CN107201485B - A kind of graphene masterbatch and preparation method and application method for enhancing copper-based material - Google Patents

A kind of graphene masterbatch and preparation method and application method for enhancing copper-based material Download PDF

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CN107201485B
CN107201485B CN201710353720.XA CN201710353720A CN107201485B CN 107201485 B CN107201485 B CN 107201485B CN 201710353720 A CN201710353720 A CN 201710353720A CN 107201485 B CN107201485 B CN 107201485B
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graphene
copper
tin
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CN107201485A (en
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陈庆
王镭迪
曾军堂
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Shandong Kupin Intelligent Technology Co ltd
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Chengdu New Keli Chemical Science Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C47/00Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/02Pretreatment of the fibres or filaments
    • C22C47/06Pretreatment of the fibres or filaments by forming the fibres or filaments into a preformed structure, e.g. using a temporary binder to form a mat-like element
    • C22C47/062Pretreatment of the fibres or filaments by forming the fibres or filaments into a preformed structure, e.g. using a temporary binder to form a mat-like element from wires or filaments only
    • C22C47/064Winding wires
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C49/00Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/14Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments

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Abstract

The invention belongs to the masterbatch preparation fields that graphene enhances composite material, provide a kind of graphene masterbatch and preparation method and application for enhancing copper-based material.It is characterized in that a kind of fine Filamentous graphene containing metallic tin;And provide the preparation method of the filiform graphene, graphene and a small amount of tin fusing are mixed, then graphene uniform is scattered in tin by spraying wire drawing repeatedly, wire drawing step by step is then carried out by wire drawing machine, form the fine Filamentous graphene masterbatch of high graphene concentration;Further provide for the application process of Filamentous graphene masterbatch, when use, which directly rotates with linear copper wire, to be wound, and Filamentous graphene masterbatch is intertwined with copper wire, to which the intensity, electric conductivity, thermal conductivity of copper wire be substantially improved.The defects of significant advantage is to overcome graphene to melt that dispersion difficulty is big, high energy consumption directly in copper, complex process, is suitable for pushing large-scale production, to promote application of the graphene in enhancing composite material.

Description

A kind of graphene masterbatch and preparation method and application method for enhancing copper-based material
Technical field
The present invention relates to the preparation fields of graphene composite material, more particularly, to a kind of stone for enhancing copper-based material Black alkene masterbatch and preparation method and application method.
Background technology
Graphene, most thin two-dimensional material, the thickness only 0.335nm of single layer.From early 20th century, scientists just to its into Research is gone.Until 2004, Univ Manchester UK physics expert An Deliehaimu and Constantine Nuo Woxiaoluo Husband is prepared for single-layer graphene using adhesive tape adhesive technology, but does not create much of a stir at that time;2005, same Man Chesi The quasi particle of the especially big researcher's confirmation graphene for learning team and Columbia University(quasiparticle)It is that massless enlightening is drawn Gram fermion(Dirac fermion), to cause the research boom of graphene.
Graphene is the two-dimentional new material being made of carbon atom, and carbon atom is formd using sp2 hydridization with honey comb like Colloidal particles, this structure is highly stable, and carbon-carbon bond bond distance only has 1.42 angstroms, and it is one that single-layer graphene, which only has 0.335nm, The two dimensional crystal structure of kind almost Perfect, graphene is considered as plane polycyclic aromatic hydrocarbons (PAH) atomic crystal.Graphene interior atoms Link it is very flexible, when applying outer force effect to graphite, two dimensional surface will Free Transform, carbon atom resets to form wave Type, to the stability of holding structure.
Graphene is the semiconductor of typical zero band gap, forms plane six-membered ring structure by sp2 hydridization, pi-electron is same The big pi bond of delocalization is formed in one plane.This unique structure makes graphene have unique property, as most thin in the world Nano material, graphene is almost fully transparent, only absorbs 2.3% light, and thermal coefficient reaches 5300W/ m.K, than Diamond and carbon nanotube higher, at room temperature electron mobility reach the 1/300 of the light velocity, resistivity only has 10-6 Ω .cm, than Copper and silver-colored resistivity are lower, are the materials of resistivity minimum in the world, but have the mechanical property of superelevation, reach 1060GPa, are demonstrate,proved Bright is the present age most firm material, 100 times harder than the best steel capital, can be used for preparing HHT higher high tensile film and with preparation The potentiality of " space elevator ".
Graphene is allowed to have bright foreground in application aspect with its exquisite structure, unmatched performance.Such as profit It is applied to electronic chip, transistor with the electron mobility of its superelevation, the light transmittance of superelevation is applied to transparent electrode, and rare leads Hot coefficient is applied to interface Heat Conduction Material, and the specific surface area of superelevation is applied to ultracapacitor, and graphene surface can allow Defect using this property so that be applied to sea water desalination, and graphene is in solar cell, biological devices, anti-biotic material etc. There is very extensive application prospect.
Height leads one that high-strength composite material is wherein important, wherein Cu-base composites have good conduction Thermal conductivity and processing performance have a wide range of applications in electronic product, aerospace and automotive field.With every field Fast development, the requirement to Cu-base composites is higher and higher, although traditional fiber and reinforced particulate can improve material Mechanical property, but often make its electrical and thermal conductivity performance reduction, therefore, research and development have excellent conductive heat conductivility simultaneously also have The Cu-base composites of high intensity become current urgent problem to be solved.Traditional high-strength copper based composites electrical and thermal conductivity It can decrease.Graphene is ideal copper-based reinforcement because of its good electrical and thermal conductivity and intensity thus.Give full play to stone It is more and more important to prepare high performance Cu-base composites for the advantage of black alkene.It has been reported that enhancing copper by graphene at present Sill mainly using melting or is ground graphene Forced Dispersion in Copper substrate.But it is limited to disperse that difficulty is big, high energy consumption, Complex process, it is difficult to large-scale production and application.
Invention content
In view of disadvantages described above, the present invention proposes a kind of graphene masterbatch for enhancing copper-based material, it is characterized in that a kind of Fine Filamentous graphene containing metallic tin;And the preparation method of the filiform graphene is provided, graphene and a small amount of tin are melted Change is mixed, and then graphene uniform is scattered in tin by spraying wire drawing repeatedly, then carries out wire drawing step by step by wire drawing machine, Form the fine Filamentous graphene masterbatch of high graphene concentration;The application process of Filamentous graphene masterbatch is further provided for, is used When directly rotate and wind with linear copper wire, Filamentous graphene masterbatch is intertwined with copper wire, to which copper wire be substantially improved Intensity, electric conductivity, thermal conductivity.Significant advantage is to overcome graphene to melt that dispersion difficulty is big, high energy consumption directly in copper, The defects of complex process, is suitable for pushing large-scale production, to promote application of the graphene in enhancing composite material.
To achieve the above object, the specific technical solution that the present invention uses is as follows:
A kind of graphene masterbatch for enhancing copper-based material, it is characterized in that a kind of Filamentous graphene containing metallic tin, Its line footpath is 0.05-0.1mm.
A kind of preparation method for enhancing the graphene masterbatch of copper-based material, it is characterised in that first graphene with it is a small amount of Tin fusing be mixed and stretched through spinneret, graphene uniform is scattered in metallic tin, wire drawing step by step is then carried out by wire drawing machine, The fine Filamentous graphene masterbatch for forming high graphene concentration, is as follows:
(1)The dispersion of graphene and tin:Tin is heated to melting in high temperature furnace, and removes impurity, then by graphene It is proportionally added into high temperature furnace, in nitrogen atmosphere, forward direction stirring certain time, then reverse agitating function certain time, it stirs repeatedly After four times, continuously decrease mixing speed, until stop, and stand after a certain period of time, move into spinning appts, by spinning appts to The nozzle of upper setting sprays to form Filamentous injection stream;Repeatedly with filiform injection 3-4 times, by spraying wire drawing by graphene It is dispersed in metallic tin;
(2)Extrusion forming:By step(1)The dispersion extrusion forming of obtained graphene and metallic tin, setting mould temperature It is 180 ~ 190 DEG C, the compound tin silk of cylindrical graphite alkene that line footpath is 10 ± 1mm is formed by squeezing;
(3)The wire drawing of graphene and tin:By step(3)The obtained compound tin silk of cylindrical graphite alkene is through excessively three wire drawings Machine, big drawing, two drawings, three are drawn, often after a wire drawing machine, are applied using molten rosin, preferably ensure that wire drawing Uniformity, compactness and rounding, to obtain line footpath in the composite filaments of 0.05-0.1mm, i.e., one kind is for enhancing Copper base material The graphene masterbatch of material.
Preferably, step(1)The mass ratio of the graphene and tin is 1:2-4.
Preferably, step(1)The primary positive and reverse agitating function time is 10 ~ 20min.
Preferably, step(1)The nozzle diameter of the injection apparatus is 0.5-1mm, and injection pressure is 1-3MPa.
Preferably, step(1)The time of repose is 20 ~ 30min, preferably eliminates bubble.
Preferably, step(3)It is described it is big draw, two draw, three draw obtained filament line footpath be respectively 1-2mm, 0.5-1mm, 0.05-0.1mm。
Graphene uniform is scattered in metallic tin by the present invention by spinneret wire drawing, is stretched step by step further across wire drawing machine, Form uniform, fine and close, round and smooth microfilament, i.e., a kind of graphene masterbatch for enhancing copper-based material.Using the microfilament as Masterbatch, high degree of dispersion is shown with copper wire for enhancing copper wire with significant advantage with good graphene wherein Prehensile, compatibility.
Further, graphene masterbatch provided by the invention, when for enhancing copper-based material, specific application method is: By screw traction, the graphene masterbatch of fine filiform is stretched and is intertwined with copper wire, forms the spiral shell with a constant pitch Curl up silk, then change lead, make it with negative direction spiral winding copper wire, then under an atmosphere of hydrogen, certain temperature, Under pressure, the composite filaments of graphene and tin and copper wire is made to carry out half hot melt heat seal, to enhance the interface bond strength of the two, from And obtain the copper-based material of graphene enhancing.
Preferably, the screw pitch of the spiral wrapping wire is 2 ~ 3mm.
Preferably, the heat-seal temperature of the composite filaments and copper wire of the graphene and tin is 80 ~ 90 DEG C;The graphene with The composite filaments of tin and the heat seal pressure of copper wire are 0.2 ~ 0.4MPa.
The present invention provides a kind of graphene masterbatch and preparation method and application for enhancing copper-based material, with existing skill Art is compared, and the feature and excellent effect protruded is:
1, the present invention provides a kind of graphene masterbatch of fine filiform, and the enhancing to copper wire is realized by winding.It carries A kind of technological means of novel graphene enhancing system copper-based material is supplied.
2, the present invention carries out repeatedly spinneret stretching after being mixed by graphene and tin fusing, realizes that graphene uniform is scattered in In metallic tin.
3, the present invention is prepared for uniform, fine and close, round and smooth microfilament by three-level wire drawing, i.e., a kind of copper-based for enhancing The graphene masterbatch of material.The masterbatch can be stretched further and be wound with copper wire when in use, can give full play to graphene sheet The superior function of body greatly promotes the mechanical property and electrical and thermal conductivity performance of copper wire.
4, present invention process process is simple, at low cost, and low energy consumption, is easy to push large-scale production.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A kind of preparation method and application method for enhancing the graphene masterbatch of copper-based material, it is specific as follows:
(1)The dispersion of graphene and tin:2kg tin is heated to melting in high temperature furnace, and removes impurity, then by 1kg Graphene is added in high temperature furnace, in nitrogen atmosphere, forward direction stirring certain time, then reverse agitating function certain time, it stirs repeatedly After four times, mixing speed is continuously decreased, until stopping, and stands 20min, spinning appts is moved into, is set upwards by spinning appts The nozzle set sprays to form Filamentous injection stream;Injection pressure is 1MPa, repeatedly with filiform injection 3 times, is drawn by spraying Graphene uniform is scattered in metallic tin by silk;
(2)Extrusion forming:By step(1)The dispersion extrusion forming of obtained graphene and metallic tin, setting mould temperature It is 180 ~ 190 DEG C, the compound tin silk of cylindrical graphite alkene that line footpath is 10 ± 1mm is formed by squeezing;
(3)The wire drawing of graphene and tin:By step(3)The obtained compound tin silk of cylindrical graphite alkene is through excessively three wire drawings Machine, big drawing, two drawings, three are drawn, often after a wire drawing machine, are applied using molten rosin, preferably ensure that wire drawing Uniformity, compactness and rounding, the filament line footpath that big drawing, two drawings, three drawings obtain is respectively 1-2mm, 0.5-1mm, 0.05- 0.1mm, to obtain line footpath in the composite filaments of 0.05-0.1mm, i.e., a kind of graphene masterbatch for enhancing copper-based material.
When for enhancing copper-based material, specific application method is:By screw traction, by the graphene of fine filiform Masterbatch is further stretched and is intertwined with copper wire, and it is 3mm to form the screw pitch with spiral wrapping wire, then changes lead, Make it with negative direction spiral winding copper wire, then under an atmosphere of hydrogen, under 80 ~ 90 DEG C, 0.2 ~ 0.4MPa pressure, makes graphene Half hot melt heat seal is carried out with copper wire with the composite filaments of tin, with the interface bond strength of both enhancings, is increased to obtain graphene Strong copper-based material.
By the test to enhancing copper wire, the tensile strength of copper wire, elongation at break significantly improve, and resistivity reduces bright It is aobvious.The significant advantage that fine Filamentous graphene masterbatch of the invention is modified copper wire is preferably shown.Specific test performance is shown in Table 1.
Embodiment 2
A kind of preparation method and application method for enhancing the graphene masterbatch of copper-based material, it is specific as follows:
(1)The dispersion of graphene and tin:2kg tin is heated to melting in high temperature furnace, and removes impurity, then by 1kg Graphene is added in high temperature furnace, in nitrogen atmosphere, forward direction stirring certain time, then reverse agitating function certain time, it stirs repeatedly After four times, mixing speed is continuously decreased, until stopping, and stands 20min, spinning appts is moved into, is set upwards by spinning appts The nozzle set sprays to form Filamentous injection stream;Injection pressure is 1MPa, repeatedly with filiform injection 3 times, is drawn by spraying Graphene uniform is scattered in metallic tin by silk;
(2)Extrusion forming:By step(1)The dispersion extrusion forming of obtained graphene and metallic tin, setting mould temperature It is 180 ~ 190 DEG C, the compound tin silk of cylindrical graphite alkene that line footpath is 10 ± 1mm is formed by squeezing;
(3)The wire drawing of graphene and tin:By step(3)The obtained compound tin silk of cylindrical graphite alkene is through excessively three wire drawings Machine, big drawing, two drawings, three are drawn, often after a wire drawing machine, are applied using molten rosin, preferably ensure that wire drawing Uniformity, compactness and rounding, the filament line footpath that big drawing, two drawings, three drawings obtain is respectively 1-2mm, 0.5-1mm, 0.05- 0.1mm, to obtain line footpath in the composite filaments of 0.05-0.1mm, i.e., a kind of graphene masterbatch for enhancing copper-based material.
When for enhancing copper-based material, specific application method is:By screw traction, by the graphene of fine filiform Masterbatch is further stretched and is intertwined with copper wire, and it is 2mm to form the screw pitch with spiral wrapping wire, then changes lead, Make it with negative direction spiral winding copper wire, then under an atmosphere of hydrogen, under one 80 ~ 90 DEG C, 0.2 ~ 0.4MPa pressure, makes graphite The composite filaments of alkene and tin carry out half hot melt heat seal with copper wire, with the interface bond strength of both enhancings, to obtain graphene The copper-based material of enhancing.
By the test to enhancing copper wire, the tensile strength of copper wire, elongation at break significantly improve, and resistivity reduces bright It is aobvious.The significant advantage that fine Filamentous graphene masterbatch of the invention is modified copper wire is preferably shown.Specific test performance is shown in Table 1.
Embodiment 3
A kind of preparation method and application method for enhancing the graphene masterbatch of copper-based material, it is specific as follows:
(1)The dispersion of graphene and tin:3kg tin is heated to melting in high temperature furnace, and removes impurity, then by 1kg Graphene is added in high temperature furnace, in nitrogen atmosphere, forward direction stirring certain time, then reverse agitating function certain time, it stirs repeatedly After four times, mixing speed is continuously decreased, until stopping, and stands 30min, spinning appts is moved into, is set upwards by spinning appts The nozzle set sprays to form Filamentous injection stream;Injection pressure is 2MPa, repeatedly with filiform injection 4 times, is drawn by spraying Graphene uniform is scattered in metallic tin by silk;
(2)Extrusion forming:By step(1)The dispersion extrusion forming of obtained graphene and metallic tin, setting mould temperature It is 180 ~ 190 DEG C, the compound tin silk of cylindrical graphite alkene that line footpath is 10 ± 1mm is formed by squeezing;
(3)The wire drawing of graphene and tin:By step(3)The obtained compound tin silk of cylindrical graphite alkene is through excessively three wire drawings Machine, big drawing, two drawings, three are drawn, often after a wire drawing machine, are applied using molten rosin, preferably ensure that wire drawing Uniformity, compactness and rounding, the filament line footpath that big drawing, two drawings, three drawings obtain is respectively 1-2mm, 0.5-1mm, 0.05- 0.1mm, to obtain line footpath in the composite filaments of 0.05-0.1mm, i.e., a kind of graphene masterbatch for enhancing copper-based material.
When for enhancing copper-based material, specific application method is:By screw traction, by the graphene of fine filiform Masterbatch is further stretched and is intertwined with copper wire, and it is 3mm to form the screw pitch with spiral wrapping wire, then changes lead, Make it with negative direction spiral winding copper wire, then under an atmosphere of hydrogen, under 80 ~ 90 DEG C, 0.2 ~ 0.4MPa pressure, makes graphene Half hot melt heat seal is carried out with copper wire with the composite filaments of tin, with the interface bond strength of both enhancings, is increased to obtain graphene Strong copper-based material.
By the test to enhancing copper wire, the tensile strength of copper wire, elongation at break significantly improve, and resistivity reduces bright It is aobvious.The significant advantage that fine Filamentous graphene masterbatch of the invention is modified copper wire is preferably shown.Specific test performance is shown in Table 1.
Embodiment 4
A kind of preparation method and application method for enhancing the graphene masterbatch of copper-based material, it is specific as follows:
(1)The dispersion of graphene and tin:2kg tin is heated to melting in high temperature furnace, and removes impurity, then by 1kg Graphene is added in high temperature furnace, in nitrogen atmosphere, forward direction stirring certain time, then reverse agitating function certain time, it stirs repeatedly After four times, mixing speed is continuously decreased, until stopping, and stands 20min, spinning appts is moved into, is set upwards by spinning appts The nozzle set sprays to form Filamentous injection stream;Injection pressure is 3MPa, repeatedly with filiform injection 4 times, is drawn by spraying Graphene uniform is scattered in metallic tin by silk;
(2)Extrusion forming:By step(1)The dispersion extrusion forming of obtained graphene and metallic tin, setting mould temperature It is 180 ~ 190 DEG C, the compound tin silk of cylindrical graphite alkene that line footpath is 10 ± 1mm is formed by squeezing;
(3)The wire drawing of graphene and tin:By step(3)The obtained compound tin silk of cylindrical graphite alkene is through excessively three wire drawings Machine, big drawing, two drawings, three are drawn, often after a wire drawing machine, are applied using molten rosin, preferably ensure that wire drawing Uniformity, compactness and rounding, the filament line footpath that big drawing, two drawings, three drawings obtain is respectively 1-2mm, 0.5-1mm, 0.05- 0.1mm, to obtain line footpath in the composite filaments of 0.05-0.1mm, i.e., a kind of graphene masterbatch for enhancing copper-based material.
When for enhancing copper-based material, specific application method is:By screw traction, by the graphene of fine filiform Masterbatch is further stretched and is intertwined with copper wire, and it is 2mm to form the screw pitch with spiral wrapping wire, then changes lead, Make it with negative direction spiral winding copper wire, then under an atmosphere of hydrogen, under 80 ~ 90 DEG C, 0.2 ~ 0.4MPa pressure, makes graphene Half hot melt heat seal is carried out with copper wire with the composite filaments of tin, with the interface bond strength of both enhancings, is increased to obtain graphene Strong copper-based material.
By the test to enhancing copper wire, the tensile strength of copper wire, elongation at break significantly improve, and resistivity reduces bright It is aobvious.The significant advantage that fine Filamentous graphene masterbatch of the invention is modified copper wire is preferably shown.Specific test performance is shown in Table 1.
Embodiment 5
A kind of preparation method and application method for enhancing the graphene masterbatch of copper-based material, it is specific as follows:
(1)The dispersion of graphene and tin:4kg tin is heated to melting in high temperature furnace, and removes impurity, then by 1kg Graphene is added in high temperature furnace, in nitrogen atmosphere, forward direction stirring certain time, then reverse agitating function certain time, it stirs repeatedly After four times, mixing speed is continuously decreased, until stopping, and stands 30min, spinning appts is moved into, is set upwards by spinning appts The nozzle set sprays to form Filamentous injection stream;Injection pressure is 1MPa, repeatedly with filiform injection 3 times, is drawn by spraying Graphene uniform is scattered in metallic tin by silk;
(2)Extrusion forming:By step(1)The dispersion extrusion forming of obtained graphene and metallic tin, setting mould temperature It is 180 ~ 190 DEG C, the compound tin silk of cylindrical graphite alkene that line footpath is 10 ± 1mm is formed by squeezing;
(3)The wire drawing of graphene and tin:By step(3)The obtained compound tin silk of cylindrical graphite alkene is through excessively three wire drawings Machine, big drawing, two drawings, three are drawn, often after a wire drawing machine, are applied using molten rosin, preferably ensure that wire drawing Uniformity, compactness and rounding, the filament line footpath that big drawing, two drawings, three drawings obtain is respectively 1-2mm, 0.5-1mm, 0.05- 0.1mm, to obtain line footpath in the composite filaments of 0.05-0.1mm, i.e., a kind of graphene masterbatch for enhancing copper-based material.
When for enhancing copper-based material, specific application method is:By screw traction, by the graphene of fine filiform Masterbatch is further stretched and is intertwined with copper wire, and it is 1mm to form the screw pitch with spiral wrapping wire, then changes lead, Make it with negative direction spiral winding copper wire, then under an atmosphere of hydrogen, under one 80 ~ 90 DEG C, 0.2 ~ 0.4MPa pressure, makes graphite The composite filaments of alkene and tin carry out half hot melt heat seal with copper wire, with the interface bond strength of both enhancings, to obtain graphene The copper-based material of enhancing.
By the test to enhancing copper wire, the tensile strength of copper wire, elongation at break significantly improve, and resistivity reduces bright It is aobvious.The significant advantage that fine Filamentous graphene masterbatch of the invention is modified copper wire is preferably shown.Specific test performance is shown in Table 1.
Table 1:
Case study on implementation Tensile strength(N/mm2 Resistivity (Ω m) Elongation at break(%)
Non-reinforced copper wire 850 1.7×10-8 45
Embodiment 1 1500 1.0×10-8 85
Embodiment 2 1600 0.75×10-8 70
Embodiment 3 1670 1.0×10-8 76
Embodiment 4 1750 0.80×10-8 78
Embodiment 5 1620 0.85×10-8 72

Claims (10)

1. a kind of graphene masterbatch for enhancing copper-based material, it is characterized in that a kind of fine Filamentous graphite containing metallic tin Alkene, line footpath 0.05-0.1mm.
2. a kind of preparation method for enhancing the graphene masterbatch of copper-based material, it is characterised in that first graphene with it is a small amount of Tin fusing is mixed to be stretched through spinneret, and graphene uniform is scattered in metallic tin, then carries out wire drawing step by step, shape by wire drawing machine At the fine Filamentous graphene masterbatch of high graphene concentration, it is as follows:
(1)The dispersion of graphene and tin:Tin is heated to melting in high temperature furnace, and removes impurity, then by graphene press than Example is added in high temperature furnace, in nitrogen atmosphere, forward direction stirring certain time, then reverse agitating function certain time, it stirs four times repeatedly Afterwards, mixing speed is continuously decreased, until stopping, and is stood after a certain period of time, is moved into spinning appts, set upwards by spinning appts The nozzle set sprays to form Filamentous injection stream;Repeatedly with filiform injection 3-4 times, by spraying wire drawing by graphene uniform It is scattered in metallic tin;
(2)Extrusion forming:By step(1)The dispersion extrusion forming of obtained graphene and metallic tin, setting mould temperature is 180 ~190 DEG C, the compound tin silk of cylindrical graphite alkene that line footpath is 10 ± 1mm is formed by squeezing;
(3)The wire drawing of graphene and tin:By step(3)The obtained compound tin silk of cylindrical graphite alkene through excessively three wire drawing machinees, Big drawing, two drawings, three draw, and often after a wire drawing machine, are applied using molten rosin, preferably ensure that the uniform of wire drawing Property, compactness and rounding, to obtain line footpath 0.05-0.1mm composite filaments, i.e., it is a kind of for enhancing copper-based material Graphene masterbatch.
3. a kind of preparation method for enhancing the graphene masterbatch of copper-based material according to claim 2, it is characterised in that: Step(1)The mass ratio of the graphene and tin is 1:2-4.
4. a kind of preparation method for enhancing the graphene masterbatch of copper-based material according to claim 2, it is characterised in that: Step(1)The primary positive and reverse agitating function time is 10~20min.
5. a kind of preparation method for enhancing the graphene masterbatch of copper-based material according to claim 2, it is characterised in that: Step(1)The nozzle diameter of the injection apparatus is 0.5-1mm, and injection pressure is 1-3MPa.
6. a kind of preparation method for enhancing the graphene masterbatch of copper-based material according to claim 2, it is characterised in that: Step(1)The time of repose is 20~30min, preferably eliminates bubble.
7. a kind of preparation method for enhancing the graphene masterbatch of copper-based material according to claim 2, it is characterised in that: Step(3)The filament line footpath that the big drawing, two drawings, three drawings obtain is respectively 1-2mm, 0.5-1mm, 0.05-0.1mm.
8. a kind of application process of the graphene masterbatch described in claim 1 for enhancing copper-based material, it is characterised in that:By The graphene masterbatch of fine filiform is stretched and is intertwined with copper wire by screw traction, forms the spiral winding with a constant pitch Silk, then changes lead, makes it with negative direction spiral winding copper wire, then under an atmosphere of hydrogen, in certain temperature, pressure Under, so that the composite filaments of graphene and tin is carried out partly hot melt heat seal with copper wire, with the interface bond strength of both enhancings, to obtain The copper-based material enhanced to graphene.
9. application process according to claim 8, it is characterised in that:The screw pitch of the spiral wrapping wire is 2~3mm.
10. application process according to claim 8, it is characterised in that:The composite filaments and copper wire of the graphene and tin Heat-seal temperature be 80~90 DEG C;The heat seal pressure of the composite filaments and copper wire of the graphene and tin is 0.2~0.4MPa.
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