CN108000916A - A kind of preparation method of single layered porous graphene enhancing carbon fiber fishing rod - Google Patents
A kind of preparation method of single layered porous graphene enhancing carbon fiber fishing rod Download PDFInfo
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- CN108000916A CN108000916A CN201711129762.1A CN201711129762A CN108000916A CN 108000916 A CN108000916 A CN 108000916A CN 201711129762 A CN201711129762 A CN 201711129762A CN 108000916 A CN108000916 A CN 108000916A
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- fishing rod
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- porous graphene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D99/00—Subject matter not provided for in other groups of this subclass
- B29D99/0046—Producing rods
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01K—ANIMAL HUSBANDRY; CARE OF BIRDS, FISHES, INSECTS; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
- A01K87/00—Fishing rods
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Abstract
The invention discloses a kind of preparation method of single layered porous graphene enhancing carbon fiber fishing rod, belong to technical field of polymer materials, it is characterized in that, expanded graphite is peeled off into graphene microchip dispersion liquid first, graphene microchip powder is made in spray drying, the porous graphene predecessor of individual layer is made in microwave treatment in NMP dispersion liquids after oxidized, activation process finally is carried out to this predecessor with highly basic, obtain the single layered porous graphene that hole enriches, aperture is larger, again with the compound obtained carbon fiber cloth material of carbon fiber, finally fishing rod is rolled into through cutting out;While the single layered porous graphene of the present invention can easily coat carbon fiber, the circulation for being again resin in fishing rod solidification process between carbon cloth provides enough passages, so that the good organic whole of continuity is formed between graphene and carbon fiber and carbon fiber itself, and then the stretching buckling strength of carbon fiber fishing rod is greatly improved, significantly increase fishing rod and fish weight.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of single layered porous graphene strengthens carbon fiber fishing rod
Preparation method.
Background technology
Existing carbon fishing rod is all to be arranged in pairs or groups by different grades of carbon cloth and be fixed on setting via pipe crimping strip winding machine
On good mould, formed by unit interval hot setting, wherein carbon cloth is usually made by carbon fibre tow pre-soaked resin.This
Fishing rod made of kind of technology have the characteristics that it is light, very, screen resilience it is good, most of high-grade fishing rods use such a skill more both at home and abroad
Art;But since carbon fibre has the characteristics of rigidity is strong, and pliability is low, the intensity that hangs within 45 degree compares under normal conditions
It is good, but to enter intensity relatively low for 90 degree of strand.
Current common fishing rod uses in the case of long-term high intensity is high-frequency, its intensity and toughness, which can decline, to be compared
It hurry up, relatively low for the low-angle strength resistance of moment, the service life of product is shorter and long-time service rigidly can also decline, and makes
With the tonality that cannot reach original design after a certain period of time, the requirement used under high intensity, high-frequency is not met.
Graphene be it is most thin in the world at present be but also most hard nano material, have that intensity is high, specific surface area is big, high
The characteristics of chemical reactivity, high fillibility, be commonly used for the reinforcing material of carbon fiber.If publication No. is in CN107189354A
A kind of preparation method of graphene nanometer sheet enhancing carbon fibre composite of state invention patent application publication, first by graphene
Nanometer sheet is distributed in the organic solvent containing a small amount of thermosetting resin and curing agent, and carbon cloth then is placed in graphene receives
The carbon cloth up to surface attachment graphene nanometer sheet is soaked in rice piece suspension, this method can make graphene nanometer sheet equal
Carbon fiber surface is adhered to evenly, is present in the interlayer of carbon cloth, and the interlayer that fibrous composite is significantly improved after curing is cut
Shearing stress, bending strength and longitudinal thermal conductivity.But carbon cloth made from this method is applied to also exist during fishing rod
Following problem:Since graphene sheet layer has excellent barrier property, carbon cloth need to be in curing oven scala media after being wound into fishing rod
The purpose of ladder type elevated cure is molded, and curing uses low-temperature heat initial stage is to allow resin to circulate between carbon fiber, is made in carbon fiber
Resin uniformly and bonding is integral, and the iris action of graphene can hinder stream of the resin between carbon fiber and graphene
It is logical, or even circulation of the resin between carbon fiber layer is hindered, cause attachment force deficiency between graphene and carbon fiber, make fishing rod
Easily it is broken under the use of high-frequency high intensity afterwards.
Further, since carbon fiber surface activity is low, poor with resin matrix wellability, the interlayer for being easy to cause composite material is cut
Shearing stress reduces, and notification number is that the Chinese invention patent of CN102787488B discloses a kind of graphene oxide splicing surface modification
The method of carbon fiber, by making graphene oxide greatly improve in carbon fiber surface uniform fold graphene oxide functionalization
The roughness of carbon fiber surface, so as to act on the interface performance for improving carbon fibre reinforced composite by grappling.But the party
Carbon fibre composite made from method be used for fishing rod there is a problem in that:The oxygen-containing functional group meeting of surface of graphene oxide and carbon
Auxiliary agent in fiber cloth reacts, and influences the comprehensive performance of coating and carbon cloth, while this kind of functional group can also be with mould
On releasing agent react, cause fishing rod rod body can not be with mould separating, therefore composite material prepared by this technique is uncomfortable
Preferably it is used for the production of fishing rod.
The content of the invention
The technical problems to be solved by the invention are in view of the deficiencies of the prior art, there is provided a kind of single layered porous graphene increases
The preparation method of strong carbon fiber fishing rod, initiatively by the porous graphene of individual layer and the compound preparation for fishing rod of carbon fiber,
It is intended to make the single-layer graphene of high intensity high-flexibility be coated on carbon fiber surface, tensile strength, the bending for improving carbon fiber are strong
Degree, and combination power is good, cladding is easy;The loose structure of graphene is that the resin circulation in fishing rod forming process in carbon cloth carries at the same time
For fully infiltrating resin between passage guarantee carbon fiber, between carbon fiber and graphene, organic whole is formed after curing, so that
Fishing rod has superhigh intensity.
The technical solution that the present invention solves above-mentioned technical problem is as follows:A kind of single layered porous graphene strengthens carbon fiber fishing rod
Preparation method, it is characterised in that carry out as follows:
(1)The preparation of single layered porous graphene:
A, in terms of 100 parts of gross weight number, 1-5 parts of expanded graphites are taken to be scattered in the solvent dissolved with dispersant, by cutting at a high speed
Cut machine and carry out high speed shear stripping, the expanded graphite of vermicular texture is peeled off into the laminated structure into less than 10 layers, obtains graphite
Alkene microplate dispersion liquid;Effect is that expanded graphite is peeled off, and the expanded graphite of vermicular texture is peeled off into less than 10 layers
Laminated structure, facilitates further oxidation processes;
The dispersant weight is the 30-80% of expanded graphite, and surplus is solvent;
The solvent is used in CMC, SDS, PVP, BYK163 using one kind in deionized water, NMP, DMF, the dispersant
It is a kind of;
B, above-mentioned graphene microchip dispersion liquid is stood into 8-24h, takes upper strata stable dispersions, stripping is made using spray drying process
Graphene microchip powder;Due in upper strata is stablized after standing dispersion liquid there are graphene microchip agglomeration is less,
It is less than 10 layers of state that can ensure obtained graphene microchip, so that for subsequently preparing single-layer graphene does basis;
C, take above-mentioned graphene microchip powder 1-3g to add into the 100-150ml concentrated sulfuric acids, add 5-20ml H while stirring2O2
In solution, lasting stirring reaction 20-90min, obtains graphene oxide dispersion at room temperature;It is such a first to peel off graphite into 10
The microplate of very thin thickness below layer carries out the technique of oxidation processes again, can ensure on every layer graphene microplate and edge all can
There is functional group, its oxidation effectiveness is much better than direct oxidation processing graphite, is more convenient for subsequently obtaining the high graphene of individual layer rate;
The H2O2The concentration of solution is 35-50%;
D, above-mentioned graphene oxide dispersion is first washed with deionized to neutrality, then is fully washed to NMP with NMP and put completely
The deionized water in graphene oxide dispersion is changed, obtains graphene oxide NMP dispersion liquids;Effect is by low-boiling solvent
Deionized water is replaced as high boiling NMP, and the wherein boiling point of NMP is 203 DEG C, higher than the reduction temperature 150- of graphene oxide
200℃;
E, above-mentioned graphene oxide NMP dispersion liquids are ultrasonically treated 1-6h, less than 10 layers of graphene oxide microplate is carried out two
Secondary stripping;Purpose is to make graphene oxide sheet peeling-off again under ultrasonication, reduces and reunites, and ensures individual layer rate;
F, the graphene oxide NMP dispersion liquids after supersound process are subjected to microwave radiation processing, microwave radiation 3- under 300-900W
10min is volatilized and burnt under microwave action to NMP whole all burnts, NMP, the heat that graphene oxide is produced in NMP burnings
Amount effect issues raw reduction reaction and the swelling surface for forming individual layer has the single layered porous graphene forerunner of pore space structure again
Thing;
G, above-mentioned single layered porous graphene predecessor is taken to be mixed with 0.5-15gKOH, in N2Under protection in tube furnace 400-1000
Activation 0.5-4h is carried out at DEG C, obtains single layered porous graphene, hole enriches aperture bigger.
Since NMP volatilizees in microwave process(203℃)And the temperature of burning is higher than the reduction temperature of graphene oxide
(150-200℃), therefore can ensure that graphene oxide fully reduces, the decomposition of graphene oxide functional group at this time can produce huge
Big pressure, makes graphene oxide is swelling again to obtain the graphene of individual layer, while the burning of NMP and the vigorous reaction of functional group
A large amount of holes can be respectively formed on every layer graphene piece surface, finally increase the poling processing technique of a step highly basic, further increase
Pore quantity level aperture on graphene sheet layer, ultimately form individual layer has porous graphene film, this graphene film
Layer is very thin, therefore causes graphene to be easy to be coated on carbon fiber with superior pliability and larger piece footpath, while more
The structure in hole can ensure the circulation of resin in carbon cloth, substantially increase the connectedness of the resin in carbon cloth, make stone
Black alkene more combines with carbon fiber.
(2)The preparation of single layered porous graphene/carbon fiber composite cloth:
A, by above-mentioned single layered porous graphene dispersion in sizing agent, graphene sizing system is obtained;The sizing agent uses ring
The weight ratio of oxygen tree fat, single layered porous graphene and sizing agent is 1 ︰ 100-1000;Effect is to be beneficial to graphene coated in carbon fibre
Dimension table face, improves stretching and the buckling strength of carbon fiber;
B, carbon fibre tow leaching is placed in above-mentioned graphene sizing system, is obtained after fully soaking through single layered porous graphene bag
The carbon fibre tow covered, then, then carbon fibre tow is laid in the release liners for scribbling epoxy resin, is prepared into by extruding
Carbon cloth;
(3)Above-mentioned carbon cloth is cut out, through mould coiling and molding, curing molding in sintering oven is then inserted, fish is made
Pole.
Further, the expansion multiplying power of the expanded graphite is more than 200 so that graphene sheet layer is more easy to be lifted off of.
Further, the shearing power 50-65Hz of the high-speed shearing machine, shear time 10-60min;Due to expanding stone
Only have edge between ink sheet layer and be in connection status, middle part spacing is larger, and expanded graphite passes through cutter in stripping process
Slit when be stripped and come under huge rotating speed, due to the very narrow only several nanometers of slit, can ensure to be stripped
Lamella below 10 layers.
Further, the step(3)In solidification process be first by the carbon cloth of coiling and molding at 60-80 DEG C
10-50min is toasted, resin is in flowable state at this time, and resin can flow between each layer of carbon cloth under the effect of gravity, ensures fishing rod
The uniform content of middle each several part resin, then heats to 120-140 DEG C of constant temperature 1-4h, and resin crosslinks cure at this temperature, fish
Pole is molded, and is finally air-cooled to room temperature.
The beneficial effects of the invention are as follows:
1. by the way that preparation of the modification for carbon fiber fishing rod is carried out to carbon fiber with the graphene with loose structure of individual layer, by
In graphene larger piece footpath and excellent pliability so that while graphene easily coats carbon fiber, and cured for fishing rod
Circulation of the resin between carbon cloth provides enough passage in journey so that graphene and carbon fiber and carbon fiber itself it
Between form the good organic whole of continuity, and then greatly improve the stretching buckling strength of carbon fiber fishing rod, significantly increase fishing rod fishing
Weight;
2. the technique of the present invention then carries out the preparation method and biography of oxidation processes by first peeling off expanded graphite into predispersion
System technique is compared, and the lamella oxidation that expanded graphite is peeled off can be made more thorough, the individual layer rate of gained graphene can be significantly
Degree improves and on every layer graphene containing abundant functional group;
It is ultrasonically treated, is weakened 3. the graphene oxide containing abundant functional group is first scattered in NMP by the technique of the present invention
Reunion situation, then be placed in micro-wave oven and carry out microwave radiation, it is higher than the reduction temperature of graphene oxide using the boiling point of NMP, because
Graphene oxide is quickly reduced during this microwave radiation, and surface functional group, which decomposes rapidly the immense pressure brought, makes graphene
Piece reexpands, and obtains the graphene of individual layer, while the vigorous combustion of NMP makes graphene surface form substantial amounts of hole, highly basic
Poling processing technique can further increase pore quantity and the aperture of graphene surface, and the loose structure of formation cures for fishing rod
When circulation of the resin between carbon cloth sufficient passage is provided.
Embodiment
Embodiment 1
A kind of preparation method of single layered porous graphene enhancing carbon fiber fishing rod, carries out as follows:
(1)The preparation of single layered porous graphene:
A, in terms of 100 parts of gross weight number, 1 part of expanded graphite is taken to be scattered in the deionized water dissolved with 0.3 part of CMC, surplus is
Deionized water, carries out high speed shear stripping by high-speed shearing machine, obtains graphene microchip dispersion liquid, the shearing of high-speed shearing machine
Power 50Hz, shear time 10min, the expansion multiplying power of expanded graphite are more than 200;
B, above-mentioned graphene microchip dispersion liquid is stood into 8h, takes upper strata stable dispersions, stripping is made using spray drying process
Graphene microchip powder;
C, above-mentioned graphene microchip powder 1g is taken to add into the 100ml concentrated sulfuric acids, it is 35% H to add 5ml concentration while stirring2O2
In solution, lasting stirring reaction 20min, obtains graphene oxide dispersion at room temperature;
D, above-mentioned graphene oxide dispersion is first washed with deionized to neutrality, then is fully washed to NMP with NMP and put completely
The deionized water in graphene oxide dispersion is changed, obtains graphene oxide NMP dispersion liquids;
E, above-mentioned graphene oxide NMP dispersion liquids are ultrasonically treated 1h;
F, the graphene oxide NMP dispersion liquids after supersound process are subjected to microwave radiation processing, microwave radiation 3min is extremely under 300W
NMP whole all burnts, obtain single layered porous graphene predecessor;
G, above-mentioned single layered porous graphene predecessor is taken to be mixed with 0.5gKOH, in N2Carried out under protection in tube furnace at 400 DEG C
0.5h is activated, obtains the single layered porous graphene of the more rich aperture bigger of hole.
(2)The preparation of single layered porous graphene/carbon fiber composite cloth:
A, by above-mentioned single layered porous graphene dispersion in sizing agent, graphene sizing system is obtained;The sizing agent uses ring
The weight ratio of oxygen tree fat, single layered porous graphene and sizing agent is 1 ︰ 1000;
B, carbon fibre tow leaching is placed in above-mentioned graphene sizing system, is obtained after fully soaking through porous graphene cladding
Carbon fibre tow, then, then carbon fibre tow is laid in the release liners for scribbling epoxy resin, and carbon fibre is prepared into by extruding
Wei Bu;
(3)Above-mentioned carbon cloth is cut out, through mould coiling and molding, curing molding in sintering oven is then inserted, fish is made
Pole, wherein solidification process then heat to 120 DEG C of perseverances for the carbon cloth of coiling and molding is toasted 10min at 60 DEG C first
Warm 1h, is finally air-cooled to room temperature.
Embodiment 2
A kind of preparation method of single layered porous graphene enhancing carbon fiber fishing rod, carries out as follows:
(1)The preparation of single layered porous graphene:
A, in terms of 100 parts of gross weight number, 3 parts of expanded graphites are taken to be scattered in the NMP dissolved with 1.5 parts of SDS, surplus NMP, leads to
Cross high-speed shearing machine and carry out high speed shear stripping, obtain graphene microchip dispersion liquid, the shearing power 58Hz of high-speed shearing machine, cuts
Time 35min is cut, the expansion multiplying power of expanded graphite is more than 200;
B, above-mentioned graphene microchip dispersion liquid is stood into 16h, takes upper strata stable dispersions, stripping is made using spray drying process
Graphene microchip powder;
C, above-mentioned graphene microchip powder 2g is taken to add into the 120ml concentrated sulfuric acids, it is 45% to add 15ml concentration while stirring
H2O2In solution, lasting stirring reaction 35min, obtains graphene oxide dispersion at room temperature;
D, above-mentioned graphene oxide dispersion is first washed with deionized to neutrality, then is fully washed to NMP with NMP and put completely
The deionized water in graphene oxide dispersion is changed, obtains graphene oxide NMP dispersion liquids;
E, above-mentioned graphene oxide NMP dispersion liquids are ultrasonically treated 4h;
F, the graphene oxide NMP dispersion liquids after supersound process are subjected to microwave radiation processing, microwave radiation 6min is extremely under 600W
NMP whole all burnts, obtain single layered porous graphene predecessor;
G, above-mentioned single layered porous graphene predecessor is taken to be mixed with 10gKOH, in N2Carried out under protection in tube furnace at 800 DEG C
2h is activated, obtains the single-layer graphene of the more rich aperture bigger of hole.
(2)The preparation of single layered porous graphene/carbon fiber composite cloth:
A, by above-mentioned single layered porous graphene dispersion in sizing agent, graphene sizing system is obtained;The sizing agent uses ring
The weight ratio of oxygen tree fat, single layered porous graphene and sizing agent is 1 ︰ 500;
B, carbon fibre tow leaching is placed in above-mentioned graphene sizing system, is obtained after fully soaking through porous graphene cladding
Carbon fibre tow, then, then carbon fibre tow is laid in the release liners for scribbling epoxy resin, carbon fiber is prepared into by extruding
Cloth;
(3)Above-mentioned carbon cloth is cut out, through mould coiling and molding, curing molding in sintering oven is then inserted, fish is made
Pole, wherein solidification process then heat to 130 DEG C of perseverances for the carbon cloth of coiling and molding is toasted 30min at 70 DEG C first
Warm 2h, is finally air-cooled to room temperature.
Embodiment 3
A kind of preparation method of single layered porous graphene enhancing carbon fiber fishing rod, carries out as follows:
(1)The preparation of single layered porous graphene:
A, in terms of 100 parts of gross weight number, 5 parts of expanded graphites are taken to be scattered in the DMF dissolved with 4.2 parts of PVP, surplus DMF, leads to
Cross high-speed shearing machine and carry out high speed shear stripping, obtain graphene microchip dispersion liquid, the shearing power 65Hz of high-speed shearing machine, cuts
Time 60min is cut, the expansion multiplying power of expanded graphite is more than 200;
B, above-mentioned graphene microchip dispersion liquid is stood into 24h, takes upper strata stable dispersions, stripping is made using spray drying process
Graphene microchip powder;
C, above-mentioned graphene microchip powder 3g is taken to add into the 150ml concentrated sulfuric acids, it is 50% to add 20ml concentration while stirring
H2O2In solution, lasting stirring reaction 90min, obtains graphene oxide dispersion at room temperature;
D, above-mentioned graphene oxide dispersion is first washed with deionized to neutrality, then is fully washed to NMP with NMP and put completely
The deionized water in graphene oxide dispersion is changed, obtains graphene oxide NMP dispersion liquids;
E, above-mentioned graphene oxide NMP dispersion liquids are ultrasonically treated 6h;
F, the graphene oxide NMP dispersion liquids after supersound process are subjected to microwave radiation processing, microwave radiation 10min is extremely under 900W
NMP whole all burnts, obtain single layered porous graphene predecessor;
G, above-mentioned single layered porous graphene predecessor is taken to be mixed with 15gKOH, in N2Carried out under protection in tube furnace at 1000 DEG C
4h is activated, obtains the single-layer graphene that hole enriches aperture bigger.
(2)The preparation of single layered porous graphene/carbon fiber composite cloth:
A, by above-mentioned single layered porous graphene dispersion in sizing agent, graphene sizing system is obtained;The sizing agent uses ring
The weight ratio of oxygen tree fat, single layered porous graphene powder and sizing agent is 1 ︰ 100;
B, carbon fibre tow leaching is placed in above-mentioned graphene sizing system, is obtained after fully soaking through porous graphene cladding
Carbon fibre tow, then, then carbon fibre tow is laid in the release liners for scribbling epoxy resin, and carbon fibre is prepared into by extruding
Wei Bu;
(3)Above-mentioned carbon cloth is cut out, through mould coiling and molding, curing molding in sintering oven is then inserted, fish is made
Pole, wherein solidification process then heat to 140 DEG C of perseverances for the carbon cloth of coiling and molding is toasted 50min at 80 DEG C first
Warm 4h, is finally air-cooled to room temperature.
Comparative example 1
Using the carbon cloth without graphene modified as raw material, carbon cloth is cut out, through mould coiling and molding, then inserts height
Curing molding in warm curing oven, is finally prepared to fishing rod, and wherein solidification process is 70 first by the carbon cloth of coiling and molding
30min is toasted at DEG C, 130 DEG C of constant temperature 2h is then heated to, is finally air-cooled to room temperature.
Comparative example 2
Fishing rod is prepared using the single-layer graphene and carbon fiber reinforced polymers that do not punch, is specifically carried out as follows:
(1)The preparation of single-layer graphene:
A, in terms of 100 parts of gross weight number, 3 parts of expanded graphites are taken to be scattered in the NMP dissolved with 1.5 parts of SDS, surplus NMP, leads to
Cross high-speed shearing machine and carry out high speed shear stripping, obtain graphene microchip dispersion liquid, the shearing power 58Hz of high-speed shearing machine, cuts
Time 35min is cut, the expansion multiplying power of expanded graphite is more than 200;
B, above-mentioned graphene microchip dispersion liquid is stood into 16h, takes upper strata stable dispersions, stripping is made using spray drying process
Graphene microchip powder;
C, above-mentioned graphene microchip powder 2g is taken to add into the 120ml concentrated sulfuric acids, it is 45% to add 15ml concentration while stirring
H2O2In solution, lasting stirring reaction 35min, obtains graphene oxide dispersion at room temperature;
D, above-mentioned graphene oxide dispersion is prepared into powder by spray drying and is placed on N in 400 DEG C of tube furnace2Protection
Lower thermal reduction 2h obtains the graphene powder of individual layer.
(2)The preparation of single-layer graphene/carbon fiber Compound Fabric:
A, above-mentioned single-layer graphene powder is scattered in sizing agent, obtains graphene sizing system;The sizing agent uses ring
The weight ratio of oxygen tree fat, single-layer graphene powder and sizing agent is 1 ︰ 500;
B, carbon fibre tow leaching is placed in above-mentioned graphene sizing system, is obtained after fully soaking through porous graphene cladding
Carbon fibre tow, then, then carbon fibre tow is laid in the release liners for scribbling epoxy resin, and carbon fibre is prepared into by extruding
Wei Bu;
(3)Above-mentioned carbon cloth is cut out, through mould coiling and molding, curing molding in sintering oven is then inserted, fish is made
Pole, wherein solidification process then heat to 130 DEG C of perseverances for the carbon cloth of coiling and molding is toasted 30min at 70 DEG C first
Warm 2h, is finally air-cooled to room temperature.
Comparative example 3
Fishing rod is prepared using the porous graphene and carbon fiber reinforced polymers of common three-dimensional structure, specifically as follows into
OK:
(1)The preparation of porous graphene:
A, crystalline flake graphite 2g is taken to add into the 120ml concentrated sulfuric acids, it is 45% H to add 15ml concentration while stirring2O2In solution, room
The lower lasting stirring reaction 35min of temperature, obtains graphene oxide dispersion;
B, above-mentioned graphene oxide dispersion is first washed with deionized to neutrality, then is fully washed to NMP with NMP and put completely
The deionized water in graphene oxide dispersion is changed, obtains graphene oxide NMP dispersion liquids;
C, the graphene oxide NMP dispersion liquids after supersound process are subjected to microwave radiation processing, it is micro- under 600W
Wave radiation 6min obtains porous graphene powdered precursor to NMP whole all burnts;
D, above-mentioned porous graphene predecessor is taken to be mixed with 10gKOH, in N2Activated under protection in tube furnace at 800 DEG C
2h, obtains the graphene of the more rich aperture bigger of hole.
(2)The preparation of porous graphene/carbon fiber Compound Fabric:
A, above-mentioned porous graphene powder is scattered in sizing agent, obtains graphene sizing system;The sizing agent uses ring
The weight ratio of oxygen tree fat, porous graphene powder and sizing agent is 1 ︰ 500;
B, carbon fibre tow leaching is placed in above-mentioned graphene sizing system, is obtained after fully soaking through porous graphene cladding
Carbon fibre tow, then, then carbon fibre tow is laid in the release liners for scribbling epoxy resin, and carbon fibre is prepared into by extruding
Wei Bu;
(3)Above-mentioned carbon cloth is cut out, through mould coiling and molding, curing molding in sintering oven is then inserted, fish is made
Pole, wherein solidification process then heat to 130 DEG C of perseverances for the carbon cloth of coiling and molding is toasted 30min at 70 DEG C first
Warm 2h, is finally air-cooled to room temperature.
Above-described embodiment and comparative example are made to the fishing rod of identical size, are respectively 5 sections, 5.4 meters long, and use
QBT1476-2004 standards are detected the static load amount of fishing rod, and test result is shown in Table 1.
The static load of 1 fishing rod of table measures test result
Fishing rod joint number | Fishing rod net weight/g | Fishing rod length/m | Fish weight/g | |
Embodiment 1 | 5 | 100 | 5.4 | 3150 |
Embodiment 2 | 5 | 102 | 5.4 | 4050 |
Embodiment 3 | 5 | 97 | 5.4 | 3350 |
Comparative example 1 | 5 | 101 | 5.4 | 2000 |
Comparative example 2 | 5 | 100 | 5.4 | 2450 |
Comparative example 3 | 5 | 99 | 5.4 | 2550 |
As can be seen from the above data, being not added with graphene in comparative example 1, the fishing rod fishing of making is again fewer than the fishing rod in embodiment
The reason for more than 1150g, this is rigidly strong mainly due to carbon cloth, and pliability is poor, can be broken under high intensity;
Fishing rod in comparative example 2 fishes reduces more than 700g than the fishing rod in embodiment again, this is because using single-layer graphene pair
Carbon fiber is modified, although the ultra-thin super flexible lamellar structure of graphene is easy to be coated on rigid carbon fiber surface,
Complete graphene has excellent iris action, and the circulation of resin can be hindered in fishing rod solidification process, cause carbon fiber and
Only connected between graphene by faint sizing agent, attachment force is extremely weak, and the in addition presence of graphene can be also hindered in carbon cloth
Circulation of the epoxy resin between carbon fiber layer, causes in fishing rod that local resin content is few, and intensity is small, therefore is easily broken;
The fishing of 3 finished fishing rods of comparative example will also reduce by 600 more than g than embodiment again, this is because the method is using common three-dimensional
The porous graphene of structure, due to the limitation of preparation method, more serious such graphene agglomeration is in three-dimensional structure, flexible
Property it is poor, compactness is poor between carbon fiber compound tense and rigid carbon-fiber, although there is no resin circulation the problem of,
Three-dimensional porous graphene cannot be coated on carbon fiber surface completely, therefore limited to the enhancing effect of carbon fiber.
Therefore, the present invention has significant creative feature.
Although the embodiment of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, those of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (4)
1. a kind of preparation method of single layered porous graphene enhancing carbon fiber fishing rod, it is characterised in that carry out as follows:
(1)The preparation of single layered porous graphene:
A, in terms of 100 parts of gross weight number, 1-5 parts of expanded graphites are taken to be scattered in the solvent dissolved with dispersant, by cutting at a high speed
Cut machine and carry out high speed shear stripping, the expanded graphite of vermicular texture is peeled off into the laminated structure into less than 10 layers, obtains graphite
Alkene microplate dispersion liquid;
The dispersant weight is the 30-80% of expanded graphite, and surplus is solvent;
The solvent is used in CMC, SDS, PVP, BYK163 using one kind in deionized water, NMP, DMF, the dispersant
It is a kind of;
B, above-mentioned graphene microchip dispersion liquid is stood into 8-24h, takes upper strata stable dispersions, stripping is made using spray drying process
Graphene microchip powder;
C, take above-mentioned graphene microchip powder 1-3g to add into the 100-150ml concentrated sulfuric acids, add 5-20ml H while stirring2O2
In solution, lasting stirring reaction 20-90min, obtains graphene oxide dispersion at room temperature;
The H2O2The concentration of solution is 35-50%;
D, above-mentioned graphene oxide dispersion is first washed with deionized to neutrality, then is fully washed to NMP with NMP and put completely
The deionized water in graphene oxide dispersion is changed, obtains graphene oxide NMP dispersion liquids;
E, above-mentioned graphene oxide NMP dispersion liquids are ultrasonically treated 1-6h, less than 10 layers of graphene oxide microplate is carried out two
Secondary stripping;
F, the graphene oxide NMP dispersion liquids after supersound process are subjected to microwave radiation processing, microwave radiation 3- under 300-900W
10min is volatilized and burnt under microwave action to NMP whole all burnts, NMP, the heat that graphene oxide is produced in NMP burnings
Amount effect issues raw reduction reaction and the swelling surface for forming individual layer has the single layered porous graphene forerunner of pore space structure again
Thing;
G, above-mentioned single layered porous graphene predecessor is taken to be mixed with 0.5-15gKOH, in N2Under protection in tube furnace 400-1000
Activation 0.5-4h is carried out at DEG C, obtains single layered porous graphene;
(2)The preparation of single layered porous graphene/carbon fiber composite cloth:
A, by above-mentioned single layered porous graphene dispersion in sizing agent, graphene sizing system is obtained;The sizing agent uses ring
The weight ratio of oxygen tree fat, single layered porous graphene and sizing agent is 1:100-1000;
B, carbon fibre tow leaching is placed in above-mentioned graphene sizing system, is obtained after fully soaking through single layered porous graphene bag
The carbon fibre tow covered, then, then carbon fibre tow is laid in the release liners for scribbling epoxy resin, is prepared into by extruding
Carbon cloth;
(3)Above-mentioned carbon cloth is cut out, through mould coiling and molding, curing molding in sintering oven is then inserted, fish is made
Pole.
2. the preparation method of porous graphene enhancing carbon fiber fishing rod according to claim 1, it is characterised in that described swollen
The expansion multiplying power of swollen graphite is more than 200.
3. the preparation method of porous graphene enhancing carbon fiber fishing rod according to claim 1, it is characterised in that the height
The shearing power 50-65Hz of fast cutter, shear time 10-60min.
4. the preparation method of porous graphene enhancing carbon fiber fishing rod according to claim 1, it is characterised in that the step
Suddenly(3)In solidification process for the carbon cloth of coiling and molding is toasted 10-50min at 60-80 DEG C first, then heat to
120-140 DEG C of constant temperature 1-4h, is finally air-cooled to room temperature.
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CN110983759A (en) * | 2019-12-19 | 2020-04-10 | 青岛墨金烯碳新材料科技有限公司 | Graphene modified carbon fiber pre-vulcanized fiber fabric and preparation method thereof |
CN111758685A (en) * | 2019-03-14 | 2020-10-13 | 古洛布莱株式会社 | Shaft for sporting goods or fishing tackle, manufacturing method, sporting goods and fishing tackle |
WO2021092788A1 (en) * | 2019-11-13 | 2021-05-20 | 远景能源有限公司 | Method and apparatus for use in manufacturing graphene-modified fiber reinforced material |
CN114655946A (en) * | 2022-04-28 | 2022-06-24 | 安徽碳华新材料科技有限公司 | High-flexibility graphene-like heat conduction structure prepared based on hydrothermal method |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN111758685A (en) * | 2019-03-14 | 2020-10-13 | 古洛布莱株式会社 | Shaft for sporting goods or fishing tackle, manufacturing method, sporting goods and fishing tackle |
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CN110983759A (en) * | 2019-12-19 | 2020-04-10 | 青岛墨金烯碳新材料科技有限公司 | Graphene modified carbon fiber pre-vulcanized fiber fabric and preparation method thereof |
CN114655946A (en) * | 2022-04-28 | 2022-06-24 | 安徽碳华新材料科技有限公司 | High-flexibility graphene-like heat conduction structure prepared based on hydrothermal method |
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