protected, improves corrosion resistance, extends working life; The structure of MULTILAYER COMPOSITE has given full play to the characteristics of layers of material performance, ensure that conductive fiber can normal work in the presence of a harsh environment Make, special equipment higher especially suitable for performance requirement and complicated working environment can be widely applied to electronic product, electricity Device, Communication Equipment, safety equipment, information are transmitted and the civil and militaries product scopes such as safety.
Description of the drawings
Fig. 1 is the process flow chart of the present invention.
Fig. 2 is copper/graphene/polymer composite fibrous microstructure schematic diagram of the present invention.
Each component is labeled as in attached drawing:1- copper fibers, 2- graphene layers, 3- polymeric layers.
Specific implementation mode
The preparation method of new copper/graphene as shown in Figure 1/polymer composite fibrous, includes the following steps:
The first step prepares the copper fiber of low surface roughness, handles high purity copper fiber surface using polishing method, prepares low surface The copper fiber of roughness;
High-purity copper fiber is polished in electrobrightening equipment, 5 μm of copper fiber diameter, electrobrightening power supply two-phase 220V selects silicon controlled rectifier (SCR), and quartz ampoule heating, titanium hanger, high-purity copper fiber is after the polishing treatment of surface, rough surface Degree reduces by 10 times or more;
Second step, prepares copper/graphene composite fibre, and high-purity copper fiber is placed in chemical vapor deposition(CVD)In tube furnace, By chemical vapor deposition, graphene is grown on copper fiber surface, to obtain copper/graphene composite fibre;
(1)Copper fiber after polishing is positioned in CVD tube furnaces, graphene layer is grown on copper fiber surface using CVD method, Wherein 1000 DEG C of growth temperature, carbon source is methane(CH4)Gas, argon gas(Ar)As current-carrying gas, hydrogen(H2)For protecting With raising graphene quality, intrinsic standoff ratio p (CH4):p(H2)=1:10,80 Pa of graphene growth pressure, growth time 40 minutes;
(2)The composite fibre that surface is grown to graphene is cooled to room temperature in CVD tube furnaces, during which keeps being passed through Ar and H2;
Third walks, and prepares copper/graphene/polymer multi-layer composite fibre, takes infiltrated with molten metal method, utilizes traction machine travel second Copper/graphene bundle of composite fibers obtained makes composite fibre by the mold of the thermoplastic polymer materials containing melting in step Beam is extracted out after obtaining good infiltration, prepares copper/graphene/polymer multi-layer composite fibre, as shown in Figure 2;
(1)It is pure high poly- by containing molten with copper/graphene fiber beam prepared by traction machine travel using infiltrated with molten metal method Object material or its polymer-modified impregnation mold, 120 ~ 300 DEG C of mould temperature make bundle of composite fibers obtain good infiltration;
(2)The composite fibre of package high polymer that will be after infiltration immerse it is cooling in sink, by fiber after cooling at the uniform velocity winding It places;
(3)The composite fibre of preparation is dried 8 hours or more for 60 ~ 120 DEG C in an oven, is put into protect in dry container and preserves.
Wherein, the high polymer is polypropylene, polyethylene, polystyrene, makrolon, acrylonitrile-styrene-butadiene Copolymer, polyamide, polybutylene terephthalate, polyethylene terephthalate, polyphenylene oxide, polyphenylene sulfide, hard polychlorostyrene second Alkene, polymethyl methacrylate, polyformaldehyde, polysulfones, polyimides, polytetrafluoroethylene (PTFE), polytrifluorochloroethylene, perfluoroethylene third The modified product of alkene, polybutylene terephthalate, chlorinated polyether or above-mentioned high polymer.
Above-described embodiment is only the better embodiment of the present invention, therefore all structures according to described in present patent application range It makes, the equivalent change or modification that feature and principle are done, is included within the scope of present patent application.

Claims (7)

1. a kind of new copper/graphene/polymer composite fibrous preparation method, which is characterized in that include the following steps:
The first step prepares the copper fiber of low surface roughness, handles high purity copper fiber surface using polishing method, prepares low surface The copper fiber of roughness;
Second step prepares copper/graphene composite fibre, high-purity copper fiber is placed in chemical vapor deposition tube furnace, is passed through Chemical vapor deposition grows graphene, to obtain copper/graphene composite fibre on copper fiber surface;
Third walks, and prepares copper/graphene/polymer multi-layer composite fibre, takes infiltrated with molten metal method, utilizes traction machine travel second Copper/graphene bundle of composite fibers obtained makes composite fibre by the mold of the thermoplastic polymer materials containing melting in step Beam is extracted out after obtaining good infiltration, prepares copper/graphene/polymer multi-layer composite fibre.
2. new copper/graphene according to claim 1/polymer composite fibrous preparation method, it is characterised in that:Institute High-purity copper fiber in the first step is stated after the polishing treatment of surface, surface roughness reduces by 10 times or more.
3. new copper/graphene according to claim 1/polymer composite fibrous preparation method, it is characterised in that:Institute It is electrochemical polishing method to state the polishing method in the first step.
4. new copper/graphene according to claim 1/polymer composite fibrous preparation method, it is characterised in that:Institute It states in second step using chemical vapor deposition during copper fiber surface grows graphene, using methane gas as carbon source, Period is passed through hydrogen into tube furnace;And in copper/graphene composite fibre cooling, argon gas and hydrogen are passed through into tube furnace.
5. new copper/graphene according to claim 1 or 4/polymer composite fibrous preparation method, feature exists In:The graphene growth time in the second step is 40min, growth pressure 80Pa.
6. new copper/graphene according to claim 1/polymer composite fibrous preparation method, it is characterised in that:Institute State high polymer be polypropylene, polyethylene, polystyrene, makrolon, acrylonitrile-butadiene-styrene copolymer, polyamide, Polybutylene terephthalate, polyethylene terephthalate, polyphenylene oxide, polyphenylene sulfide, Hard PVC, polymethylacrylic acid Methyl esters, polyformaldehyde, polysulfones, polyimides, polytetrafluoroethylene (PTFE), polytrifluorochloroethylene, perfluoroethylene-propylene, poly terephthalic acid fourth The modified product of diester, chlorinated polyether or above-mentioned high polymer.
7. new copper/graphene according to claim 1/polymer composite fibrous preparation method, it is characterised in that:Institute It states and the bundle of composite fibers for the package high polymer extracted out after infiltration is immersed to cooling in sink, composite fibre after cooling in third step At the uniform velocity it is wound on reel;The composite fibre of winding is dried 8 hours or more for 60 ~ 120 DEG C in an oven after coiling, it is dry to be put into guarantor It is preserved in container.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113412047A (en) * 2021-07-06 2021-09-17 西安工业大学 Copper-based graphene coating structure and preparation method thereof

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102560415A (en) * 2012-01-20 2012-07-11 中国科学院上海硅酸盐研究所 Three-dimensional graphene/metal line or metal wire composite structure and preparation method thereof
CN103225076A (en) * 2013-05-10 2013-07-31 南京信息工程大学 Wear-resistant graphene surface modification method
CN103714972A (en) * 2013-11-25 2014-04-09 浙江大学 Linear secure high-energy-density supercapacitor and preparation method thereof
CN103730186A (en) * 2013-12-31 2014-04-16 美特科技(苏州)有限公司 Graphene wire and production method thereof
CN103794298A (en) * 2014-01-23 2014-05-14 中国科学院过程工程研究所 Preparation method for graphene wires
CN104916453A (en) * 2015-04-17 2015-09-16 浙江大学 Coaxial graphene fiber supercapacitor and manufacturing method thereof
CN205140534U (en) * 2015-11-11 2016-04-06 江苏中超控股股份有限公司 Graphite alkene coating film aviation wire
CN105506579A (en) * 2015-12-15 2016-04-20 南京工程学院 Preparation method of graphene coated silicon carbide nanowire
WO2016094244A1 (en) * 2014-12-10 2016-06-16 Schlumberger Canada Limited Corrosion resistant coating and conductor
CN105986302A (en) * 2016-07-04 2016-10-05 常州大学 Technique for preparing protective coating on copper surface
CN106816423A (en) * 2017-01-21 2017-06-09 山东科大鼎新电子科技有限公司 A kind of Graphene bonding brass wire and preparation method thereof
CN106910549A (en) * 2017-03-23 2017-06-30 福建甲子信息技术股份有限公司 A kind of polytetrafluoroethylene (PTFE)/graphene wire and preparation method thereof

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102560415A (en) * 2012-01-20 2012-07-11 中国科学院上海硅酸盐研究所 Three-dimensional graphene/metal line or metal wire composite structure and preparation method thereof
CN103225076A (en) * 2013-05-10 2013-07-31 南京信息工程大学 Wear-resistant graphene surface modification method
CN103714972A (en) * 2013-11-25 2014-04-09 浙江大学 Linear secure high-energy-density supercapacitor and preparation method thereof
CN103730186A (en) * 2013-12-31 2014-04-16 美特科技(苏州)有限公司 Graphene wire and production method thereof
CN103794298A (en) * 2014-01-23 2014-05-14 中国科学院过程工程研究所 Preparation method for graphene wires
WO2016094244A1 (en) * 2014-12-10 2016-06-16 Schlumberger Canada Limited Corrosion resistant coating and conductor
CN104916453A (en) * 2015-04-17 2015-09-16 浙江大学 Coaxial graphene fiber supercapacitor and manufacturing method thereof
CN205140534U (en) * 2015-11-11 2016-04-06 江苏中超控股股份有限公司 Graphite alkene coating film aviation wire
CN105506579A (en) * 2015-12-15 2016-04-20 南京工程学院 Preparation method of graphene coated silicon carbide nanowire
CN105986302A (en) * 2016-07-04 2016-10-05 常州大学 Technique for preparing protective coating on copper surface
CN106816423A (en) * 2017-01-21 2017-06-09 山东科大鼎新电子科技有限公司 A kind of Graphene bonding brass wire and preparation method thereof
CN106910549A (en) * 2017-03-23 2017-06-30 福建甲子信息技术股份有限公司 A kind of polytetrafluoroethylene (PTFE)/graphene wire and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
梁勇明等: "铜箔形貌对石墨烯生长质量影响的表面氧化法评判", 《机械工程材料》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113412047A (en) * 2021-07-06 2021-09-17 西安工业大学 Copper-based graphene coating structure and preparation method thereof
CN113412047B (en) * 2021-07-06 2022-02-22 西安工业大学 Copper-based graphene coating structure and preparation method thereof

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