CN107578859B - A kind of preparation method of graphene/copper niobium Multicore composite material - Google Patents
A kind of preparation method of graphene/copper niobium Multicore composite material Download PDFInfo
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Abstract
The present invention provides a kind of graphene/copper niobium Multicore composite material preparation method, this method comprises: one, copper scale and niobium powder high-energy ball milling are obtained to refinement powder；Two, refinement powder is fitted into oxygen-free copper pipe and obtains tubulature complex；Three, it will be heat-treated after tubulature complex drawing；Four, the tubulature complex drawing after heat treatment is obtained into monofilamentary composite wire material；Five, 7 core composite wires are made in the once-combined molding of monofilamentary composite wire material；Six, the 7 secondary composite moldings of core composite wire are made 72Core composite wire；Seven, by 72Composite molding is made 7 to core composite wire three times3Core composite wire；Eight, by 73Core composite wire is packed into the niobium pipe for being coated with graphene, and graphene/copper niobium composite wire is made in thermally treated and drawing；Nine, graphene/copper niobium Multicore composite material is made through tubulature, soldering and sealing, hot extrusion and drawing in graphene/copper niobium composite wire, and the graphene uniform in the present invention is distributed in Multicore composite material, improves the intensity and electric conductivity of wire rod.
Description
Technical field
The invention belongs to high temperature superconductor technology fields, and in particular to a kind of preparation of graphene/copper niobium Multicore composite material
Method.
Background technique
Copper alloy with high strength and high conductivity has because of the intensity and excellent conductivity with superelevation in pulse magnetic field conductor field
Be widely applied.The copper alloy with high strength and high conductivity developed both at home and abroad at present mainly has: Cu/Nb-Ag, Cu/Nb-Cu, Cu-
Ag, Cu-Nb and Cu-Ta, wherein Cu-Nb alloy because tensile strength and conductivity matching preferably, preparation process is simple, and cost is relatively low
First choice as pulse magnetic field material.
Graphene is the two dimensional crystal for the only one layer of atomic thickness being made of carbon atom, is presently found most thin, strong
Degree maximum, a kind of strongest novel nano-material of electrical and thermal conductivity performance, 200 times more taller than best steel of breaking strength.
Graphene also has stronger elastic property, and stretch range can reach the 20% of own dimensions；Its resistivity ratio copper or silver are lower,
With excellent electric conductivity.
Currently, Cu/Nb composite material is mainly used for the conductor material of pulse magnet, it is expected to be applied to high current transmission in the future
Conducting wire and ELECTROMAGNETIC WEAPON, this proposes very high requirement to the performance of Cu/Nb composite material.Traditional Cu/Nb composite wire knot
Structure is using copper as matrix, and Nb core filaments are reinforcement, using bundle drawing method technology, is prepared by repeatedly compound and heat treatment technics
At.Can not be compound again using Cu/Nb wire rod prepared by this method, already close to the theoretic limit, intensity is typically maintained in
Between 800MPa~900MPa, and the breakthrough of pulse magnet and ELECTROMAGNETIC WEAPON needs the intensity of wire rod in 1GPa or more, even more
It is high.Currently, graphene is doped to copper-based composite wire, promotion core material size further refines and the interface Cu/Nb increases to mention
Rising the compound wire rod performance of Cu/Nb becomes research hotspot.It is disclosed in the patent of invention that application publication number is CN106448799A
A kind of preparation method of graphene enhancing copper niobium Multicore composite material obtains first by Graphene powder, niobium powder and copper powder mixed processing
The niobium copper composite powder of graphene enhancing, then obtains that intensity is larger, ductility is good and conductive by tubulature, drawing and composite molding
The strong copper niobium Multicore composite material of property；Graphene powder is prepared wire rod by the invention, and graphene divides in wire rod
Cloth is not uniform enough, is easy conglomeration, is not easy to form layer structure, affects the intensity and electric conductivity of copper niobium Multicore composite material
It further increases.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of graphene/copper
The preparation method of niobium Multicore composite material.Graphene molten liquid is coated in niobium pipe outer wall by this method, is formed after solidification uniformly steady
Fixed graphene dispersion layer prepares graphene/copper niobium composite wire in conjunction with techniques such as heat treatment, drawing and hot extrusions, this is multiple
Zygonema material has the characteristics that intensity height and electric conductivity are strong, and this method is flexible and convenient, suitable for preparing various shapes and ruler
Very little Multicore composite material.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of graphene/copper niobium Multicore composite material
Preparation method, which is characterized in that method includes the following steps:
Step 1: copper scale and niobium powder are carried out high-energy ball milling after mixing, refinement powder is obtained；The copper scale and niobium powder
Mass ratio be 1:1；The purity of the niobium powder is 99.99%；
Step 2: refinement powder obtained in step 1 is fitted into the first oxygen-free copper pipe, then by the first oxygen-free copper pipe
Both ends be sealed, obtain tubulature complex；It is described refinement powder charge weight be tubulature composite quality 10%~
60%；
Step 3: tubulature complex obtained in step 2 is carried out the first drawing of multi-pass, then it is heat-treated；Institute
The pass reduction of the first drawing is stated less than 10%；
Step 4: the tubulature complex after being heat-treated in step 3 is carried out the second drawing of multi-pass, it is compound to obtain single
Wire rod；The pass reduction of second drawing is less than 15%；
Step 5: monofilamentary composite wire material obtained in step 4 is carried out once-combined molding, 7 core composite wires are made；
The once-combined molding uses clustered drawing, the detailed process of the clustered drawing are as follows:
Monofilamentary composite wire material is successively carried out scale, shearing, aligning and pickling processes by step 501；
Monofilamentary composite wire material boundling in 7 steps 501 after pickling processes is assembled into the second oxygen-free copper by step 502
Then Guan Zhong is heat-treated, copper pipe complex is obtained；
Copper pipe complex obtained in step 502 is carried out the drawing of multi-pass third by step 503, obtains 7 core recombination lines
Material；The pass reduction of the third drawing is less than 21%；
Step 6: 7 core composite wires obtained in step 5 are carried out secondary composite molding, it is made 72Core composite wire；
The method that the secondary composite molding uses is identical as clustered drawing described in step 5；
Step 7: by obtained in step 672Core composite wire carries out composite molding three times, is made 73Core composite wire；
The method that the composite molding three times uses is identical as clustered drawing described in step 5；
Step 8: by obtained in step 773Graphene/copper niobium composite wire, detailed process is made in core composite wire
Are as follows:
Graphene molten liquid is coated uniformly on the outer wall of niobium pipe by step 801, and graphene-niobium pipe is obtained after solidification；Institute
The graphene thickness stated in graphene-niobium pipe outer wall is less than 1mm；
Step 802, by 73Core composite wire is encased in graphene-niobium pipe, obtains composite pipe body；
Composite pipe body obtained in step 802 is fitted into third oxygen-free copper pipe by step 803, successively carry out heat treatment and
The 4th drawing of multi-pass obtains graphene/copper niobium composite wire；The pass reduction of 4th drawing is less than 15%；
Step 9: graphene/copper niobium Multicore composite is made in graphene obtained in step 8/copper niobium composite wire
Material, detailed process are as follows:
Graphene/copper niobium composite wire is successively truncated, is aligned, pickling and drying process by step 901；
Step 902 takes graphene/copper niobium composite wire after being dried in 19 steps 901 to be packed into the 4th oxygen-free copper
Then Guan Zhong fills the gap in the 4th oxygen-free copper pipe between graphene/copper niobium composite wire with copper plunger, then to filled
The both ends of 4th oxygen-free copper pipe carry out vacuum electron beam soldering and sealing；
The 4th oxygen-free copper pipe after vacuum electron beam soldering and sealing is successively carried out hot extrusion and the drawing of multi-pass the 5th by step 903
It pulls out, obtains graphene/copper niobium Multicore composite material；The pass reduction of 5th drawing is less than 12%.
A kind of above-mentioned graphene/copper niobium Multicore composite material preparation method, which is characterized in that height described in step 1
The time of energy ball milling is 20h~40h.
Above-mentioned a kind of graphene/copper niobium Multicore composite material preparation method, which is characterized in that Step 3: step 502
Temperature with heat treatment described in step 803 is 800 DEG C~1000 DEG C, and the time is 60h.
Above-mentioned a kind of graphene/copper niobium Multicore composite material preparation method, which is characterized in that single described in step 4
7 core composite wires described in core composite wire, step 5,7 described in step 627 described in core composite wire, step 73Core is multiple
Graphene described in zygonema material and step 8/copper niobium composite wire cross-sectional shape is regular hexagon；The regular hexagon
Opposite side distance be 2.5mm~2.7mm.
Above-mentioned a kind of graphene/copper niobium Multicore composite material preparation method, which is characterized in that described in step 903
The temperature of hot extrusion is 600 DEG C~700 DEG C, and soaking time is 2h~6h, and extrusion ratio is 10~42.
The preparation process of graphene molten liquid in step 801 are as follows: first using crystalline flake graphite as raw material, using Hummers
Method prepares graphene oxide, then uses high-temperature reducing process, and graphene oxide is placed in in closed reducing atmosphere the system that heats
Standby graphene, then melted under conditions of graphene is placed in 900 DEG C~1000 DEG C and obtain graphene molten liquid.
Compared with the prior art, the present invention has the following advantages:
1, graphene molten liquid is coated in niobium pipe outer wall by the present invention, increases the surface area of graphene, due to graphene
Layer structure with flowing, slip property is preferable, and niobium pipe can be dispersed in subsequent drawing and hot extrusion process
Outer wall, form stable graphene layer, be conducive to play the features such as graphene intensity is high, ductility is good, electric conductivity is strong.
2, the graphene in the present invention and copper niobium composite wire by being heat-treated, drawing and hot extrusion prepare graphene/copper
Niobium composite wire, which has copper niobium composite wire-niobium pipe-graphene-copper pipe multilayer sandwiched structure, so that copper niobium
Between contact area increase, therefore the intensity of composite wire and electric conductivity improve.
3, the present invention carries out ball milling to niobium powder and copper scale mixed-powder using high-energy ball milling, keeps the granularity of powder further thin
Change, powder mixing is more uniform, and the metallurgical bonding between powder faster, refines powder after heat treatment, the expansion between copper niobium
Scattered degree is bigger, and the binding performance at copper niobium interface is improved.
4, the copper-clad set of different size is encased in after the graphene in the present invention/copper niobium composite wire processing with copper plunger
In, graphene/copper niobium Multicore composite material of a variety of shapes and sizes can be prepared through vacuum electron beam soldering and sealing, hot extrusion, drawing,
Flexible design, it is easy to adjust.
Below by embodiment, invention is further described in detail.
Specific embodiment
Embodiment 1
The present embodiment the following steps are included:
Step 1: copper scale and niobium powder high-energy ball milling 20h after mixing are obtained refinement powder；The copper scale and niobium powder
Mass ratio be 1:1；The purity of the niobium powder is 99.99%；
Step 2: refinement powder obtained in step 1 is packed into, outer diameter is 10.5mm, wall thickness 2.0mm, length are
In the first oxygen-free copper pipe of 400mm, then the both ends of the first oxygen-free copper pipe are sealed, obtain tubulature complex；It is described thin
The charge weight for changing powder is the 10% of tubulature composite quality；
Step 3: tubulature complex obtained in step 2 is carried out the first drawing of multi-pass, the drawing die used is successively
Are as follows: Φ 10.3mm, Φ 9.89mm, Φ 9.43mm, Φ 9.2mm, Φ 8.86mm and Φ 8.66mm, wherein Φ indicates round drawing die
Diameter, then in 800 DEG C of heat treatment 60h；The pass reduction of first drawing of multi-pass is 4%~9%；
Step 4: the tubulature complex after being heat-treated in step 3 is carried out the second drawing of multi-pass, the drawing die used
Successively are as follows: Φ 8.5mm, Φ 8.16mm, Φ 7.97mm, Φ 7.66mm, Φ 7.15mm, Φ 7.0mm, Φ 6.6mm, Φ 6.3mm, Φ
6.0mm, Φ 5.57mm, Φ 5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 450 DEG C/2h), Φ
4.9mm、Φ4.7mm、Φ4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ
3.26mm, Φ 3.13mm, Φ 3.0mm, Φ 2.80mm, Φ 2.76mm and S2.70mm, wherein Φ indicates round drawing mode diameter, S
It indicates six side's mould opposite side distances, finally obtains the monofilamentary composite wire material that cross section is regular hexagon, the opposite side distance of the orthohexagonal is
2.70mm；
Step 5: monofilamentary composite wire material obtained in step 4 is carried out once-combined molding, 7 core composite wires are made；
The once-combined molding uses clustered drawing, the detailed process of the clustered drawing are as follows:
Monofilamentary composite wire material is successively carried out scale, shearing, aligning and pickling processes by step 501；
Monofilamentary composite wire material boundling in 7 steps 501 after pickling processes is assembled into outer diameter and is by step 502
11.5mm, wall thickness 2.0mm, in the second oxygen-free copper pipe that length is 400mm, then the isothermal holding 60h at 800 DEG C, obtains
Copper pipe complex；
Step 503, by copper pipe complex obtained in step 502 carry out the drawing of multi-pass third, the drawing die used according to
It is secondary are as follows: Φ 11.4mm, Φ 10.87mm, Φ 10.3mm, Φ 9.2mm, Φ 8.5mm, Φ 8.16mm, Φ 7.97mm, Φ 7.74mm,
Φ 7.15mm, Φ 7.0mm, Φ 6.6mm, Φ 6.3mm, Φ 6.0mm, Φ 5.57mm, Φ 5.4mm, Φ 5.1mm, Φ 4.9mm (
Once made annealing treatment after this passage drawing: 450 DEG C/2h), Φ 4.7mm, Φ 4.5mm, Φ 4.3mm, Φ 4.13mm, Φ
4.0mm, Φ 3.81mm, Φ 3.68mm, Φ 3.4mm, Φ 3.26mm, Φ 3.13mm, Φ 3.0mm, Φ 2.80mm, Φ 2.76mm and
S2.70mm, wherein Φ indicates that round drawing mode diameter, S indicate six side's mould opposite side distances, and finally obtaining cross section is regular hexagon
7 core composite wires, the opposite side distance of the regular hexagon are 2.70mm；
Step 6: 7 core composite wires obtained in step 5 are carried out secondary composite molding, it is made 72Core composite wire；
The method that the secondary composite molding uses is identical as the clustered drawing described in step 5, the clustered drawing it is specific
Process are as follows:
7 core composite wires are successively carried out scale, shearing, aligning and pickling processes by step 601；
7 core composite wire boundlings in 7 steps 601 after pickling processes are assembled into outer diameter and are by step 602
12.5mm, wall thickness 2.5mm, in the second oxygen-free copper pipe that length is 400mm, then the isothermal holding 60h at 800 DEG C, obtains
Copper pipe complex；
Step 603, by copper pipe complex obtained in step 602 carry out the drawing of multi-pass third, the drawing die used according to
It is secondary are as follows: Φ 12.16mm, Φ 11.97mm, Φ 11.64mm, Φ 11.4mm, Φ 10.3mm, Φ 9.2mm, Φ 8.5mm, Φ
8.16mm、Φ7.97mm、Φ7.74mm、Φ7.15mm、Φ7.0mm、Φ6.6mm、Φ6.3mm、Φ6.0mm、Φ5.57mm、Φ
5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 450 DEG C/2h), Φ 4.9mm, Φ 4.7mm, Φ
4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ3.26mm、Φ3.13mm、Φ
3.0mm, Φ 2.80mm, Φ 2.76mm and S2.70mm, wherein Φ indicates that round drawing mode diameter, S indicate six side's mould opposite side distances,
Finally obtain 7 that cross section is regular hexagon2Core composite wire, the opposite side distance of the regular hexagon are 2.70mm；
Step 7: by obtained in step 672Core composite wire carries out composite molding three times, is made 73Core composite wire；
The method that the composite molding three times uses is identical as clustered drawing described in step 5, the clustered drawing it is specific
Process are as follows:
Step 701, by 72Core composite wire successively carries out scale, shearing, aligning and pickling processes；
Step 702, by 7 steps 701 after pickling processes 72Core composite wire boundling is assembled into outer diameter and is
12.5mm, wall thickness 2.5mm, in the second oxygen-free copper pipe that length is 400mm, then the isothermal holding 60h at 800 DEG C, obtains
Copper pipe complex；
Step 703, by copper pipe complex obtained in step 702 carry out the drawing of multi-pass third, the drawing die used according to
It is secondary are as follows: Φ 12.16mm, Φ 11.97mm, Φ 11.64mm, Φ 11.4mm, Φ 10.3mm, Φ 9.2mm, Φ 8.5mm, Φ
8.16mm、Φ7.97mm、Φ7.74mm、Φ7.15mm、Φ7.0mm、Φ6.6mm、Φ6.3mm、Φ6.0mm、Φ5.57mm、Φ
5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 450 DEG C/2h), Φ 4.9mm, Φ 4.7mm, Φ
4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ3.26mm、Φ3.13mm、Φ
3.0mm, Φ 2.80mm, Φ 2.76mm and S2.70mm, wherein Φ indicates that round drawing mode diameter, S indicate six side's mould opposite side distances,
Finally obtain 7 that cross section is regular hexagon3Core composite wire, the opposite side distance of the regular hexagon are 2.70mm；
Step 8: by obtained in step 773Graphene/copper niobium composite wire, detailed process is made in core composite wire
Are as follows:
Graphene molten liquid is coated uniformly on the outer wall that outer diameter is 11.5mm, wall thickness is 1.67mm niobium pipe by step 801
On, graphene-niobium pipe is obtained after solidification；Graphene in the graphene-niobium pipe outer wall is with a thickness of 0.1mm；
Step 802, by 73Core composite wire is encased in graphene-niobium pipe, obtains composite pipe body；
Step 803, by composite pipe body obtained in step 802 loading outer diameter be 13.5mm, wall thickness 1.0mm, length are
In the third oxygen-free copper pipe of 400mm, in 800 DEG C of processing 60h, the 4th drawing of multi-pass is then carried out, the drawing die used is successively
Are as follows: Φ 8.16mm, Φ 7.97mm, Φ 7.74mm, Φ 7.15mm, Φ 7.0mm, Φ 6.6mm, Φ 6.3mm, Φ 6.0mm, Φ
5.57mm, Φ 5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 450 DEG C/2h), Φ 4.9mm, Φ
4.7mm、Φ4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ3.26mm、Φ
3.13mm, Φ 3.0mm, Φ 2.80mm, Φ 2.76mm and S2.70mm, wherein Φ indicates that round drawing mode diameter, S indicate six sides
Mould opposite side distance, finally obtains graphene/copper niobium core composite wire that cross section is regular hexagon, and the opposite side distance of the regular hexagon is
2.70mm；
Step 9: graphene/copper niobium Multicore composite is made in graphene obtained in step 8/copper niobium composite wire
Material, detailed process are as follows:
Graphene/copper niobium composite wire is successively truncated, is aligned, pickling and drying process by step 901；
Step 902, take in 19 steps 901 be dried after graphene/copper niobium composite wire be packed into outer diameter be
65.0mm, wall thickness 17.8mm, in the 4th oxygen-free copper pipe that length is 200mm, the 4th oxygen-free copper pipe then is filled with copper plunger
Gap between middle graphene/copper niobium composite wire, then vacuum electron beam is carried out to the both ends of filled 4th oxygen-free copper pipe
Soldering and sealing；
Step 903, by the 4th oxygen-free copper pipe after vacuum electron beam soldering and sealing in 600 DEG C of hot extrusion 2h, extrusion ratio 10, so
Afterwards carry out the 5th drawing of multi-pass, the drawing die used is successively are as follows: Φ 8.16mm, Φ 7.97mm, Φ 7.74mm, Φ 7.15mm,
Φ 7.0mm, Φ 6.6mm and Φ 6.3mm, wherein Φ indicates round drawing mode diameter, obtains graphene/copper niobium Multicore composite
Material.
Graphene manufactured in the present embodiment/copper niobium Multicore composite material core number is 19 × 73Core, through detecting, the wire rod
Intensity is 664MPa, and the intensity compared to the same size wire rod of conventional method preparation improves 20%；The wire rod conductance is 67%
IACS, the resistivity compared to the same size wire rod of conventional method preparation reduce 9%.
Embodiment 2
The present embodiment the following steps are included:
Step 1: copper scale and niobium powder high-energy ball milling 25h after mixing are obtained refinement powder；The copper scale and niobium powder
Mass ratio be 1:1；The purity of the niobium powder is 99.99%；
Step 2: refinement powder obtained in step 1 is packed into, outer diameter is 10.5mm, wall thickness 2.0mm, length are
In the first oxygen-free copper pipe of 400mm, then the both ends of the first oxygen-free copper pipe are sealed, obtain tubulature complex；It is described thin
The charge weight for changing powder is the 20% of tubulature composite quality；
Step 3: tubulature complex obtained in step 2 is carried out the first drawing of multi-pass, the drawing die used is successively
Are as follows: Φ 10.3mm, Φ 9.89mm, Φ 9.43mm, Φ 9.2mm, Φ 8.86mm and Φ 8.66mm, wherein Φ indicates round drawing die
Diameter, then in 850 DEG C of heat treatment 60h；
Step 4: the tubulature complex after being heat-treated in step 3 is carried out the second drawing of multi-pass, the drawing die used
Successively are as follows: Φ 8.5mm, Φ 8.16mm, Φ 7.97mm, Φ 7.66mm, Φ 7.15mm, Φ 7.0mm, Φ 6.6mm, Φ 6.3mm, Φ
6.0mm, Φ 5.57mm, Φ 5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 500 DEG C/2.5h), Φ
4.9mm、Φ4.7mm、Φ4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ
3.26mm, Φ 3.13mm, Φ 3.0mm, Φ 2.80mm, Φ 2.76mm and S2.60mm, wherein Φ indicates round drawing mode diameter, S
It indicates six side's mould opposite side distances, finally obtains the monofilamentary composite wire material that cross section is regular hexagon, the opposite side distance of the orthohexagonal is
2.60mm；
Step 5: carrying out once-combined molding to monofilamentary composite wire material obtained in step 4,7 core composite wires are made；
The once-combined molding uses clustered drawing, the detailed process of the clustered drawing are as follows:
Monofilamentary composite wire material is successively carried out scale, shearing, aligning and pickling processes by step 501；
Monofilamentary composite wire material boundling in 7 steps 501 after pickling processes is assembled into outer diameter and is by step 502
11.5mm, wall thickness 2.0mm, in the second oxygen-free copper pipe that length is 400mm, then the isothermal holding 60h at 850 DEG C, obtains
Copper pipe complex；
Step 503, by copper pipe complex obtained in step 502 carry out the drawing of multi-pass third, the drawing die used according to
It is secondary are as follows: Φ 11.4mm, Φ 10.87mm, Φ 10.3mm, Φ 9.2mm, Φ 8.5mm, Φ 8.16mm, Φ 7.97mm, Φ 7.74mm,
Φ 7.15mm, Φ 7.0mm, Φ 6.6mm, Φ 6.3mm, Φ 6.0mm, Φ 5.57mm, Φ 5.4mm, Φ 5.1mm, Φ 4.9mm (
Once made annealing treatment after this passage drawing: 500 DEG C/2.5h), Φ 4.7mm, Φ 4.5mm, Φ 4.3mm, Φ 4.13mm, Φ
4.0mm, Φ 3.81mm, Φ 3.68mm, Φ 3.4mm, Φ 3.26mm, Φ 3.13mm, Φ 3.0mm, Φ 2.80mm, Φ 2.76mm and
S2.60mm, wherein Φ indicates that round drawing mode diameter, S indicate six side's mould opposite side distances, and finally obtaining cross section is regular hexagon
7 core composite wires, the opposite side distance of the regular hexagon are 2.60mm；
Step 6: 7 core composite wires obtained in step 5 are carried out secondary composite molding, it is made 72Core composite wire；
The method that the secondary composite molding uses is identical as the clustered drawing described in step 5, the clustered drawing it is specific
Process are as follows:
7 core composite wires are successively carried out scale, shearing, aligning and pickling processes by step 601；
7 core composite wire boundlings in 7 steps 601 after pickling processes are assembled into outer diameter and are by step 602
12.5mm, wall thickness 2.5mm, in the second oxygen-free copper pipe that length is 400mm, then the isothermal holding 60h at 850 DEG C, obtains
Copper pipe complex；
Step 603, by copper pipe complex obtained in step 602 carry out the drawing of multi-pass third, the drawing die used according to
It is secondary are as follows: Φ 12.16mm, Φ 11.97mm, Φ 11.64mm, Φ 11.4mm, Φ 10.3mm, Φ 9.2mm, Φ 8.5mm, Φ
8.16mm、Φ7.97mm、Φ7.74mm、Φ7.15mm、Φ7.0mm、Φ6.6mm、Φ6.3mm、Φ6.0mm、Φ5.57mm、Φ
5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 500 DEG C/2.5h), Φ 4.9mm, Φ 4.7mm, Φ
4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ3.26mm、Φ3.13mm、Φ
3.0mm, Φ 2.80mm, Φ 2.76mm and S2.60mm, wherein Φ indicates that round drawing mode diameter, S indicate six side's mould opposite side distances,
Finally obtain 7 that cross section is regular hexagon2Core composite wire, the opposite side distance of the regular hexagon are 2.60mm；
Step 7: by obtained in step 672Core composite wire carries out composite molding three times, is made 73Core composite wire；
The method that the composite molding three times uses is identical as clustered drawing described in step 5, the clustered drawing it is specific
Process are as follows:
Step 701, by 72Core composite wire successively carries out scale, shearing, aligning and pickling processes；
Step 702, by 7 steps 701 after pickling processes 72Core composite wire boundling is assembled into outer diameter and is
12.5mm, wall thickness 2.5mm, in the second oxygen-free copper pipe that length is 400mm, then the isothermal holding 60h at 850 DEG C, obtains
Copper pipe complex；
Step 703, by copper pipe complex obtained in step 702 carry out the drawing of multi-pass third, the drawing die used according to
It is secondary are as follows: Φ 12.16mm, Φ 11.97mm, Φ 11.64mm, Φ 11.4mm, Φ 10.3mm, Φ 9.2mm, Φ 8.5mm, Φ
8.16mm、Φ7.97mm、Φ7.74mm、Φ7.15mm、Φ7.0mm、Φ6.6mm、Φ6.3mm、Φ6.0mm、Φ5.57mm、Φ
5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 500 DEG C/2.5h), Φ 4.9mm, Φ 4.7mm, Φ
4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ3.26mm、Φ3.13mm、Φ
3.0mm, Φ 2.80mm, Φ 2.76mm, Φ 2.68mm and S2.60mm, wherein Φ indicates that round drawing mode diameter, S indicate six sides
Mould opposite side distance finally obtains 7 that cross section is regular hexagon3Core composite wire, the opposite side distance of the regular hexagon are 2.60mm；
Step 8: by obtained in step 773Graphene/copper niobium composite wire, detailed process is made in core composite wire
Are as follows:
Graphene molten liquid is coated uniformly on the outer wall that outer diameter is 11.5mm, wall thickness is 1.67mm niobium pipe by step 801
On, graphene-niobium pipe is obtained after solidification；Graphene in the graphene-niobium pipe outer wall is with a thickness of 0.2mm；
Step 802, by 73Core composite wire is encased in graphene-niobium pipe, obtains composite pipe body；
Step 803, by composite pipe body obtained in step 802 loading outer diameter be 13.5mm, wall thickness 1.0mm, length are
In the third oxygen-free copper pipe of 400mm, in 850 DEG C of processing 60h, the 4th drawing of multi-pass is then carried out, the drawing die used is successively
Are as follows: Φ 8.16mm, Φ 7.97mm, Φ 7.74mm, Φ 7.15mm, Φ 7.0mm, Φ 6.6mm, Φ 6.3mm, Φ 6.0mm, Φ
5.57mm, Φ 5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 500 DEG C/2.5h), Φ 4.9mm, Φ
4.7mm、Φ4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ3.26mm、Φ
3.13mm, Φ 3.0mm, Φ 2.80mm, Φ 2.76mm and S2.60mm, wherein Φ indicates that round drawing mode diameter, S indicate six sides
Mould opposite side distance, finally obtains graphene/copper niobium core composite wire that cross section is regular hexagon, and the opposite side distance of the regular hexagon is
2.60mm；
Step 9: graphene/copper niobium Multicore composite is made in graphene obtained in step 8/copper niobium composite wire
Material, detailed process are as follows:
Graphene/copper niobium composite wire is successively truncated, is aligned, pickling and drying process by step 901；
Step 902, take in 19 steps 901 be dried after graphene/copper niobium composite wire be packed into outer diameter be
65.0mm, wall thickness 17.8mm, in the 4th oxygen-free copper pipe that length is 200mm, the 4th oxygen-free copper pipe then is filled with copper plunger
Gap between middle graphene/copper niobium composite wire, then vacuum electron beam is carried out to the both ends of filled 4th oxygen-free copper pipe
Soldering and sealing；
Step 903, by the 4th oxygen-free copper pipe after vacuum electron beam soldering and sealing in 650 DEG C of hot extrusion 3h, extrusion ratio 20, so
Afterwards carry out the 5th drawing of multi-pass, the drawing die used is successively are as follows: Φ 8.16mm, Φ 7.97mm, Φ 7.74mm, Φ 7.15mm,
Φ 7.0mm, Φ 6.6mm and Φ 6.3mm, wherein Φ indicates round drawing mode diameter, obtains graphene/copper niobium Multicore composite
Material.
Graphene manufactured in the present embodiment/copper niobium Multicore composite material core number is 19 × 73Core, through detecting, the wire rod
Intensity is 835MPa, and the intensity compared to the same size wire rod of conventional method preparation improves 25%；The wire rod conductance is 85%
IACS, the resistivity compared to the same size wire rod of conventional method preparation reduce 6%.
Embodiment 3
The present embodiment the following steps are included:
Step 1: copper scale and niobium powder high-energy ball milling 30h after mixing are obtained refinement powder；The copper scale and niobium powder
Mass ratio be 1:1；The purity of the niobium powder is 99.99%；
Step 2: refinement powder obtained in step 1 is packed into, outer diameter is 10.5mm, wall thickness 2.0mm, length are
In the first oxygen-free copper pipe of 400mm, then the both ends of the first oxygen-free copper pipe are sealed, obtain tubulature complex；It is described thin
The charge weight for changing powder is the 30% of tubulature composite quality；
Step 3: tubulature complex obtained in step 2 is carried out the first drawing of multi-pass, the drawing die used is successively
Are as follows: Φ 10.3mm, Φ 9.89mm, Φ 9.43mm, Φ 9.2mm, Φ 8.86mm and Φ 8.66mm, wherein Φ indicates round drawing die
Diameter, then in 900 DEG C of heat treatment 60h；
Step 4: the tubulature complex after being heat-treated in step 3 is carried out the second drawing of multi-pass, the drawing die used
Successively are as follows: Φ 8.5mm, Φ 8.16mm, Φ 7.97mm, Φ 7.66mm, Φ 7.15mm, Φ 7.0mm, Φ 6.6mm, Φ 6.3mm, Φ
6.0mm, Φ 5.57mm, Φ 5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 550 DEG C/2.5h), Φ
4.9mm、Φ4.7mm、Φ4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ
3.26mm, Φ 3.13mm, Φ 3.0mm, Φ 2.80mm, Φ 2.76mm and S2.65mm, wherein Φ indicates round drawing mode diameter, S
It indicates six side's mould opposite side distances, finally obtains the monofilamentary composite wire material that cross section is regular hexagon, the opposite side distance of the orthohexagonal is
2.65mm；
Step 5: monofilamentary composite wire material obtained in step 4 is carried out once-combined molding, 7 core composite wires are made；
The once-combined molding uses clustered drawing, the detailed process of the clustered drawing are as follows:
Monofilamentary composite wire material is successively carried out scale, shearing, aligning and pickling processes by step 501；
Monofilamentary composite wire material boundling in 7 steps 501 after pickling processes is assembled into outer diameter and is by step 502
11.5mm, wall thickness 2.0mm, in the second oxygen-free copper pipe that length is 400mm, then the isothermal holding 60h at 900 DEG C, obtains
Copper pipe complex；
Copper pipe complex obtained in step 502 is carried out the drawing of multi-pass third by step 503, step 503, is used
Drawing die is successively are as follows: Φ 11.4mm, Φ 10.87mm, Φ 10.3mm, Φ 9.2mm, Φ 8.5mm, Φ 8.16mm, Φ 7.97mm, Φ
7.74mm、Φ7.15mm、Φ7.0mm、Φ6.6mm、Φ6.3mm、Φ6.0mm、Φ5.57mm、Φ5.4mm、Φ5.1mm、Φ
4.9mm (once being made annealing treatment after this passage drawing: 550 DEG C/2.5h), Φ 4.7mm, Φ 4.5mm, Φ 4.3mm, Φ
4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ3.26mm、Φ3.13mm、Φ3.0mm、Φ2.80mm、
Φ 2.76mm and S2.65mm, wherein Φ indicates that round drawing mode diameter, S indicate six side's mould opposite side distances, and finally obtaining cross section is
7 core composite wires of regular hexagon, the opposite side distance of the regular hexagon are 2.65mm；
Step 6: 7 core composite wires obtained in step 5 are carried out secondary composite molding, it is made 72Core composite wire；
The method that the secondary composite molding uses is identical as the clustered drawing described in step 5, the clustered drawing it is specific
Process are as follows:
7 core composite wires are successively carried out scale, shearing, aligning and pickling processes by step 601；
7 core composite wire boundlings in 7 steps 601 after pickling processes are assembled into outer diameter and are by step 602
12.5mm, wall thickness 2.5mm, in the second oxygen-free copper pipe that length is 400mm, then the isothermal holding 60h at 900 DEG C, obtains
Copper pipe complex；
Step 603, by copper pipe complex obtained in step 602 carry out the drawing of multi-pass third, the drawing die used according to
It is secondary are as follows: Φ 12.16mm, Φ 11.97mm, Φ 11.64mm, Φ 11.4mm, Φ 10.3mm, Φ 9.2mm, Φ 8.5mm, Φ
8.16mm、Φ7.97mm、Φ7.74mm、Φ7.15mm、Φ7.0mm、Φ6.6mm、Φ6.3mm、Φ6.0mm、Φ5.57mm、Φ
5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 550 DEG C/2.5h), Φ 4.9mm, Φ 4.7mm, Φ
4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ3.26mm、Φ3.13mm、Φ
3.0mm, Φ 2.80mm, Φ 2.76mm and S2.65mm, wherein Φ indicates that round drawing mode diameter, S indicate six side's mould opposite side distances,
Finally obtain 7 that cross section is regular hexagon2Core composite wire, the opposite side distance of the regular hexagon are 2.65mm；
Step 7: by obtained in step 672Core composite wire carries out composite molding three times, is made 73Core composite wire；
The method that the composite molding three times uses is identical as clustered drawing described in step 5, the clustered drawing it is specific
Process are as follows:
Step 701, by 72Core composite wire successively carries out scale, shearing, aligning and pickling processes；
Step 702, by 7 steps 701 after pickling processes 72Core composite wire boundling is assembled into outer diameter and is
12.5mm, wall thickness 2.5mm, in the second oxygen-free copper pipe that length is 400mm, then the isothermal holding 60h at 900 DEG C, obtains
Copper pipe complex；
Step 703, by copper pipe complex obtained in step 702 carry out the drawing of multi-pass third, the drawing die used according to
It is secondary are as follows: Φ 12.16mm, Φ 11.97mm, Φ 11.64mm, Φ 11.4mm, Φ 10.3mm, Φ 9.2mm, Φ 8.5mm, Φ
8.16mm、Φ7.97mm、Φ7.74mm、Φ7.15mm、Φ7.0mm、Φ6.6mm、Φ6.3mm、Φ6.0mm、Φ5.57mm、Φ
5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 550 DEG C/2.5h), Φ 4.9mm, Φ 4.7mm, Φ
4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ3.26mm、Φ3.13mm、Φ
3.0mm, Φ 2.80mm, Φ 2.76mm, Φ 2.68mm and S2.65mm, wherein Φ indicates that round drawing mode diameter, S indicate six sides
Mould opposite side distance finally obtains 7 that cross section is regular hexagon3Core composite wire, the opposite side distance of the regular hexagon are 2.65mm；
Step 8: by obtained in step 773Graphene/copper niobium composite wire, detailed process is made in core composite wire
Are as follows:
Graphene molten liquid is coated uniformly on the outer wall that outer diameter is 11.5mm, wall thickness is 1.67mm niobium pipe by step 801
On, graphene-niobium pipe is obtained after solidification；Graphene in the graphene-niobium pipe outer wall is with a thickness of 0.3mm；
Step 802, by 73Core composite wire is encased in graphene-niobium pipe, obtains composite pipe body；
Step 803, by composite pipe body obtained in step 802 loading outer diameter be 13.5mm, wall thickness 1.0mm, length are
In the third oxygen-free copper pipe of 400mm, in 900 DEG C of processing 60h, the 4th drawing of multi-pass is then carried out, the drawing die used is successively
Are as follows: Φ 8.16mm, Φ 7.97mm, Φ 7.74mm, Φ 7.15mm, Φ 7.0mm, Φ 6.6mm, Φ 6.3mm, Φ 6.0mm, Φ
5.57mm, Φ 5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 550 DEG C/2.5h), Φ 4.9mm, Φ
4.7mm、Φ4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ3.26mm、Φ
3.13mm, Φ 3.0mm, Φ 2.80mm, Φ 2.76mm and S2.65mm, wherein Φ indicates that round drawing mode diameter, S indicate six sides
Mould opposite side distance, finally obtains graphene/copper niobium core composite wire that cross section is regular hexagon, and the opposite side distance of the regular hexagon is
2.65mm；
Step 9: graphene/copper niobium Multicore composite is made in graphene obtained in step 8/copper niobium composite wire
Material, detailed process are as follows:
Graphene/copper niobium composite wire is successively truncated, is aligned, pickling and drying process by step 901；
Step 902, take in 19 steps 901 be dried after graphene/copper niobium composite wire be packed into outer diameter be
65.0mm, wall thickness 17.8mm, in the 4th oxygen-free copper pipe that length is 200mm, the 4th oxygen-free copper pipe then is filled with copper plunger
Gap between middle graphene/copper niobium composite wire, then vacuum electron beam is carried out to the both ends of filled 4th oxygen-free copper pipe
Soldering and sealing；
Step 903, by the 4th oxygen-free copper pipe after vacuum electron beam soldering and sealing in 700 DEG C of hot extrusion 4h, extrusion ratio 30, so
Afterwards carry out the 5th drawing of multi-pass, the drawing die used is successively are as follows: Φ 8.16mm, Φ 7.97mm, Φ 7.74mm, Φ 7.15mm,
Φ 7.0mm, Φ 6.6mm and Φ 6.3mm, wherein Φ indicates round drawing mode diameter, obtains graphene/copper niobium Multicore composite
Material.
Graphene manufactured in the present embodiment/copper niobium Multicore composite material core number is 19 × 73Core, through detecting, the wire rod
Intensity is 807MPa, and the intensity compared to the same size wire rod of conventional method preparation improves 18%；The wire rod conductance is 78%
IACS, the resistivity compared to the same size wire rod of conventional method preparation reduce 7%
Embodiment 4
The present embodiment the following steps are included:
Step 1: copper scale and niobium powder high-energy ball milling 35h after mixing are obtained refinement powder；The copper scale and niobium powder
Mass ratio be 1:1；The purity of the niobium powder is 99.99%；
Step 2: refinement powder obtained in step 1 is packed into, outer diameter is 10.5mm, wall thickness 2.0mm, length are
In the first oxygen-free copper pipe of 400mm, then the both ends of the first oxygen-free copper pipe are sealed, obtain tubulature complex；It is described thin
The charge weight for changing powder is the 45% of tubulature composite quality；
Step 3: tubulature complex obtained in step 2 is carried out the first drawing of multi-pass, the drawing die used is successively
Are as follows: Φ 10.3mm, Φ 9.89mm, Φ 9.43mm, Φ 9.2mm, Φ 8.86mm and Φ 8.66mm, wherein Φ indicates round drawing die
Diameter, then in 950 DEG C of heat treatment 60h；
Step 4: the tubulature complex after being heat-treated in step 3 is carried out the second drawing of multi-pass, the drawing die used
Successively are as follows: Φ 8.5mm, Φ 8.16mm, Φ 7.97mm, Φ 7.66mm, Φ 7.15mm, Φ 7.0mm, Φ 6.6mm, Φ 6.3mm, Φ
6.0mm, Φ 5.57mm, Φ 5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 450 DEG C/2h), Φ
4.9mm、Φ4.7mm、Φ4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ
3.26mm, Φ 3.13mm, Φ 3.0mm, Φ 2.80mm, Φ 2.76mm, Φ 2.68mm and S2.55mm, wherein Φ indicates round drawing
Draft diameter, S indicate six side's mould opposite side distances, finally obtain the monofilamentary composite wire material that cross section is regular hexagon, the orthohexagonal
Opposite side distance be 2.55mm；
Step 5: monofilamentary composite wire material obtained in step 4 is carried out once-combined molding, 7 core composite wires are made；
The once-combined molding uses clustered drawing, the detailed process of the clustered drawing are as follows:
Monofilamentary composite wire material is successively carried out scale, shearing, aligning and pickling processes by step 501；
Monofilamentary composite wire material boundling in 7 steps 501 after pickling processes is assembled into outer diameter and is by step 502
11.5mm, wall thickness 2.0mm, in the second oxygen-free copper pipe that length is 400mm, then the isothermal holding 60h at 950 DEG C, obtains
Copper pipe complex；
Step 503, by copper pipe complex obtained in step 502 carry out the drawing of multi-pass third, the drawing die used according to
It is secondary are as follows: Φ 11.4mm, Φ 10.87mm, Φ 10.3mm, Φ 9.2mm, Φ 8.5mm, Φ 8.16mm, Φ 7.97mm, Φ 7.74mm,
Φ 7.15mm, Φ 7.0mm, Φ 6.6mm, Φ 6.3mm, Φ 6.0mm, Φ 5.57mm, Φ 5.4mm, Φ 5.1mm, Φ 4.9mm (
Once made annealing treatment after this passage drawing: 450 DEG C/2h), Φ 4.7mm, Φ 4.5mm, Φ 4.3mm, Φ 4.13mm, Φ
4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ3.26mm、Φ3.13mm、Φ3.0mm、Φ2.80mm、Φ2.76mm、
Φ 2.68mm and S2.55mm, wherein Φ indicates that round drawing mode diameter, S indicate six side's mould opposite side distances, and finally obtaining cross section is
7 core composite wires of regular hexagon, the opposite side distance of the regular hexagon are 2.55mm；
Step 6: 7 core composite wires obtained in step 5 are carried out secondary composite molding, it is made 72Core composite wire；
The method that the secondary composite molding uses is identical as the clustered drawing described in step 5, the clustered drawing it is specific
Process are as follows:
7 core composite wires are successively carried out scale, shearing, aligning and pickling processes by step 601；
7 core composite wire boundlings in 7 steps 601 after pickling processes are assembled into outer diameter and are by step 602
12.5mm, wall thickness 2.5mm, in the second oxygen-free copper pipe that length is 400mm, then the isothermal holding 60h at 950 DEG C, obtains
Copper pipe complex；
Step 603, by copper pipe complex obtained in step 602 carry out the drawing of multi-pass third, the drawing die used according to
It is secondary are as follows: Φ 12.16mm, Φ 11.97mm, Φ 11.64mm, Φ 11.4mm, Φ 10.3mm, Φ 9.2mm, Φ 8.5mm, Φ
8.16mm、Φ7.97mm、Φ7.74mm、Φ7.15mm、Φ7.0mm、Φ6.6mm、Φ6.3mm、Φ6.0mm、Φ5.57mm、Φ
5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 450 DEG C/2h), Φ 4.9mm, Φ 4.7mm, Φ
4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ3.26mm、Φ3.13mm、Φ
3.0mm, Φ 2.80mm, Φ 2.76mm, Φ 2.68mm and S2.55mm, wherein Φ indicates that round drawing mode diameter, S indicate six sides
Mould opposite side distance finally obtains 7 that cross section is regular hexagon2Core composite wire, the opposite side distance of the regular hexagon are 2.55mm；
Step 7: by obtained in step 672Core composite wire carries out composite molding three times, is made 73Core composite wire；
The method that the composite molding three times uses is identical as clustered drawing described in step 5, the clustered drawing it is specific
Process are as follows:
Step 701, by 72Core composite wire successively carries out scale, shearing, aligning and pickling processes；
Step 702, by 7 steps 701 after pickling processes 72Core composite wire boundling is assembled into outer diameter and is
12.5mm, wall thickness 2.5mm, in the second oxygen-free copper pipe that length is 400mm, then the isothermal holding 60h at 950 DEG C, obtains
Copper pipe complex；
Step 703, by copper pipe complex obtained in step 702 carry out the drawing of multi-pass third, the drawing die used according to
It is secondary are as follows: Φ 12.16mm, Φ 11.97mm, Φ 11.64mm, Φ 11.4mm, Φ 10.3mm, Φ 9.2mm, Φ 8.5mm, Φ
8.16mm、Φ7.97mm、Φ7.74mm、Φ7.15mm、Φ7.0mm、Φ6.6mm、Φ6.3mm、Φ6.0mm、Φ5.57mm、Φ
5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 450 DEG C/2h), Φ 4.9mm, Φ 4.7mm, Φ
4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ3.26mm、Φ3.13mm、Φ
3.0mm, Φ 2.80mm, Φ 2.76mm, Φ 2.68mm and S2.55mm, wherein Φ indicates that round drawing mode diameter, S indicate six sides
Mould opposite side distance finally obtains 7 that cross section is regular hexagon3Core composite wire, the opposite side distance of the regular hexagon are 2.55mm；
Step 8: by obtained in step 773Graphene/copper niobium composite wire, detailed process is made in core composite wire
Are as follows:
Graphene molten liquid is coated uniformly on the outer wall that outer diameter is 11.5mm, wall thickness is 1.67mm niobium pipe by step 801
On, graphene-niobium pipe is obtained after solidification；Graphene in the graphene-niobium pipe outer wall is with a thickness of 0.4mm；
Step 802, by 73Core composite wire is encased in graphene-niobium pipe, obtains composite pipe body；
Step 803, by composite pipe body obtained in step 802 loading outer diameter be 13.5mm, wall thickness 1.0mm, length are
In the third oxygen-free copper pipe of 400mm, in 950 DEG C of processing 60h, the 4th drawing of multi-pass is then carried out, the drawing die used is successively
Are as follows: Φ 8.16mm, Φ 7.97mm, Φ 7.74mm, Φ 7.15mm, Φ 7.0mm, Φ 6.6mm, Φ 6.3mm, Φ 6.0mm, Φ
5.57mm, Φ 5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 450 DEG C/2h), Φ 4.9mm, Φ
4.7mm、Φ4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ3.26mm、Φ
3.13mm, Φ 3.0mm, Φ 2.80mm, Φ 2.76mm and S2.55mm, wherein Φ indicates that round drawing mode diameter, S indicate six sides
Mould opposite side distance, finally obtains graphene/copper niobium core composite wire that cross section is regular hexagon, and the opposite side distance of the regular hexagon is
2.55mm；
Step 9: graphene/copper niobium Multicore composite is made in graphene obtained in step 8/copper niobium composite wire
Material, detailed process are as follows:
Graphene/copper niobium composite wire is successively truncated, is aligned, pickling and drying process by step 901；
Step 902, take in 19 steps 901 be dried after graphene/copper niobium composite wire be packed into outer diameter be
65.0mm, wall thickness 17.8mm, in the 4th oxygen-free copper pipe that length is 200mm, the 4th oxygen-free copper pipe then is filled with copper plunger
Gap between middle graphene/copper niobium composite wire, then vacuum electron beam is carried out to the both ends of filled 4th oxygen-free copper pipe
Soldering and sealing；
Step 903, by the 4th oxygen-free copper pipe after vacuum electron beam soldering and sealing in 700 DEG C of hot extrusion 5h, extrusion ratio 35, so
Afterwards carry out the 5th drawing of multi-pass, the drawing die used is successively are as follows: Φ 8.16mm, Φ 7.97mm, Φ 7.74mm, Φ 7.15mm,
Φ 7.0mm, Φ 6.6mm and Φ 6.3mm, wherein Φ indicates round drawing mode diameter, obtains graphene/copper niobium Multicore composite
Material.
Graphene manufactured in the present embodiment/copper niobium Multicore composite material core number is 19 × 73Core, through detecting: the wire rod
Intensity is 536MPa, and the intensity compared to the same size wire rod of conventional method preparation improves 20%；The wire rod conductance is 77%
IACS, the resistivity compared to the same size wire rod of conventional method preparation reduce 9%.
Embodiment 5
The present embodiment the following steps are included:
Step 1: copper scale and niobium powder high-energy ball milling 40h after mixing are obtained refinement powder；The copper scale and niobium powder
Mass ratio be 1:1；The purity of the niobium powder is 99.99%；
Step 2: refinement powder obtained in step 1 is packed into, outer diameter is 10.5mm, wall thickness 2.0mm, length are
In the first oxygen-free copper pipe of 400mm, then the both ends of the first oxygen-free copper pipe are sealed, obtain tubulature complex；It is described thin
The charge weight for changing powder is the 60% of tubulature composite quality；
Step 3: tubulature complex obtained in step 2 is carried out the first drawing of multi-pass, the drawing die used is successively
Are as follows: Φ 10.3mm, Φ 9.89mm, Φ 9.43mm, Φ 9.2mm, Φ 8.86mm and Φ 8.66mm, wherein Φ indicates round drawing die
Diameter, then in 1000 DEG C of heat treatment 60h；
Step 4: the tubulature complex after being heat-treated in step 3 is carried out the second drawing of multi-pass, the drawing die used
Successively are as follows: Φ 8.5mm, Φ 8.16mm, Φ 7.97mm, Φ 7.66mm, Φ 7.15mm, Φ 7.0mm, Φ 6.6mm, Φ 6.3mm, Φ
6.0mm, Φ 5.57mm, Φ 5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 650 DEG C/4h), Φ
4.9mm、Φ4.7mm、Φ4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ
3.26mm, Φ 3.13mm, Φ 3.0mm, Φ 2.80mm, Φ 2.76mm, Φ 2.68mm and S2.50mm, wherein Φ indicates round drawing
Draft diameter, S indicate six side's mould opposite side distances, finally obtain the monofilamentary composite wire material that cross section is regular hexagon, the orthohexagonal
Opposite side distance be 2.50mm；
Step 5: monofilamentary composite wire material obtained in step 4 is carried out once-combined molding, 7 core composite wires are made；
The once-combined molding uses clustered drawing, the detailed process of the clustered drawing are as follows:
Monofilamentary composite wire material is successively carried out scale, shearing, aligning and pickling processes by step 501；
Monofilamentary composite wire material boundling in 7 steps 501 after pickling processes is assembled into outer diameter and is by step 502
11.5mm, wall thickness 2.0mm, in the second oxygen-free copper pipe that length is 400mm, then the isothermal holding 60h at 1000 DEG C, obtains
Copper pipe complex；
Step 503, by copper pipe complex obtained in step 502 carry out the drawing of multi-pass third, the drawing die used according to
It is secondary are as follows: Φ 11.4mm, Φ 10.87mm, Φ 10.3mm, Φ 9.2mm, Φ 8.5mm, Φ 8.16mm, Φ 7.97mm, Φ 7.74mm,
Φ 7.15mm, Φ 7.0mm, Φ 6.6mm, Φ 6.3mm, Φ 6.0mm, Φ 5.57mm, Φ 5.4mm, Φ 5.1mm, Φ 4.9mm (
Once made annealing treatment after this passage drawing: 650 DEG C/4h), Φ 4.7mm, Φ 4.5mm, Φ 4.3mm, Φ 4.13mm, Φ
4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ3.26mm、Φ3.13mm、Φ3.0mm、Φ2.80mm、Φ2.76mm、
Φ 2.68mm and S2.50mm, wherein Φ indicates that round drawing mode diameter, S indicate six side's mould opposite side distances, and finally obtaining cross section is
7 core composite wires of regular hexagon, the opposite side distance of the regular hexagon are 2.50mm；
Step 6: 7 core composite wires obtained in step 5 are carried out secondary composite molding, it is made 72Core composite wire；
The method that the secondary composite molding uses is identical as the clustered drawing described in step 5, the clustered drawing it is specific
Process are as follows:
7 core composite wires are successively carried out scale, shearing, aligning and pickling processes by step 601；
7 core composite wire boundlings in 7 steps 601 after pickling processes are assembled into outer diameter and are by step 602
12.5mm, wall thickness 2.5mm, in the second oxygen-free copper pipe that length is 400mm, then the isothermal holding 60h at 1000 DEG C, obtains
Copper pipe complex；
Step 603, by copper pipe complex obtained in step 602 carry out the drawing of multi-pass third, the drawing die used according to
It is secondary are as follows: Φ 12.16mm, Φ 11.97mm, Φ 11.64mm, Φ 11.4mm, Φ 10.3mm, Φ 9.2mm, Φ 8.5mm, Φ
8.16mm、Φ7.97mm、Φ7.74mm、Φ7.15mm、Φ7.0mm、Φ6.6mm、Φ6.3mm、Φ6.0mm、Φ5.57mm、Φ
5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 650 DEG C/4h), Φ 4.9mm, Φ 4.7mm, Φ
4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ3.26mm、Φ3.13mm、Φ
3.0mm, Φ 2.80mm, Φ 2.76mm, Φ 2.68mm and S2.50mm, wherein Φ indicates that round drawing mode diameter, S indicate six sides
Mould opposite side distance finally obtains 7 that cross section is regular hexagon2Core composite wire, the opposite side distance of the regular hexagon are 2.50mm；
Step 7: by obtained in step 672Core composite wire carries out composite molding three times, is made 73Core composite wire；
The method that the composite molding three times uses is identical as clustered drawing described in step 5, the clustered drawing it is specific
Process are as follows:
Step 701, by 72Core composite wire successively carries out scale, shearing, aligning and pickling processes；
Step 702, by 7 steps 701 after pickling processes 72Core composite wire boundling is assembled into outer diameter and is
12.5mm, wall thickness 2.5mm, in the second oxygen-free copper pipe that length is 400mm, then the isothermal holding 60h at 1000 DEG C, obtains
Copper pipe complex；
Step 703, by copper pipe complex obtained in step 702 carry out the drawing of multi-pass third, the drawing die used according to
It is secondary are as follows: Φ 12.16mm, Φ 11.97mm, Φ 11.64mm, Φ 11.4mm, Φ 10.3mm, Φ 9.2mm, Φ 8.5mm, Φ
8.16mm、Φ7.97mm、Φ7.74mm、Φ7.15mm、Φ7.0mm、Φ6.6mm、Φ6.3mm、Φ6.0mm、Φ5.57mm、Φ
5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 650 DEG C/4h), Φ 4.9mm, Φ 4.7mm, Φ
4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ3.26mm、Φ3.13mm、Φ
3.0mm, Φ 2.80mm, Φ 2.76mm, Φ 2.68mm and S2.50mm, wherein Φ indicates that round drawing mode diameter, S indicate six sides
Mould opposite side distance finally obtains 7 that cross section is regular hexagon3Core composite wire, the opposite side distance of the regular hexagon are 2.50mm；
Step 8: by obtained in step 773Graphene/copper niobium composite wire, detailed process is made in core composite wire
Are as follows:
Graphene molten liquid is coated uniformly on the outer wall that outer diameter is 11.5mm, wall thickness is 1.67mm niobium pipe by step 801
On, graphene-niobium pipe is obtained after solidification；Graphene in the graphene-niobium pipe outer wall is with a thickness of 0.5mm；
Step 802, by 73Core composite wire is encased in graphene-niobium pipe, obtains composite pipe body；
Step 803, by composite pipe body obtained in step 802 loading outer diameter be 13.5mm, wall thickness 1.0mm, length are
In the third oxygen-free copper pipe of 400mm, in 1000 DEG C of processing 60h, the 4th drawing of multi-pass is then carried out, the drawing die used is successively
Are as follows: Φ 8.16mm, Φ 7.97mm, Φ 7.74mm, Φ 7.15mm, Φ 7.0mm, Φ 6.6mm, Φ 6.3mm, Φ 6.0mm, Φ
5.57mm, Φ 5.4mm, Φ 5.1mm (once being made annealing treatment after this passage drawing: 650 DEG C/4h), Φ 4.9mm, Φ
4.7mm、Φ4.5mm、Φ4.3mm、Φ4.13mm、Φ4.0mm、Φ3.81mm、Φ3.68mm、Φ3.4mm、Φ3.26mm、Φ
3.13mm, Φ 3.0mm, Φ 2.80mm, Φ 2.76mm and S2.50mm, wherein Φ indicates that round drawing mode diameter, S indicate six sides
Mould opposite side distance, finally obtains graphene/copper niobium core composite wire that cross section is regular hexagon, and the opposite side distance of the regular hexagon is
2.50mm；
Step 9: graphene/copper niobium Multicore composite is made in graphene obtained in step 8/copper niobium composite wire
Material, detailed process are as follows:
Graphene/copper niobium composite wire is successively truncated, is aligned, pickling and drying process by step 901；
Step 902, take in 19 steps 901 be dried after graphene/copper niobium composite wire be packed into outer diameter be
65.0mm, wall thickness 17.8mm, in the 4th oxygen-free copper pipe that length is 200mm, the 4th oxygen-free copper pipe then is filled with copper plunger
Gap between middle graphene/copper niobium composite wire, then vacuum electron beam is carried out to the both ends of filled 4th oxygen-free copper pipe
Soldering and sealing；
Step 903, by the 4th oxygen-free copper pipe after vacuum electron beam soldering and sealing in 700 DEG C of hot extrusion 6h, extrusion ratio 42, so
Afterwards carry out the 5th drawing of multi-pass, the drawing die used is successively are as follows: Φ 8.16mm, Φ 7.97mm, Φ 7.74mm, Φ 7.15mm,
Φ 7.0mm, Φ 6.6mm and Φ 6.3mm, wherein Φ indicates round drawing mode diameter, obtains graphene/copper niobium Multicore composite
Material.
Graphene manufactured in the present embodiment/copper niobium Multicore composite material core number is 19 × 73Core, through detecting: the wire rod
Intensity is 724MPa, and the intensity compared to the same size wire rod of conventional method preparation improves 15%；The wire rod conductance is 81%
IACS, the resistivity compared to the same size wire rod of conventional method preparation reduce 8%.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way.It is all according to invention skill
Art any simple modification, change and equivalence change substantially to the above embodiments, still fall within technical solution of the present invention
Protection scope in.
Claims (5)
1. a kind of graphene/copper niobium Multicore composite material preparation method, which is characterized in that method includes the following steps:
Step 1: copper scale and niobium powder are carried out high-energy ball milling after mixing, refinement powder is obtained；The matter of the copper scale and niobium powder
The ratio between amount is 1:1；The purity of the niobium powder is 99.99%；
Step 2: refinement powder obtained in step 1 is fitted into the first oxygen-free copper pipe, then by the two of the first oxygen-free copper pipe
End is sealed, and obtains tubulature complex；The charge weight of the refinement powder is the 10%~60% of tubulature composite quality；
Step 3: tubulature complex obtained in step 2 is carried out the first drawing of multi-pass, then it is heat-treated；Described
The pass reduction of one drawing is less than 10%；
Step 4: the tubulature complex after being heat-treated in step 3 is carried out the second drawing of multi-pass, monofilamentary composite wire material is obtained；
The pass reduction of second drawing is less than 15%；
Step 5: monofilamentary composite wire material obtained in step 4 is carried out once-combined molding, 7 core composite wires are made；It is described
Once-combined molding uses clustered drawing, the detailed process of the clustered drawing are as follows:
Monofilamentary composite wire material is successively carried out scale, shearing, aligning and pickling processes by step 501；
Monofilamentary composite wire material boundling in 7 steps 501 after pickling processes is assembled into the second oxygen-free copper pipe by step 502,
Then it is heat-treated, obtains copper pipe complex；
Copper pipe complex obtained in step 502 is carried out the drawing of multi-pass third by step 503, obtains 7 core composite wires；Institute
The pass reduction of third drawing is stated less than 21%；
Step 6: 7 core composite wires obtained in step 5 are carried out secondary composite molding, it is made 72Core composite wire；Described two
The method that secondary composite molding uses is identical as clustered drawing described in step 5；
Step 7: by obtained in step 672Core composite wire carries out composite molding three times, is made 73Core composite wire；It is described
The method that composite molding uses three times is identical as clustered drawing described in step 5；
Step 8: by obtained in step 773Graphene/copper niobium composite wire, detailed process is made in core composite wire are as follows:
Graphene molten liquid is coated uniformly on the outer wall of niobium pipe by step 801, and graphene-niobium pipe is obtained after solidification；The stone
Graphene thickness in black alkene-niobium pipe outer wall is less than 1mm；
Step 802, by 73Core composite wire is encased in graphene-niobium pipe, obtains composite pipe body；
Composite pipe body obtained in step 802 is fitted into third oxygen-free copper pipe by step 803, successively carries out heat treatment and multiple tracks
Secondary 4th drawing obtains graphene/copper niobium composite wire；The pass reduction of 4th drawing is less than 15%；
Step 9: graphene/copper niobium Multicore composite material is made in graphene obtained in step 8/copper niobium composite wire, have
Body process are as follows:
Graphene/copper niobium composite wire is successively truncated, is aligned, pickling and drying process by step 901；
Step 902 takes graphene/copper niobium composite wire after being dried in 19 steps 901 to be fitted into the 4th oxygen-free copper pipe,
Then the gap in the 4th oxygen-free copper pipe between graphene/copper niobium composite wire is filled with copper plunger, then to the filled 4th
The both ends of oxygen-free copper pipe carry out vacuum electron beam soldering and sealing；
The 4th oxygen-free copper pipe after vacuum electron beam soldering and sealing is successively carried out the 5th drawing of hot extrusion and multi-pass by step 903, is obtained
To graphene/copper niobium Multicore composite material；The pass reduction of 5th drawing is less than 12%.
2. a kind of graphene according to claim 1/copper niobium Multicore composite material preparation method, which is characterized in that step
The time of high-energy ball milling described in rapid one is 20h~40h.
3. a kind of graphene according to claim 1/copper niobium Multicore composite material preparation method, which is characterized in that step
The temperature of heat treatment described in rapid three, step 502 and step 803 is 800 DEG C~1000 DEG C, and the time is 60h.
4. a kind of graphene according to claim 1/copper niobium Multicore composite material preparation method, which is characterized in that step
Monofilamentary composite wire material described in rapid four, 7 core composite wires described in step 5,7 described in step 62Core composite wire, step
7 described in seven3Graphene described in core composite wire and step 8/copper niobium composite wire cross-sectional shape is positive six sides
Shape；The opposite side distance of the regular hexagon is 2.5mm~2.7mm.
5. a kind of graphene according to claim 1/copper niobium Multicore composite material preparation method, which is characterized in that step
The temperature of hot extrusion described in rapid 903 is 600 DEG C~700 DEG C, and soaking time is 2h~6h, and extrusion ratio is 10~42.
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