CN108000916B - 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
- Publication number
- CN108000916B CN108000916B CN201711129762.1A CN201711129762A CN108000916B CN 108000916 B CN108000916 B CN 108000916B CN 201711129762 A CN201711129762 A CN 201711129762A CN 108000916 B CN108000916 B CN 108000916B
- Authority
- CN
- China
- Prior art keywords
- graphene
- carbon fiber
- fishing rod
- single layered
- porous graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 300
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 208
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 60
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 60
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 69
- 239000006185 dispersion Substances 0.000 claims abstract description 63
- 239000004744 fabric Substances 0.000 claims abstract description 49
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 24
- 239000010439 graphite Substances 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 239000002356 single layer Substances 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 18
- 238000007711 solidification Methods 0.000 claims abstract description 13
- 230000008023 solidification Effects 0.000 claims abstract description 13
- 238000001694 spray drying Methods 0.000 claims abstract description 8
- 241000251468 Actinopterygii Species 0.000 claims abstract description 6
- 238000005520 cutting process Methods 0.000 claims abstract 2
- 238000004513 sizing Methods 0.000 claims description 36
- 239000000835 fiber Substances 0.000 claims description 28
- 239000010410 layer Substances 0.000 claims description 26
- 238000000465 moulding Methods 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 238000010008 shearing Methods 0.000 claims description 17
- 239000003822 epoxy resin Substances 0.000 claims description 14
- 229920000647 polyepoxide Polymers 0.000 claims description 14
- 230000005855 radiation Effects 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 8
- 238000001994 activation Methods 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 230000008961 swelling Effects 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 230000004087 circulation Effects 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 4
- -1 carbon fiber Compound Chemical class 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 210000000262 cochlear duct Anatomy 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01K—ANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
- A01K87/00—Fishing rods
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Carbon And Carbon Compounds (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a kind of preparation methods 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 removed into graphene microchip dispersion liquid first, graphene microchip powder is made in spray drying, the porous graphene predecessor of single layer is made in microwave treatment in NMP dispersion liquid after aoxidizing, finally this predecessor is activated with highly basic, obtain that hole is abundant, the biggish single layered porous graphene in aperture, again with the compound obtained carbon fiber cloth material of carbon fiber, fishing rod finally is rolled into through cutting out;While single layered porous graphene of the invention can easily coat carbon fiber, enough channels are provided again for circulation of the resin between carbon cloth in fishing rod solidification process, so that forming the good organic whole of continuity between graphene and carbon fiber and carbon fiber itself, and then the stretching buckling strength of carbon fiber fishing rod is greatly improved, it significantly increases fishing rod and fishes 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 enhancing carbon fiber fishing rod
Preparation method.
Background technique
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 mold, formed by unit time 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, the fishing rod of most of top grades mostly uses such skill both at home and abroad
Art;But since carbon fibre has rigidity strong, the low feature of flexibility, the intensity that hangs within 45 degree compares under normal conditions
It is good, but to enter intensity lower for 90 degree of strand.
Current common fishing rod uses in long-term high-intensitive high-frequency situation, and intensity and toughness, which can decline, to be compared
Fastly, lower for the low-angle strength resistance of moment, the service life of product is shorter and long-time service rigidity can also decline, and makes
With the tonality that cannot reach original design after a certain period of time, do not meet in requirement that is high-intensitive, being used under high-frequency.
It is but also most hard nano material that graphene, which is most thin in the world at present, has intensity height, large specific surface area, height
The characteristics of chemical reactivity, high fillibility, it is 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 is then placed in graphene and is received
It is impregnated in rice piece suspension up to the carbon cloth of surface attachment graphene nanometer sheet, this method can make graphene nanometer sheet equal
It is adhered to carbon fiber surface evenly, is present in the interlayer of carbon cloth, the interlayer that fibrous composite is significantly improved after solidification is cut
Shearing stress, bending strength and longitudinal thermal conductivity.But carbon cloth made from this method be applied to fishing rod when there is also
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 molding, solidification initial stage uses low-temperature heat is that resin is allowed to circulate between carbon fiber, is made in carbon fiber
Resin uniformly and bond integral, and the barrier 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, lead to attachment force deficiency between graphene and carbon fiber, is made into fishing rod
It is easily broken under the use of high-frequency high intensity afterwards.
In addition, since carbon fiber surface activity is low, it is poor with resin matrix wellability, it is easy to cause the interlayer of composite material to cut
Shearing stress reduces, and it is modified that the Chinese invention patent that notification number is CN102787488B discloses a kind of graphene oxide splicing surface
The method of carbon fiber is greatly improved by making graphene oxide in carbon fiber surface uniform fold graphene oxide functionalization
The roughness of carbon fiber surface, to act on the interface performance for improving carbon fibre reinforced composite by anchoring.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 mold
On release agent react, cause fishing rod rod body can not be with mould separating, therefore the composite material of this technique preparation is uncomfortable
Preferably it is used for the production of fishing rod.
Summary of the invention
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide a kind of single layered porous graphene increasing
The preparation method of strong carbon fiber fishing rod, initiatively by the porous graphene of single layer and the compound preparation for being used for fishing rod of carbon fiber,
It is intended to that the single-layer graphene of high-intensitive high-flexibility is made to be coated on carbon fiber surface, tensile strength, the bending for improving carbon fiber are strong
Degree, and binding force is good, cladding is easy;The porous structure of graphene is that the resin circulation in fishing rod forming process in carbon cloth mentions simultaneously
Guarantee sufficiently to infiltrate resin between carbon fiber, between carbon fiber and graphene for channel, organic whole is formed after solidification, to make
Fishing rod has superhigh intensity.
The technical scheme to solve the above technical problems is that a kind of single layered porous graphene enhances carbon fiber fishing rod
Preparation method, which is characterized in that as follows carry out:
(1) preparation of single layered porous graphene:
A, it in terms of 100 parts of total weight number, takes 1-5 parts of expanded graphites to be scattered in the solvent dissolved with dispersing agent, passes through height
Fast cutter carries out high speed shear removing, and the expanded graphite of vermicular texture is removed into 10 layers of laminated structure below, is obtained
Graphene microchip dispersion liquid;Effect is removed to expanded graphite, by the removing of the expanded graphite of vermicular texture at 10 layers with
Under laminated structure, facilitate further oxidation processes;
The dispersant weight is the 30-80% of expanded graphite, and surplus is solvent;
The solvent uses one of deionized water, NMP, DMF, and the dispersing agent uses CMC, SDS, PVP, BYK163
One of;
B, above-mentioned graphene microchip dispersion liquid is stood into 8-24h, takes upper layer stable dispersions, be made using spray drying process
The graphene microchip powder of removing;Due to after standing in the stable dispersion liquid in upper layer there are graphene microchip agglomeration is less,
Therefore it can guarantee that obtained graphene microchip is 10 layers of state below, to do base for the subsequent single-layer graphene for preparing
Plinth;
C, it takes above-mentioned graphene microchip powder 1-3g to be added into the 100-150ml concentrated sulfuric acid, 5-20ml is added while stirring
H2O2In solution, it is persistently stirred to react 20-90min at room temperature, obtains graphene oxide dispersion;It is such first to remove graphite
The technique for carrying out oxidation processes again at the very thin microplate of 10 layers of thickness below, can guarantee in every layer of graphene microchip and edge
There will be a functional group, oxidation effectiveness is much better than direct oxidation processing graphite, is more convenient for subsequent obtaining the high graphite of single layer rate
Alkene;
The H2O2The concentration of solution is 35-50%;
D, above-mentioned graphene oxide dispersion is first washed with deionized to neutrality, then is sufficiently washed with NMP complete to NMP
Total replacement falls the deionized water in graphene oxide dispersion, obtains graphene oxide NMP dispersion liquid;Effect is will be low-boiling
Solvent deionized water is replaced as high boiling NMP, and wherein the boiling point of NMP is 203 DEG C, higher than the reduction temperature of graphene oxide
150-200℃;
E, by above-mentioned graphene oxide NMP dispersion liquid be ultrasonically treated 1-6h, by 10 layers of graphene oxide microplate below into
The secondary removing of row;Purpose is to keep graphene oxide sheet peeling-off again under ultrasonication, reduces and reunites, and guarantees single layer rate;
F, the graphene oxide NMP dispersion liquid after ultrasonic treatment is subjected to microwave radiation processing, microwave spoke under 300-900W
3-10min is penetrated to NMP whole all burnt, NMP volatilizees and burns under microwave action, and graphene oxide burns in NMP to be generated
Heat effect issue raw reduction reaction and again it is swelling formed single layer surface with hole configurations single layered porous graphene
Predecessor;
G, above-mentioned single layered porous graphene predecessor is taken to mix with 0.5-15gKOH, in N2Under protection in tube furnace 400-
Activation 0.5-4h is carried out at 1000 DEG C, obtains single layered porous graphene, it is bigger that hole enriches aperture.
Since the temperature of NMP volatilization (203 DEG C) and burning is higher than the reduction temperature of graphene oxide in microwave process
(150-200 DEG C), therefore can guarantee that graphene oxide sufficiently restores, the decomposition of graphene oxide functional group can generate huge at this time
Big pressure makes the graphene oxide swelling graphene for obtaining single layer again, while the burning of NMP and the vigorous reaction of functional group
A large amount of holes can be respectively formed on every layer of graphene film surface, finally increase the activation process of a step highly basic, further increase
Pore quantity grade aperture on graphene sheet layer, ultimately form single layer has porous graphene film, this graphene film
Layer is very thin, therefore there is superior flexibility and biggish diameter graphene to be made to be easy to be coated on carbon fiber, while more
The structure in hole can guarantee the circulation of resin in carbon cloth, substantially increase the connectivity of the resin in carbon cloth, make stone
Black alkene more combines with carbon fiber.
(2) 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 is adopted
With epoxy resin, the weight ratio of single layered porous graphene and sizing agent is 1 ︰ 100-1 ︰ 1000;Effect is to be conducive to graphene coated
In carbon fiber surface, stretching and the buckling strength of carbon fiber are improved;
B, carbon fibre tow leaching is placed in above-mentioned graphene sizing system, is obtained after sufficiently soaking through single layered porous graphite
The carbon fibre tow of alkene cladding, then, then carbon fibre tow is laid in the release paper for being coated with epoxy resin, is made by squeezing
For at carbon cloth;
(3) above-mentioned carbon cloth is cut out, through mold coiling and molding, is then placed in curing molding in sintering oven, system
At fishing rod.
Further, the expansion multiplying power of the expanded graphite is greater than 200, so that graphene sheet layer is easier 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 column pitch is larger, and expanded graphite passes through cutter in stripping process
Slit when be stripped and come under huge revolving speed, due to the very narrow only several nanometers of slit, can guarantee to be stripped
Lamella at 10 layers or less.
Further, the solidification process in the step (3) is 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, guarantees fishing rod
The uniform content of middle each section resin then heats to 120-140 DEG C of constant temperature 1-4h, at this temperature resin crosslinking curing, fish
Pole molding, is finally air-cooled to room temperature.
The beneficial effects of the present invention are:
1. by carrying out the system that modification is used for carbon fiber fishing rod to carbon fiber with the graphene with porous structure of single layer
It is standby, due to graphene larger piece diameter and excellent flexibility, while so that graphene easily coats carbon fiber, and it is solid for fishing rod
Circulation of the resin between carbon cloth provides enough channels during change, so that graphene and carbon fiber and carbon fiber are certainly
The good organic whole of continuity is formed between body, and then greatly improves the stretching buckling strength of carbon fiber fishing rod, significantly increases fish
Fishing pole weight;
First expanded graphite is removed into predispersion 2. technique of the invention passes through, then carries out the preparation method of oxidation processes
Compared with traditional handicraft, the oxidation of lamella that expanded graphite can be made to remove is more thorough, and the single layer rate of gained graphene can be with
It increases substantially and functional group rich on every layer of graphene;
It is ultrasonically treated 3. technique of the invention first disperses the graphene oxide containing abundant functional group in NMP,
Weaken reunion situation, then be placed in micro-wave oven and carry out microwave radiation, the reduction temperature of graphene oxide is higher than using the boiling point of NMP
Degree, therefore graphene oxide is quickly restored during microwave radiation, surface functional group, which decomposes rapidly bring immense pressure, to be made
Graphene film reexpands, and obtains the graphene of single layer, while the vigorous combustion of NMP makes graphene surface form a large amount of hole
Hole, highly basic activation process can further increase pore quantity and the aperture of graphene surface, and the porous structure of formation is
Circulation of the resin between carbon cloth provides sufficient channel when fishing rod solidifies.
Specific embodiment
Embodiment 1
A kind of preparation method of single layered porous graphene enhancing carbon fiber fishing rod, carries out as follows:
(1) preparation of single layered porous graphene:
A, in terms of 100 parts of total weight number, 1 part of expanded graphite is taken to be scattered in the deionized water dissolved with 0.3 part of CMC, it is remaining
Amount is deionized water, carries out high speed shear removing by high-speed shearing machine, obtains graphene microchip dispersion liquid, high-speed shearing machine
The expansion multiplying power of shearing power 50Hz, shear time 10min, expanded graphite are greater than 200;
B, above-mentioned graphene microchip dispersion liquid is stood into 8h, takes upper layer stable dispersions, stripping is made using spray drying process
From graphene microchip powder;
C, above-mentioned graphene microchip powder 1g is taken to be added into the 100ml concentrated sulfuric acid, it is 35% that 5ml concentration is added while stirring
H2O2In solution, it is persistently stirred to react 20min at room temperature, obtains graphene oxide dispersion;
D, above-mentioned graphene oxide dispersion is first washed with deionized to neutrality, then is sufficiently washed with NMP complete to NMP
Total replacement falls the deionized water in graphene oxide dispersion, obtains graphene oxide NMP dispersion liquid;
E, above-mentioned graphene oxide NMP dispersion liquid is ultrasonically treated 1h;
F, the graphene oxide NMP dispersion liquid after ultrasonic treatment is subjected to microwave radiation processing, microwave radiation under 300W
3min obtains single layered porous graphene predecessor to NMP whole all burnt;
G, above-mentioned single layered porous graphene predecessor is taken to mix with 0.5gKOH, in N2Under protection in tube furnace at 400 DEG C
Activation 0.5h is carried out, the bigger single layered porous graphene in the richer aperture of hole is obtained.
(2) 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 is adopted
With epoxy resin, the weight ratio of 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 sufficiently soaking through porous graphene packet
Then the carbon fibre tow covered, then carbon fibre tow is laid in the release paper for being coated with epoxy resin, is prepared by extruding
Carbon cloth;
(3) above-mentioned carbon cloth is cut out, through mold coiling and molding, is then placed in curing molding in sintering oven, system
At fishing rod, wherein solidification process is that the carbon cloth of coiling and molding is toasted 10min at 60 DEG C first, then heats to 120
DEG C constant temperature 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) preparation of single layered porous graphene:
A, in terms of 100 parts of total weight number, 3 parts of expanded graphites are taken to be scattered in the NMP dissolved with 1.5 parts of SDS, surplus is
NMP carries out high speed shear removing by high-speed shearing machine, obtains graphene microchip dispersion liquid, the shearing power of high-speed shearing machine
The expansion multiplying power of 58Hz, shear time 35min, expanded graphite are greater than 200;
B, above-mentioned graphene microchip dispersion liquid is stood into 16h, takes upper layer stable dispersions, stripping is made using spray drying process
From graphene microchip powder;
C, above-mentioned graphene microchip powder 2g is taken to be added into the 120ml concentrated sulfuric acid, 15ml concentration is added while stirring is
45%H2O2In solution, it is persistently stirred to react 35min at room temperature, obtains graphene oxide dispersion;
D, above-mentioned graphene oxide dispersion is first washed with deionized to neutrality, then is sufficiently washed with NMP complete to NMP
Total replacement falls the deionized water in graphene oxide dispersion, obtains graphene oxide NMP dispersion liquid;
E, above-mentioned graphene oxide NMP dispersion liquid is ultrasonically treated 4h;
F, the graphene oxide NMP dispersion liquid after ultrasonic treatment is subjected to microwave radiation processing, microwave radiation under 600W
6min obtains single layered porous graphene predecessor to NMP whole all burnt;
G, above-mentioned single layered porous graphene predecessor is taken to mix with 10gKOH, in N2Under protection in tube furnace at 800 DEG C
Activation 2h is carried out, the bigger single-layer graphene in the richer aperture of hole is obtained.
(2) 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 is adopted
With epoxy resin, the weight ratio of 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 sufficiently soaking through porous graphene packet
Then the carbon fibre tow covered, then carbon fibre tow is laid in the release paper for being coated with epoxy resin, is prepared into carbon by extruding
Fiber cloth;
(3) above-mentioned carbon cloth is cut out, through mold coiling and molding, is then placed in curing molding in sintering oven, system
At fishing rod, wherein solidification process is that the carbon cloth of coiling and molding is toasted 30min at 70 DEG C first, then heats to 130
DEG C constant temperature 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) preparation of single layered porous graphene:
A, in terms of 100 parts of total weight number, 5 parts of expanded graphites are taken to be scattered in the DMF dissolved with 4.2 parts of PVP, surplus is
DMF carries out high speed shear removing by high-speed shearing machine, obtains graphene microchip dispersion liquid, the shearing power of high-speed shearing machine
The expansion multiplying power of 65Hz, shear time 60min, expanded graphite are greater than 200;
B, above-mentioned graphene microchip dispersion liquid is stood for 24 hours, takes upper layer stable dispersions, stripping is made using spray drying process
From graphene microchip powder;
C, above-mentioned graphene microchip powder 3g is taken to be added into the 150ml concentrated sulfuric acid, 20ml concentration is added while stirring is
50%H2O2In solution, it is persistently stirred to react 90min at room temperature, obtains graphene oxide dispersion;
D, above-mentioned graphene oxide dispersion is first washed with deionized to neutrality, then is sufficiently washed with NMP complete to NMP
Total replacement falls the deionized water in graphene oxide dispersion, obtains graphene oxide NMP dispersion liquid;
E, above-mentioned graphene oxide NMP dispersion liquid is ultrasonically treated 6h;
F, the graphene oxide NMP dispersion liquid after ultrasonic treatment is subjected to microwave radiation processing, microwave radiation under 900W
10min obtains single layered porous graphene predecessor to NMP whole all burnt;
G, above-mentioned single layered porous graphene predecessor is taken to mix with 15gKOH, in N2Under protection in tube furnace at 1000 DEG C
Activation 4h is carried out, hole is obtained and enriches the bigger single-layer graphene in aperture.
(2) 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 is adopted
With epoxy resin, the weight ratio of 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 sufficiently soaking through porous graphene packet
Then the carbon fibre tow covered, then carbon fibre tow is laid in the release paper for being coated with epoxy resin, is prepared by extruding
Carbon cloth;
(3) above-mentioned carbon cloth is cut out, through mold coiling and molding, is then placed in curing molding in sintering oven, system
At fishing rod, wherein solidification process is that the carbon cloth of coiling and molding is toasted 50min at 80 DEG C first, then heats to 140
DEG C constant temperature 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 mold coiling and molding, is then set
Enter curing molding in sintering oven, be finally prepared to fishing rod, wherein solidification process is first by the carbon cloth of coiling and molding
30min is toasted at 70 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) preparation of single-layer graphene:
A, in terms of 100 parts of total weight number, 3 parts of expanded graphites are taken to be scattered in the NMP dissolved with 1.5 parts of SDS, surplus is
NMP carries out high speed shear removing by high-speed shearing machine, obtains graphene microchip dispersion liquid, the shearing power of high-speed shearing machine
The expansion multiplying power of 58Hz, shear time 35min, expanded graphite are greater than 200;
B, above-mentioned graphene microchip dispersion liquid is stood into 16h, takes upper layer stable dispersions, stripping is made using spray drying process
From graphene microchip powder;
C, above-mentioned graphene microchip powder 2g is taken to be added into the 120ml concentrated sulfuric acid, 15ml concentration is added while stirring is
45%H2O2In solution, it is persistently stirred to react 35min at room temperature, obtains graphene oxide dispersion;
D, above-mentioned graphene oxide dispersion is prepared into powder by spray drying and is placed on N in 400 DEG C of tube furnace2
The lower thermal reduction 2h of protection obtains the graphene powder of single layer.
(2) single-layer graphene/carbon fiber Compound Fabric preparation:
A, it disperses above-mentioned single-layer graphene powder in sizing agent, obtains graphene sizing system;The sizing agent is adopted
With epoxy resin, the weight ratio of 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 sufficiently soaking through porous graphene packet
Then the carbon fibre tow covered, then carbon fibre tow is laid in the release paper for being coated with epoxy resin, is prepared by extruding
Carbon cloth;
(3) above-mentioned carbon cloth is cut out, through mold coiling and molding, is then placed in curing molding in sintering oven, system
At fishing rod, wherein solidification process is that the carbon cloth of coiling and molding is toasted 30min at 70 DEG C first, then heats to 130
DEG C constant temperature 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
It carries out:
(1) preparation of porous graphene:
A, crystalline flake graphite 2g is taken to be added into the 120ml concentrated sulfuric acid, it is 45%H that 15ml concentration is added while stirring2O2Solution
In, it is persistently stirred to react 35min at room temperature, obtains graphene oxide dispersion;
B, above-mentioned graphene oxide dispersion is first washed with deionized to neutrality, then is sufficiently washed with NMP complete to NMP
Total replacement falls the deionized water in graphene oxide dispersion, obtains graphene oxide NMP dispersion liquid;
C, the graphene oxide NMP dispersion liquid after ultrasonic treatment is subjected to microwave radiation processing, microwave radiation under 600W
6min obtains porous graphene powdered precursor to NMP whole all burnt;
D, above-mentioned porous graphene predecessor is taken to mix with 10gKOH, in N2It is carried out at 800 DEG C in tube furnace under protection
2h is activated, the bigger graphene in the richer aperture of hole is obtained.
(2) porous graphene/carbon fiber Compound Fabric preparation:
A, it disperses above-mentioned porous graphene powder in sizing agent, obtains graphene sizing system;The sizing agent is adopted
With epoxy resin, the weight ratio of 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 sufficiently soaking through porous graphene packet
Then the carbon fibre tow covered, then carbon fibre tow is laid in the release paper for being coated with epoxy resin, is prepared by extruding
Carbon cloth;
(3) above-mentioned carbon cloth is cut out, through mold coiling and molding, is then placed in curing molding in sintering oven, system
At fishing rod, wherein solidification process is that the carbon cloth of coiling and molding is toasted 30min at 70 DEG C first, then heats to 130
DEG C constant temperature 2h, is finally air-cooled to room temperature.
Above-described embodiment and comparative example be made to the fishing rod of identical size, it is respectively 5 sections, 5.4 meters long, and use
QBT1476-2004 standard detects 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 of production is fished again than the fish in embodiment
Pole lacks 1150g or more, and it is rigidly strong that this is mainly due to carbon cloths, and the reason of flexibility difference can be broken under high intensity;
Fishing rod in comparative example 2, which fishes, reduces 700g or more than the fishing rod in embodiment again, this is because using mono-layer graphite
Alkene modifies carbon fiber, although the ultra-thin super flexible lamellar structure of graphene is easy to be coated on rigid carbon fiber surface
Face, but complete graphene has excellent barrier action, and the circulation of resin can be hindered in fishing rod solidification process, leads to carbon fiber
It is only connected by faint sizing agent between dimension and graphene, attachment force is extremely weak, and in addition the presence of graphene can also hinder carbon cloth
In circulation of the epoxy resin between carbon fiber layer, lead in fishing rod that local resin content is few, intensity is small, therefore easily occurs disconnected
It splits;
The fishing of 3 finished fishing rods of comparative example again than embodiment also than reduce 600g or more, this is because the method is using common
The porous graphene of three-dimensional structure, due to the limitation of preparation method, more serious such graphene agglomeration is in three-dimensional structure,
Flexibility is poor, and compactness is poor between carbon fiber compound tense and rigid carbon-fiber, although the problem of there is no resin circulations,
But three-dimensional porous graphene cannot be coated on carbon fiber surface completely, therefore limited to the reinforcing effect of carbon fiber.
Therefore, the present invention has significant creative feature.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (4)
1. a kind of preparation method of single layered porous graphene enhancing carbon fiber fishing rod, which is characterized in that carry out as follows:
(1) preparation of single layered porous graphene:
A, in terms of 100 parts of total weight number, 1-5 parts of expanded graphites are taken to be scattered in the solvent dissolved with dispersing agent, by cutting at a high speed
It cuts machine and carries out high speed shear removing, the expanded graphite of vermicular texture is removed into 10 layers of laminated structure below, graphite is obtained
Alkene microplate dispersion liquid;
The dispersant weight is the 30-80% of expanded graphite, and surplus is solvent;
The solvent uses one of deionized water, NMP, DMF, and the dispersing agent is using in CMC, SDS, PVP, BYK163
It is a kind of;
B, above-mentioned graphene microchip dispersion liquid is stood into 8-24h, takes upper layer stable dispersions, removing is made using spray drying process
Graphene microchip powder;
C, it takes above-mentioned graphene microchip powder 1-3g to be added into the 100-150ml concentrated sulfuric acid, 5-20ml H is added while stirring2O2
In solution, it is persistently stirred to react 20-90min at room temperature, obtains graphene oxide dispersion;
The H2O2The concentration of solution is 35-50%;
D, above-mentioned graphene oxide dispersion is first washed with deionized to neutrality, then is sufficiently washed to NMP with NMP and is set completely
The deionized water in graphene oxide dispersion is changed, graphene oxide NMP dispersion liquid is obtained;
E, above-mentioned graphene oxide NMP dispersion liquid is ultrasonically treated 1-6h, 10 layers of graphene oxide microplate below is carried out two
Secondary removing;
F, the graphene oxide NMP dispersion liquid after ultrasonic treatment is subjected to microwave radiation processing, microwave radiation 3- under 300-900W
10min is volatilized and is burnt under microwave action to NMP whole all burnt, NMP, the heat that graphene oxide is generated in NMP burning
Amount effect issues raw reduction reaction and the swelling surface for forming single layer has the single layered porous graphene forerunner of hole configurations again
Object;
G, above-mentioned single layered porous graphene predecessor is taken to mix 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) 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 resin, single layered porous graphene and sizing agent is 1 ︰ 100-1 ︰ 1000;
B, carbon fibre tow leaching is placed in above-mentioned graphene sizing system, is obtained after sufficiently soaking through single layered porous graphene packet
Then the carbon fibre tow covered, then carbon fibre tow is laid in the release paper for being coated with epoxy resin, is prepared by extruding
Carbon cloth;
(3) above-mentioned carbon cloth is cut out, through mold coiling and molding, is then placed in curing molding in sintering oven, fish is made
Pole.
2. the preparation method of porous graphene enhancing carbon fiber fishing rod according to claim 1, which is characterized in that described swollen
The expansion multiplying power of swollen graphite is greater than 200.
3. the preparation method of porous graphene enhancing carbon fiber fishing rod according to claim 1, which is characterized 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, which is characterized in that the step
Suddenly the solidification process in (3) is that the carbon cloth of coiling and molding is toasted 10-50min at 60-80 DEG C first, is then heated to
120-140 DEG C of constant temperature 1-4h, is finally air-cooled to room temperature.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711129762.1A CN108000916B (en) | 2017-11-15 | 2017-11-15 | A kind of preparation method of single layered porous graphene enhancing carbon fiber fishing rod |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711129762.1A CN108000916B (en) | 2017-11-15 | 2017-11-15 | A kind of preparation method of single layered porous graphene enhancing carbon fiber fishing rod |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108000916A CN108000916A (en) | 2018-05-08 |
CN108000916B true CN108000916B (en) | 2019-08-02 |
Family
ID=62052847
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711129762.1A Active CN108000916B (en) | 2017-11-15 | 2017-11-15 | A kind of preparation method of single layered porous graphene enhancing carbon fiber fishing rod |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108000916B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020146268A (en) * | 2019-03-14 | 2020-09-17 | グローブライド株式会社 | Golf club and method for manufacturing shaft of golf club |
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 |
CN110983759B (en) * | 2019-12-19 | 2022-08-02 | 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 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SG186811A1 (en) * | 2010-06-25 | 2013-02-28 | Univ Singapore | Methods of forming graphene by graphite exfoliation |
CN102787488B (en) * | 2012-07-30 | 2013-12-25 | 哈尔滨工业大学 | Method for preparing graphene oxide grafting surface modification carbon fiber |
US10064400B2 (en) * | 2015-06-02 | 2018-09-04 | G-Rods International Llc | Fishing rod with graphene and method of manufacturing |
-
2017
- 2017-11-15 CN CN201711129762.1A patent/CN108000916B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN108000916A (en) | 2018-05-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108000916B (en) | A kind of preparation method of single layered porous graphene enhancing carbon fiber fishing rod | |
CN103046151B (en) | Graphene blend regenerated cellulose fiber and preparation method thereof | |
JP5097203B2 (en) | Planar heating element using carbon microfiber and method for producing the same | |
KR101726822B1 (en) | Ultrafine carbon fibers and their preparation method | |
CN105648579A (en) | Superfine graphene fibers and method for preparing same | |
CN105355949A (en) | Preparation method of nanofiber composite proton exchange membrane | |
WO2017214741A1 (en) | Process for preparing chitosan/polyvinyl alcohol composite electrically-conductive nanofibre | |
CN104963098A (en) | Method for preparing electrostatic spinning perfluocarbon polymer nanofiber membrane | |
CN111809406A (en) | Method for manufacturing superfine fiber suede leather with electromagnetic shielding function | |
JP7031778B2 (en) | Gas diffusion layer and gas diffusion electrode for polymer electrolyte fuel cells and their manufacturing method | |
CN108058417B (en) | A kind of preparation method of graphene elasticity screen cloth enhancing carbon fiber fishing rod | |
CN102615840A (en) | Production equipment and using method for thermoplastic pultrusion product | |
CN109371475A (en) | A kind of spinning process of ultra-high molecular weight polyethylene | |
JP2019534231A (en) | Method for producing graphite sheet | |
KR102191092B1 (en) | Thermoplastic resin matrix fiber and carbon fiber-reinforced thermoplastic plastic composite having excellent impregnation property produced therefrom and manufacturing method thereof | |
CN109098029A (en) | A kind of manufacturing method of novel carbon fiber heating paper | |
CN103114495B (en) | A kind of carbon paper for electrode diffusion layer of fuel cell and preparation method thereof | |
Yao et al. | Biomimetic and flexible high-performance carbon paper prepared by welding three-dimensional carbon fiber network with polyphenylene sulfide spherical sites for fuel cell gas diffusion layer | |
CN103448251B (en) | For the preparation of the polytetrafluoroethylfiber fiber film of superfine fibre | |
CN107916580A (en) | A kind of preparation method of weatherability high-strength waterproof cloth | |
JP5297701B2 (en) | Method for producing electrode substrate for polymer electrolyte fuel cell | |
WO2016159352A1 (en) | Porous electrode base material and manufacturing method therefor | |
CN102154723B (en) | Method for preparing polyacrylonitrile-based carbon fiber precursors without skin-core structure | |
CN106044742A (en) | Method for preparing pitch-based carbon fiber self-bonding network material | |
CN108642884A (en) | The preparation method and its resulting materials of a kind of painted graphite alkene fiber and application |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |