CN106637923A - Method of quickly and continuously depositing graphene on surface of electric-conductive fibers - Google Patents

Method of quickly and continuously depositing graphene on surface of electric-conductive fibers Download PDF

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Publication number
CN106637923A
CN106637923A CN201610907586.9A CN201610907586A CN106637923A CN 106637923 A CN106637923 A CN 106637923A CN 201610907586 A CN201610907586 A CN 201610907586A CN 106637923 A CN106637923 A CN 106637923A
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graphene
conductive fiber
graphene oxide
carbon fiber
successive sedimentation
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黄玉东
王彩凤
黎俊
孙少凡
刘丽
赵敏
谢飞
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating 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
    • D06M11/73Treating 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
    • D06M11/74Treating 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
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00Electrophoretic coating characterised by the process
    • C25D13/02Electrophoretic coating characterised by the process with inorganic material
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16Synthetic fibres, other than mineral fibres
    • D06M2101/18Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16Synthetic fibres, other than mineral fibres
    • D06M2101/30Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40Fibres of carbon

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

A method of quickly and continuously depositing graphene on surface of electric-conductive fibers. The invention relates to the technical field of surface modification of electric-conductive fibers and aims to solve the problems that a conventional electrophoretic deposition method in the prior art is long in electrophoretic time, is not-homogeneous in deposition and is low in increase range on mechanical performances of the electric-conductive fibers. The method includes the steps of: 1) preparing an graphene oxide solution; 2) desizing the electric-conductive fibers; 3) preparing an electrophoretic solution; 4) performing electrophoretic deposition of graphene oxide with ultrasonic assistance; and 5) thermal-reducing the electric-conductive fibers on which the graphene oxide is deposited. The method is used for surface modification for fibers.

Description

A kind of method in the quick successive sedimentation Graphene of conductive fiber surfaces
Technical field
The present invention relates to the modified technical field of conductive fiber surfaces.
Background technology
Carbon fiber (CF) has high specific strength and specific modulus, light weight, high temperature resistant, resistance to chemical attack, heat conduction and electric conductivity It is excellent, it is a kind of important structural material reinforcement the features such as thermal coefficient of expansion is little, carbon fiber and carbon fibre composite exist The fields such as Aero-Space, defence and military, machine-building are widely used.
The interface binding intensity of carbon fiber and matrix is the mechanical property principal element for determining carbon fibre composite, well Interface cohesion can effectively transmit stress, and then improve the mechanical property of material.But, undressed carbon fiber surface Inertia is big, weaker with the interface cohesion of resin matrix, so as to have impact on giving full play to for carbon fibre composite excellent properties.It is logical Often carbon fiber is surface-treated, to strengthen the interface binding intensity of its composite, so as to improve the boundary of composite Face mechanical property.Graphene imparts its excellent physics, chemistry, calorifics, optics and mechanics etc. with its unique honeycomb Performance.Especially Graphene can promote polymer composite and Graphene in polymer composite as phase is strengthened Between stress transmission.
Conventional carbon fiber surface modification method mainly has chemical vapor deposition, coating and chemical graft etc., these methods Can introduce Graphene to improve its interface performance between resin on the surface of carbon fiber, but often lead to its mechanical property The greater loss of energy, pollutes environment, and efficiency is low and cumbersome, is difficult industrialization.In recent years, the side of useful electrophoretic deposition Method can improve fibre in carbon fiber surface deposited oxide Graphene or CNT on the premise of fibrous mechanical property is not damaged The interface performance of dimension resin.But some shortcomings are there is also, as sedimentation time length, deposits uneven, and typically all do electricity with water , there is electrolysis water phenomenon in the solution of solution liquid, result in GO weak with the adhesion of carbon fiber during energization.Therefore, it is badly in need of at present a kind of New carbon fiber modifying technology, i.e., form the strong graphene layer of uniform, fine and close and adhesion in the short time in carbon fiber surface, to the greatest extent May strengthen the mechanical property of fiber while Interface Properties of Carbon Fibers Reinforced Composites is improved.The present invention adopts ultrasonic wave added Graphene oxide is deposited to continuous carbon fiber surface, and thermal reduction by electrophoretic deposition in isopropanol electrophoresis liquid, super It is prepared for a layer graphene layer in short time, it is to avoid GO reunites in electrophoresis process causes deposition uneven, while improve The mechanical property and interface performance of carbon fiber, and be expected to implement industrialization.
The content of the invention
The invention aims to solve the electrophoresis time length of conventional electrophoretic deposition process presence, deposit uneven and lead The little problem of electric fibrous mechanical property increase rate, and provide a kind of in the quick successive sedimentation Graphene of conductive fiber surfaces Method.
The method in the quick successive sedimentation Graphene of conductive fiber surfaces of the present invention is carried out according to the following steps:
First, the preparation of graphene oxide solution:By graphene oxide and dispersant in a solvent, using ultrasonic cleaning Machine 1~3h of ultrasound forms finely dispersed graphene oxide solution;
2nd, conductive fiber goes slurry to process:Conductive fiber beam and acetone are separately added into the extraction tube of apparatus,Soxhlet's and are carried In taking bottle, heat to the acetone in extraction flask, heating-up temperature is 75-85 DEG C, makes acetone gasify, and by connecting tube condensation is ascended into Device, the liquid that congeals into is instilled in extraction tube, extracts the sizing agent on conductive fiber beam surface;Acetone liquid level reaches necessarily in pipe to be extracted Highly, extraction flask is flowed into dissolved with the acetone Jing siphon pipes of sizing agent;Flow into the acetone in extraction flask to continue to be heated gasification, rise And condensation, then instill in extraction tube, so to move in circles, the time maintains 12-48h;
3rd, the preparation of electrophoresis liquid:Slaine is added in finely dispersed graphene oxide solution prepared by step one, 0.5~1h of ultrasound, metal ion can adsorb on the surface of graphene oxide, so that graphene oxide positively charged;Then use again 10~the 20min of centrifugation of 5000~10000r/min, takes supernatant, as electrophoresis liquid;
4th, ultrasonic wave added electrophoretic deposition graphene oxide:Ultrasonic wave added electrophoretic deposition system is in continuous carbon fiber bundle The reaction generating means of surface uniform deposition graphene oxide, it is, by electrophoresis apparatus, electrolytic cell, roller assembly, to be cleaned by ultrasonic instrument Composition;Roller assembly is put into electrolytic cell, and continuous conductive fiber beam is through roller bearing and submerges in electrophoresis liquid, stainless by punching Steel cylinder, then Jing roller bearings lay out electrolytic cell, the stainless steel cylinder that punches in a cell is connected as positive pole with the negative pole of electrophoresis apparatus, conduction Fiber is connected as negative pole with the positive pole of electrophoresis apparatus, and two electrode distances are 1~2cm, and on-load voltage is 120~180V;Overall Electrolytic cell is placed in ultrasonic cleaning instrument, under the collective effect of electric field and ultrasound, adsorbing metal ions and positively charged oxidation Graphene can be moved to the negative electrode with its oppositely charged, and then be adsorbed on the surface of conductive fiber;Deposition 30S~10 minute Afterwards, the conductive fiber ethanol of adsorption and oxidation Graphene and water are cleaned 1 minute respectively repeatedly, that is, obtains deposited oxide Graphene Conductive fiber;
5th, the conductive fiber of thermal reduction deposited oxide Graphene:The conductive fiber of the deposited oxide Graphene for preparing is put Heat 1-4h in 150-250 DEG C of vacuum drying oven, obtain the conductive fiber of thermal reduction deposited oxide Graphene.
The dispersant is PVP (PVP), glyceryl monostearate (GMS) or ethylene group bis-stearamides (EBS)。
The solvent is isopropanol, water, ethanol or dimethylformamide.
The conductive fiber is carbon fiber, polyacetylene fibres or polyaniline fiber.
The slaine is lithium perchlorate or magnesium nitrate.
Advantage of the present invention relative to prior art:
The present invention is the method using excusing from death auxiliary electrophoretic deposition, deposits to graphene oxide in aqueous isopropanol and leads Electric fiber surface and thermal reduction, the electrophoresis time for solving the presence of conventional electrophoretic deposition process is long, and tradition needs 1 hour or so, The present invention shorten to 30S~10min;The comparison that conventional electrophoretic deposited graphite alkene is reunited is more, and the present invention's does not reunite and deposit Uniformly;Fibrous mechanical property increase rate is little, and the mechanical property of conventional electrophoretic deposition conductive fiber improves 10% or so, the present invention 30%~40% can be improved and this kind of method also has environmental protection, it is dangerous low, the advantages of controllability is strong.In addition, at high temperature Epoxy ring-opening during reason in graphene oxide layer can occur chemical reaction with the oxygen-containing functional group of conductive fiber surfaces, Denatured conductive fibre reinforcement is set not only to there is mechanical engagement effect, the graphene oxide and conductive fiber of partial reduction with matrix Between formed chemical bond Graphene is firmly adsorbed in conductive fiber surfaces, improve the surface energy and wellability of conductive fiber Can, so as to enhance the shear strength of composite material interface.Meanwhile, the Graphene of small pieces can repair the defect of conductive fiber surfaces Further substantially increase the tensile strength of conductive fiber.
Description of the drawings
Fig. 1 is ultrasonic wave added electrophoretic deposition schematic diagram, wherein 1 is carbon fiber bundle, 2 is electrolytic cell, and 3 is to have children outside the state plan cleaning device, 4 For electrophoresis apparatus, 5 are punching stainless steel cylinder, and 6 is roller assembly, and 7 is electrophoresis liquid, and 8 is water.
Fig. 2 is the scanning electron microscope (SEM) photograph of the untreated carbon fiber of embodiment 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of carbon fiber after the deposited oxide Graphene of embodiment 1.
Fig. 4 is the scanning electron microscope (SEM) photograph of carbon fiber after the deposited oxide Graphene of embodiment 1.
Fig. 5 be embodiment 1 before modified after carbon fiber surface contact angle, wherein 1 for go starch carbon fiber, 2 be carbon fiber/ GO, 3 is carbon fiber/RGO, and 4 is the contact angle of water, and 5 is the contact angle of diiodomethane.
Fig. 6 be embodiment 1 before modified after carbon fiber surface energy, wherein 1 for go starch carbon fiber, 2 be carbon fiber/GO, 3 are Carbon fiber/RGO, 4 is capillary polar component, and 5 is capillary dispersive component.
Fig. 7 is that before modified the monofilament tensile strength of rear carbon fiber and the interface shearing of carbon fiber/epoxy resin are strong for embodiment 1 Degree, wherein 1 to go to starch carbon fiber, 2 is carbon fiber/GO, and 3 is carbon fiber/RGO, and 4 is monofilament tensile strength, and 5 is carbon fiber/ring The interface shear strength of oxygen tree fat.
Specific embodiment
Technical solution of the present invention is not limited to act specific embodiment set forth below, also including between each specific embodiment Any reasonable combination.
Specific embodiment one:The method in the quick successive sedimentation Graphene of conductive fiber surfaces of present embodiment press with Lower step is carried out:
First, the preparation of graphene oxide solution:By graphene oxide and dispersant in a solvent, using ultrasonic cleaning Machine 1~3h of ultrasound forms finely dispersed graphene oxide solution;
2nd, conductive fiber goes slurry to process:Conductive fiber beam and acetone are separately added into the extraction tube of apparatus,Soxhlet's and are carried In taking bottle, heat to the acetone in extraction flask, heating-up temperature is 75-85 DEG C, makes acetone gasify, and by connecting tube condensation is ascended into Device, the liquid that congeals into is instilled in extraction tube, extracts the sizing agent on conductive fiber beam surface;Acetone liquid level reaches necessarily in pipe to be extracted Highly, extraction flask is flowed into dissolved with the acetone Jing siphon pipes of sizing agent;Flow into the acetone in extraction flask to continue to be heated gasification, rise And condensation, then instill in extraction tube, so to move in circles, the time maintains 12-48h;
3rd, the preparation of electrophoresis liquid:Slaine is added in finely dispersed graphene oxide solution prepared by step one, 0.5~1h of ultrasound;Then supernatant is taken, as electrophoresis liquid with the 10~20min of centrifugation of 5000~10000r/min again;
4th, ultrasonic wave added electrophoretic deposition graphene oxide:Ultrasonic wave added electrophoretic deposition system is by electrophoresis apparatus, electrolytic cell, rolling Shaft device, is cleaned by ultrasonic instrument composition;Roller assembly is put into electrolytic cell, and continuous conductive fiber beam is through roller bearing and the electrophoresis that submerges In liquid, electrolytic cell is laid out by the stainless steel cylinder that punches, then Jing roller bearings, the stainless steel cylinder that punches in a cell is used as positive pole and electrophoresis The negative pole of instrument is connected, and conductive fiber is connected as negative pole with the positive pole of electrophoresis apparatus, and two electrode distances are 1~2cm, and on-load voltage is 120~180V;Overall electrolytic cell is placed in ultrasonic cleaning instrument, under the collective effect of electric field and ultrasound, adsorbing metal ions And positively charged graphene oxide can be moved to the negative electrode with its oppositely charged, and then adsorb the table in conductive fiber Face;Behind deposition 30S~10 minute, the conductive fiber ethanol of adsorption and oxidation Graphene and water are distinguished into cleaning 1 minute repeatedly, i.e., Obtain the conductive fiber of deposited oxide Graphene;
5th, the conductive fiber of thermal reduction deposited oxide Graphene:The conductive fiber of the deposited oxide Graphene for preparing is put Heat 1-4h in 150-250 DEG C of vacuum drying oven, obtain the conductive fiber of thermal reduction deposited oxide Graphene.
Specific embodiment two:From unlike specific embodiment one, the dispersant is polyethylene to present embodiment Than pyrrolidone, glyceryl monostearate or ethylene group bis-stearamides.Other steps are identical with specific embodiment one with parameter.
Specific embodiment three:Present embodiment from unlike specific embodiment one, the solvent be isopropanol, Water, ethanol or dimethylformamide.Other steps are identical with specific embodiment one with parameter.
Specific embodiment four:Present embodiment from unlike specific embodiment one, the graphene oxide and point The mass ratio of powder is 1:(0.5~8).Other steps are identical with specific embodiment one with parameter.
Specific embodiment five:Present embodiment from unlike specific embodiment one, the graphene oxide and point The mass ratio of powder is 1:1.Other steps are identical with specific embodiment one with parameter.
Specific embodiment six:Present embodiment from unlike specific embodiment one, the matter of the graphene oxide Amount is (0.5g~2g) with the volume ratio of solvent:(100mL~500mL).Other steps and parameter and the phase of specific embodiment one Together.
Specific embodiment seven:From unlike specific embodiment one, the conductive fiber is that carbon is fine to present embodiment Dimension, aramid fiber or poly- to penylene benzo-dioxazole fiber.Other steps are identical with specific embodiment one with parameter.
Specific embodiment eight:From unlike specific embodiment one, the slaine is perchloric acid to present embodiment Lithium or magnesium nitrate.Other steps are identical with specific embodiment one with parameter.
Specific embodiment nine:Present embodiment from unlike specific embodiment one, the slaine with oxidation stone The mass ratio of black alkene is 1:(0.5~2).Other steps are identical with specific embodiment one with parameter.
Embodiment 1
The method in the quick successive sedimentation Graphene of conductive fiber surfaces of the present embodiment is carried out according to the following steps:
First, the preparation of graphene oxide solution:1g graphene oxides and 1g PVPs are dispersed in into 300mL different In propyl alcohol, using supersonic cleaning machine ultrasound 2h finely dispersed graphene oxide solution is formed;
2nd, carbon fiber goes slurry to process:Carbon fiber bundle and acetone are separately added into the extraction tube and extraction flask of apparatus,Soxhlet's In, heating to the acetone in extraction flask, heating-up temperature is 80 DEG C, makes acetone gasify, and by connecting tube condenser is ascended into, and is congealed into Liquid is instilled in extraction tube, extracts the sizing agent on carbon fiber bundle surface;Acetone liquid level reach a certain height in pipe to be extracted, dissolved with The acetone Jing siphon pipes of sizing agent flow into extraction flask;Flow into the acetone in extraction flask to continue to be heated gasification, rise and condense, so Instill in extraction tube afterwards, so move in circles, the time maintains 18h;
3rd, the preparation of electrophoresis liquid:2g magnesium nitrates are added into finely dispersed graphene oxide solution prepared by step one In, ultrasonic 1h, magnesium ion can adsorb on the surface of graphene oxide, so that graphene oxide positively charged;Then use again The centrifugation 15min of 5000r/min, takes supernatant, as electrophoresis liquid;
4th, ultrasonic wave added electrophoretic deposition graphene oxide:Ultrasonic wave added electrophoretic deposition system is in continuous carbon fiber bundle The reaction generating means of surface uniform deposition graphene oxide, it is, by electrophoresis apparatus, electrolytic cell, roller assembly, to be cleaned by ultrasonic instrument Composition;Roller assembly is put into electrolytic cell, and continuous carbon fiber bundle is through roller bearing and submerges in electrophoresis liquid, by the stainless steel that punches Cylinder, then Jing roller bearings lay out electrolytic cell, the stainless steel cylinder that punches in a cell is connected as positive pole with the negative pole of electrophoresis apparatus, carbon fiber It is connected with the positive pole of electrophoresis apparatus as negative pole, two electrode distances are 2cm, and on-load voltage is 150V;Overall electrolytic cell is placed in super In sound cleaning device, under the collective effect of electric field and ultrasound, adsorbing metal ions and positively charged graphene oxide can to The negative electrode movement of its oppositely charged, and then adsorb on the surface of carbon fiber;After depositing 2 minutes, by adsorption and oxidation Graphene Carbon fiber ethanol and water clean 1 minute repeatedly respectively, that is, obtain the carbon fiber of deposited oxide Graphene;
5th, the carbon fiber of thermal reduction deposited oxide Graphene:The carbon fiber of the deposited oxide Graphene for preparing is placed in 200 Heat 2h in DEG C vacuum drying oven, obtain the carbon fiber of thermal reduction deposited oxide Graphene.
It is 2 minutes that the method for this excusing from death auxiliary electrophoretic deposition of the present embodiment shortens electrophoresis time;Scanning electron microscope (SEM) photograph can To find out that the GO of deposition is evenly distributed on the surface of carbon fiber;While fiber lifts 69.9% with the interface shear strength of resin Fibrous mechanical property lifts 34.6%;And continuous processing method contributes to industrialized production.
Fig. 2 is the scanning electron microscope (SEM) photograph of untreated carbon fiber.It can be seen that untreated carbon fiber surface is very smooth.Figure 3 is carbon fiber/GO, it can be seen that cover a thin layer graphene oxide after deposited oxide Graphene on carbon fiber surface, and Fig. 4 is Carbon fiber/RGO, heating rear oxidation Graphene ftractures to form the structure of this tilting, and the structure of this tilting can just increase fibre The mechanical interlocking of dimension and resin.
Fig. 5 is the contact angle for depositing the water of carbon fiber and diiodomethane after GO and thermal reduction.As can be seen that modified carbon The contact angle of fiber is reduced, and this is that also have a large amount of oxygen-containing reasons that can also roll into a ball GO due to deposited surface.Fig. 6 before modified after carbon The surface energy of fiber, it can be seen that modified surface energy increases, the surface energy highest of carbon fiber/GO, this is because it contains There are most polarity oxygen-containing functional groups.Fig. 7 be before modified after carbon fiber monofilament tensile strength and the boundary of carbon fiber epoxy Face shear strength.The monofilament tensile strength of modified carbon fiber is significantly improved, this is because the defect quilt of carbon fiber surface GO fills up reparation, while deposition equally has the GO of big π keys to act on the P-P of carbon fiber, contributes to energy absorption under loads.Carbon The intensity highest of fiber/RGO, this is because under high temperature, the epoxy radicals on GO surfaces and the hydroxyl of carbon fiber surface or carboxyl reaction Generate firm chemical bond.The interface shear strength of modified carbon fiber is significantly improved, and the surface energy on the one hand increasing is carried High wellability of the carbon fiber with epoxy resin, on the other hand the extra coarse degree of modified carbon fiber surface increase, increased fiber With the mechanical interlocking of resin.The interface shear strength highest of carbon fiber/RGO, this is because under high temperature, the epoxy radicals on GO surfaces Firm chemical bond is generated with the hydroxyl of carbon fiber surface or carboxyl reaction so that the adhesion between RGO and carbon fiber increases.
Constituent content before and after the electrophoresis of table 1 and heat treated carbon fiber
Table 1 is electrophoresis and the XPS constituent content analysis before and after heat treated carbon fiber.After deposition GO, carbon fiber/GO surfaces Oxygen element content increases, it was demonstrated that really deposition has gone up GO to carbon fiber surface.And after being heat-treated, the content of oxygen element decreases, But or go slurry carbon fiber high than untreated, it was demonstrated that reduction belongs to partial reduction.

Claims (9)

1. a kind of method in the quick successive sedimentation Graphene of conductive fiber surfaces, it is characterised in that:The method is according to the following steps Carry out:
First, the preparation of graphene oxide solution:By graphene oxide and dispersant in a solvent, it is super using supersonic cleaning machine 1~3h of sound forms finely dispersed graphene oxide solution;
2nd, conductive fiber goes slurry to process:Conductive fiber beam and acetone are separately added into the extraction tube and extraction flask of apparatus,Soxhlet's In, heating to the acetone in extraction flask, heating-up temperature is 75-85 DEG C, and the heat time is 12-48h;
3rd, the preparation of electrophoresis liquid:Slaine is added in finely dispersed graphene oxide solution prepared by step one, ultrasound 0.5~1h;Then supernatant is taken, as electrophoresis liquid with the 10~20min of centrifugation of 5000~10000r/min again;
4th, ultrasonic wave added electrophoretic deposition graphene oxide:Ultrasonic wave added electrophoretic deposition system is by electrophoresis apparatus, electrolytic cell, roller bearing dress Put and be cleaned by ultrasonic instrument composition;Roller assembly is put into electrolytic cell, and continuous conductive fiber beam is through roller bearing and electrophoresis liquid of submerging In, electrolytic cell is laid out by the stainless steel cylinder that punches, then Jing roller bearings, the stainless steel cylinder that punches in a cell is used as positive pole and electrophoresis apparatus Negative pole be connected, conductive fiber is connected as negative pole with the positive pole of electrophoresis apparatus, and two electrode distances are 1~2cm, and on-load voltage is 120~180V;Overall electrolytic cell is placed in ultrasonic cleaning instrument, under the collective effect of electric field and ultrasound, adsorbing metal ions And positively charged graphene oxide can be moved to the negative electrode with its oppositely charged, and then adsorb the table in conductive fiber Face;Behind deposition 30S~10 minute, the conductive fiber ethanol of adsorption and oxidation Graphene and water are distinguished into cleaning 1 minute repeatedly, i.e., Obtain the conductive fiber of deposited oxide Graphene;
5th, the conductive fiber of thermal reduction deposited oxide Graphene:The conductive fiber of the deposited oxide Graphene for preparing is placed in Heat 1-4h in 150-250 DEG C of vacuum drying oven, obtain the conductive fiber of thermal reduction deposited oxide Graphene.
2. a kind of method in the quick successive sedimentation Graphene of conductive fiber surfaces according to claim 1, its feature exists In:The dispersant is PVP, glyceryl monostearate or ethylene group bis-stearamides.
3. a kind of method in the quick successive sedimentation Graphene of conductive fiber surfaces according to claim 1, its feature exists In:The solvent is isopropanol, water, ethanol or dimethylformamide.
4. a kind of method in the quick successive sedimentation Graphene of conductive fiber surfaces according to claim 1, its feature exists In:The mass ratio of the graphene oxide and dispersant is 1:(0.5~8).
5. a kind of method in the quick successive sedimentation Graphene of conductive fiber surfaces according to claim 1 or 4, its feature It is:The mass ratio of the graphene oxide and dispersant is 1:1.
6. a kind of method in the quick successive sedimentation Graphene of conductive fiber surfaces according to claim 1, its feature exists In:The quality of the graphene oxide is (0.5g~2g) with the volume ratio of solvent:(100mL~500mL).
7. a kind of method in the quick successive sedimentation Graphene of conductive fiber surfaces according to claim 1, its feature exists In:The conductive fiber is carbon fiber, polyacetylene fibres or polyaniline fiber.
8. a kind of method in the quick successive sedimentation Graphene of conductive fiber surfaces according to claim 1, its feature exists In:The slaine is lithium perchlorate or magnesium nitrate.
9. a kind of method in the quick successive sedimentation Graphene of conductive fiber surfaces according to claim 1, its feature exists In:The slaine is 1 with the mass ratio of graphene oxide:(0.5~2).
CN201610907586.9A 2016-10-17 2016-10-17 Method of quickly and continuously depositing graphene on surface of electric-conductive fibers Pending CN106637923A (en)

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CN108774879A (en) * 2018-07-06 2018-11-09 东华大学 A kind of preparation method of graphene coated conductive fiber
CN108951204A (en) * 2018-05-24 2018-12-07 武汉纺织大学 A method of Electrochemical Dyeing is carried out to conductive yarn with bipseudoindoxyl dye
CN109972386A (en) * 2017-12-27 2019-07-05 东丽先端材料研究开发(中国)有限公司 A kind of conductive yarn and its product
CN110016803A (en) * 2019-04-04 2019-07-16 碳翁(北京)科技有限公司 A kind of high temperature resistant fibre electroheating and its application
CN110022623A (en) * 2019-04-04 2019-07-16 碳翁(北京)科技有限公司 A kind of preparation and application of high temperature resistant fibre electroheating
CN114934387A (en) * 2022-05-25 2022-08-23 中国科学院宁波材料技术与工程研究所 High-thermal-conductivity carbon fiber and continuous preparation method

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CN108286187A (en) * 2017-12-26 2018-07-17 山东大学 A kind of preparation method of silane coupling agent auxiliary electrophoretic deposition initiated oxidation graphene modified carbon fiber
CN109972386A (en) * 2017-12-27 2019-07-05 东丽先端材料研究开发(中国)有限公司 A kind of conductive yarn and its product
CN108951204A (en) * 2018-05-24 2018-12-07 武汉纺织大学 A method of Electrochemical Dyeing is carried out to conductive yarn with bipseudoindoxyl dye
CN108774879A (en) * 2018-07-06 2018-11-09 东华大学 A kind of preparation method of graphene coated conductive fiber
CN110016803A (en) * 2019-04-04 2019-07-16 碳翁(北京)科技有限公司 A kind of high temperature resistant fibre electroheating and its application
CN110022623A (en) * 2019-04-04 2019-07-16 碳翁(北京)科技有限公司 A kind of preparation and application of high temperature resistant fibre electroheating
CN110022623B (en) * 2019-04-04 2020-01-10 碳翁(北京)科技有限公司 Preparation and application of high-temperature-resistant electric heating fiber
CN114934387A (en) * 2022-05-25 2022-08-23 中国科学院宁波材料技术与工程研究所 High-thermal-conductivity carbon fiber and continuous preparation method
CN114934387B (en) * 2022-05-25 2024-04-05 中国科学院宁波材料技术与工程研究所 High-heat-conductivity carbon fiber and continuous preparation method

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