CN104532548A - In-situ growth method for carbon nano tubes (CNTs) on carbon fiber surface - Google Patents
In-situ growth method for carbon nano tubes (CNTs) on carbon fiber surface Download PDFInfo
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Abstract
The invention belongs to the technical field of composite materials. An in-situ growth method for carbon nano tubes (CNTs) on a carbon fiber surface is that the controlled surface treatment is carried out on carbon fibers by adopting an electrochemical process, so as to control the quantity and the distribution of active points on the carbon fiber surface; a catalyst is loaded by adopting a solution infiltration method, so that the catalyst can be uniformly distribute on the carbon fiber surface. The in-situ growth method for the (CNTs) on the carbon fiber surface comprises the steps of treating the surfaces of the carbon fibers; loading the catalyst; reducing the catalyst; promoting the growing of the CNTs; the surfaces treatment of the carbon fibers is carried out by adopting the electrochemical process; the electrolyte concentration is 1 to 10wt.%, the electrolyzing current is 0.1 to 1.5A, and the electrolyzing is carried out for 1 to 15min. The method is mild in processing condition, simple to operate and easy to control; the fiber intensity is lost little; the damage ratio of multifilament tensile strength is less than 10%; the CNTs are uniformly and densely distributed on the carbon fiber surface, and the loading quantity and the distribution density are controllable; the interlayer scission strength of a composite material can be improved by more than 13%; the method is applicable to the field of processing of carbon fiber reinforced resin based composite materials, and particularly applied to the field of processing of the carbon fiber reinforced resin based composite materials with high requirements on interlayer adhering performances.
Description
Technical field
The invention belongs to technical field of composite materials, relate to surface treatment of carbon fibers technology, the technology of special design CNT growth in situ.
Background technology
Because the carbon atom in carbon fiber exists with graphite laminate structure, its surface is in chemical inertness, therefore carbon fiber and resin matrix adhesive property poor, cause that carbon fibre composite boundary strength is low, interlayer performance is poor, have impact on its application under some special construction.
For improving carbon fiber and basal body interface combination, adopt the method for adding carbon nano-tube modification.Because specific surface area of carbon nanotube is large, easy reunion, for solving CNT dispersion in the composite and orientation problem, carrying out both at home and abroad in carbon fiber surface direct growth aligned carbon nanotube technical study, having prepared CNT-carbon fiber multi-dimension composite reinforcing material.
Carbon fiber surface in-situ growing carbon nano tube generally adopts chemical vapour deposition technique.Carbon fiber surface is carried in by catalyst particle, the kind becoming vapor phase growth is brilliant, carbon source is direct at carbon fiber surface carbon nano-tube under the catalytic action of catalyst, the distribution of catalyst determines the distribution of CNTs at carbon fiber surface, and the bonding strength of catalyst and carbon fiber substrate determines CNTs and carbon fiber bonding strength.
Disclose a kind of method direct spreading of catalyst n i powder being deposited on carbon cloth CNTs in CN 1868869A, namely in proportion Ni powder and distillation S powder are mixed also spreading and, on carbon cloth, in high temperature furnace, carry out deposition CNTs.The method of spreading catalyst is difficult to realize catalyst being uniformly distributed at fiber surface on microcosmic, and catalyst granules is large, and CNTs skewness, can not form effective connection with between carbon cloth, easily come off.
A kind of substrate method of improvement is disclosed directly in carbon fiber surface carbon nano tube array grows in CN 102351166, the mixing pre-treatment of heat treatment and strong acid treatment is adopted to carry out surface treatment to carbon fiber, increase carbon fiber surface activity point, improve the loading of catalyst, thus improve the deposition of carbon fiber surface CNT.But sustain damage through the surface texture of the carbon fiber of strong acid treatment, cause carbon fiber strength to decline, fracture load is reduced to 192.31N from 240.94N, intensity reduces by 20.2%; After growth CNTs, carbon fiber strength reduces by 35.1%.
" Growth of carbon nanotubes on the surface of carbon fibers " (Carbon, 2008,60% red fuming nitric acid (RFNA) surface oxidation treatment carbon fiber is adopted 46:365-389), fiber surface degree of roughness significantly improves, although add the absorption of catalyst at carbon fiber surface, CNTs is at carbon fiber surface skewness.
" KOH-impregnation-reduction method prepares different metal nano-catalyst coating and application thereof at carbon fiber surface " (charcoal element, 2007, (2) employing KOH Treatment of Carbon surface: 43-47) is described, fiber surface is made to become uneven, improve the distributing homogeneity of catalyst nano-particles, but carbon fiber surface pattern obviously changes, degree of roughness increases, serious to carbon fiber surface surface damage.
Although existing process for treating surface can realize improving the object that fiber surface situation improves nanotube growth point, distribution and the bond strength of nanotube effectively can not be controlled.
Summary of the invention
The present invention aims to provide a kind of chemical deposition at carbon fiber surface in-situ growing carbon nano tube, solves the problem that CNT reduces at carbon fiber surface skewness and carbon fiber bulk strength.
The object of the present invention is achieved like this: adopt electrochemical process to carry out controlled surface process to carbon fiber, by suitable Electrolytic conditions, controls active site quantity and the distribution of carbon fiber surface, reduce the damage to carbon fiber body construction; Adopt solution dipping method loading catalyst, realize catalyst being uniformly distributed at carbon fiber surface; Adopt chemical vapour deposition technique growth CNTs, thus realize CNTs controlled distribution, reduce the loss of carbon fiber bulk strength.
The method of the carbon fiber surface growth in situ CNTs that the present invention relates to, comprise surface treatment of carbon fibers, catalyst loading, catalyst reduction and CNTs and grow operation, it is characterized in that: described surface treatment of carbon fibers adopts electrochemical oxidation process, and electrolytic condition is: concentration of electrolyte is 1-10wt.%; Faradaic current 0.1-1.5A, electrolysis time 1-15min; Described electrolyte is the one in sulfuric acid, NaOH, ammonium salt aqueous solution.
The method of the carbon fiber surface growth in situ CNTs that the present invention relates to, comprise surface treatment of carbon fibers, catalyst loading, catalyst reduction and CNTs and grow operation, it is characterized in that: described electrolytic condition is: electrolyte is the ammonium salt solution of 3 ~ 8wt.%, Faradaic current 0.2 ~ 1.2A, electrolysis time 1-10min.
The method of the carbon fiber surface growth in situ CNTs that the present invention relates to, comprise surface treatment of carbon fibers, catalyst loading, catalyst reduction and CNTs and grow operation, it is characterized in that: described catalyst loading procedure complex catalyst precursor bulk concentration is not less than 0.01mol/L, dip time 5-60min.
The method of the carbon fiber surface growth in situ CNTs that the present invention relates to, comprise surface treatment of carbon fibers, catalyst loading, catalyst reduction and CNTs and grow operation, it is characterized in that: described catalyst loading procedure complex catalyst precursor bulk concentration 0.05 ~ 0.2mol/L.
The method of the carbon fiber surface growth in situ CNTs that the present invention relates to, comprise surface treatment of carbon fibers, catalyst loading, catalyst reduction and CNTs and grow operation, it is characterized in that: described catalyst reduction condition for heat up under inert gas shielding, at 300-650 DEG C, high-purity hydrogen constant temperature reduction 0-120min; Described CNTs growth heats up under inert gas shielding, constant temperature growth 3-120min under 400-850 DEG C of condition.
The method of the carbon fiber surface growth in situ CNTs that the present invention relates to, comprises surface treatment of carbon fibers, catalyst loading, catalyst reduction and CNTs and grows operation, it is characterized in that:
(1) carbon fiber surface electrochemical treatments: electrolyte is the ammonium salt solution of 3 ~ 8wt.%, Faradaic current 0.2 ~ 1.2A, electrolysis time 1-10min;
(2) catalyst loads: adopt solution dipping method to load, complex catalyst precursor bulk concentration is 0.05 ~ 0.2mol/L, and dip time is 5-60min; A kind of or wherein several combination in the ethanolic solution of the salt of described catalyst precursor chosen from Fe, cobalt, nickel;
(3) catalyst reduction: heat up under nitrogen atmosphere protection, 400-550 DEG C of constant temperature reductase 12 0-60min;
(4) CNTs growth: heat up under nitrogen atmosphere protection, 500-750 DEG C of constant temperature 5-30min; Carbon-source gas is acetylene, ethene or its combination, and the flow-rate ratio of carbon-source gas and hydrogen is 1:(1 ~ 6).
The present invention relates to the method for carbon fiber surface growth in situ CNTs, treatment conditions relax, simple to operate, be easy to control.Fibre strength loss is little, and multifilament loss of tensile strength rate is lower than 10%, and carbon fiber surface CNTs is evenly distributed, fine and close, heap(ed) capacity and distribution density controlled, composite interlayer shear strength improves more than 13%.Be applicable to carbon fiber enhancement resin base composite material manufacture field, be specially adapted to require high carbon fiber enhancement resin base composite material manufacture field to layers cementing performance.
Detailed description of the invention
Below embodiments of the invention are described in detail: the present embodiment is implemented under taking the present invention as technical scheme prerequisite, give detailed embodiment and concrete operating process, but protection scheme of the present invention are not limited to following embodiment.
embodiment 1
Process 2h under beautiful for east T700 carbon fiber is placed in 400 DEG C of nitrogen atmospheres, remove fiber surface sizing agent.
Carbon fiber is placed in 2wt% carbonic hydroammonium electrolyte, electrolytic treatments 1min under 1.0A current strength, Electrochemical surface modification process is carried out to carbon fiber, washing, drying.
By impregnated carbon fiber after surface treatment in 0.05mol/L cobalt nitrate solution, dipping 10min, room temperature is dried.
The carbon fiber of loading catalyst is placed in CVD stove, passes into high pure nitrogen, drain air, be warming up to 500 DEG C, close nitrogen, change logical high-purity hydrogen, constant temperature 30min.
Close hydrogen, change logical nitrogen, be warming up to 600 DEG C, then pass into hydrogen, ethene.Carbon-source gas: hydrogen=1:2(flow-rate ratio), constant temperature 30min.Stop heating, close ethene and hydrogen, be down to after room temperature until furnace temperature, close nitrogen, take out sample, namely obtain CNT-carbon fiber complex.
This CNTs-CF complex surfaces CNTs is evenly distributed, and coverage rate is high, the diameter 80-150nm of CNTs, length 300-700nm, and multifilament TENSILE STRENGTH is 4.66GPa, declines 4.9% before more untreated.The high-strength high-toughness epoxy polymer matrix composites interlaminar shear strength adopting this CNTs-CF to strengthen is 107.32MPa, improves 13.1% before untreated.
comparative example 1
Adopt the material system identical with embodiment 1, in 60 DEG C of concentrated nitric acid solutions, process 30min, the CNTs-CF complex nanotube skewness obtained, growth rate is low, its multifilament TENSILE STRENGTH 3.65GPa, decline 25.5% than before process, the interlaminar shear strength of composite is 96.65MPa.
Data show, the TENSILE STRENGTH of the CNTs-CF that the TENSILE STRENGTH of CNTs-CF complex prepared by the present invention obtains compared with acid treatment improves 27.6%, and the interlaminar shear strength of composite improves 11.0%.
embodiment 2
Yangzhou T300 grade carbon fiber fabric is placed in acetone and soaks 5h, remove fiber surface sizing agent.
Carbon fiber is placed in 7wt% sulfuric acid electrolyte, electrolytic treatments 12min under 0.5A current strength, Electrochemical surface modification process is carried out to carbon fiber, washing, drying.
By impregnated carbon fiber after surface treatment in 0.3mol/L iron nitrate solution, dipping 50min, room temperature is dried.
The carbon fiber of loading catalyst is placed in CVD stove, passes into high pure nitrogen, drain air, be warming up to 450 DEG C, directly pass into hydrogen, acetylene.Carbon-source gas: hydrogen=1:6(flow-rate ratio), constant temperature 60min.Stop heating, close acetylene and hydrogen, be down to after room temperature until furnace temperature, close nitrogen, take out sample, namely obtain CNTs-CF complex.
This CNTs-CF complex CNTs is evenly distributed at carbon fiber surface, densification, and the diameter 60-100nm of CNTs, length 600nm-2 μm, multifilament TENSILE STRENGTH 3.38MPa decline 5.3% before more untreated.The high-strength high-toughness epoxy polymer matrix composites TENSILE STRENGTH adopting this CNTs-CF to strengthen is 884.45MPa, and interlaminar shear strength is 98.53MPa, improves 12.7% before more untreated.
embodiment 3
The surperficial T700 grade carbon fiber without sizing agent is placed in 3wt% ammonium sulfate electrolyte, electrolytic treatments 6min under 0.3A current strength, Electrochemical surface modification process is carried out to carbon fiber, washing, drying.
By impregnated carbon fiber after surface treatment in 0.1mol/L nickel nitrate solution, dipping 15min, room temperature is dried.
The carbon fiber of loading catalyst is placed in CVD stove, passes into high pure nitrogen, drain air, be warming up to 400 DEG C, close nitrogen, change logical high-purity hydrogen, constant temperature 20min.
Close hydrogen, change logical nitrogen, be warming up to 500 DEG C, then pass into hydrogen, methane.Carbon-source gas: hydrogen=1:3(flow-rate ratio), constant temperature 45min.Stop heating, close methane and hydrogen, be down to after room temperature until furnace temperature, close nitrogen, take out sample, namely obtain CNTs-CF complex.
This CNTs-CF complex CNTs is evenly distributed at carbon fiber surface, the diameter 50-150nm of CNTs, length 800nm-1.5 μm.Multifilament TENSILE STRENGTH is 4.56GPa, declines 3.5% before more untreated.The high-strength high-toughness epoxy polymer matrix composites interlaminar shear strength adopting this CNTs-CF to strengthen is 99.8MPa, improves 13.2% before more untreated.
Comparative example 2
Adopt the material system identical with embodiment 3, the treatment conditions of 30min are processed in 60 DEG C of concentrated nitric acid solutions, the CNTs-CF complex nanotube skewness obtained, growth rate is low, its multifilament TENSILE STRENGTH 3.64GPa, the interlaminar shear strength adopting the high-strength high-toughness epoxy polymer matrix composites prepared with embodiment 3 same process is 88.7MPa.
Data show, the TENSILE STRENGTH of the CNTs-CF that the TENSILE STRENGTH of CNTs-CF complex prepared by the present invention obtains compared with acid treatment improves 25.3%, and the interlaminar shear strength of composite improves 12.5%.
embodiment 4
Weihai is expanded under T700 grade carbon fiber is placed in 400 DEG C of nitrogen atmospheres and process 3h, remove fiber surface sizing agent.
Carbon fiber is placed in 4wt% carbonic hydroammonium electrolyte, electrolytic treatments 4min under 0.8A current strength, Electrochemical surface modification process is carried out to carbon fiber, washing, drying.
By impregnated carbon fiber after surface treatment in 0.15mol/L iron nitrate solution, dipping 30min, room temperature is dried.
The carbon fiber of loading catalyst is placed in CVD stove, passes into high pure nitrogen, drain air, be warming up to 550 DEG C, close nitrogen, change logical high-purity hydrogen, constant temperature 60min.
Close hydrogen, change logical nitrogen, then be warming up to 700 DEG C, then pass into hydrogen, acetylene.Carbon-source gas: hydrogen=1:1(flow-rate ratio), constant temperature 20min.Stop heating, close acetylene and hydrogen, be down to after room temperature until furnace temperature, close nitrogen, take out sample, namely obtain CNTs-CF complex.
This CNTs-CF complex CNTs is evenly distributed, densification, the diameter 80-170nm of CNTs, length 400-700nm, and multifilament TENSILE STRENGTH is 4.46GPa, declines 8.9% before more untreated.The high-strength high-toughness epoxy polymer matrix composites interlaminar shear strength adopting this CNTs-CF to strengthen is 105.4MPa, improves 13.3% before more untreated.
embodiment 5
Process 2h under middle simple T700 grade carbon fiber fabric is placed in 450 DEG C of nitrogen atmospheres, remove fiber surface sizing agent.
Carbon fiber is placed in 9wt% ammonium dihydrogen phosphate (ADP) electrolyte, electrolytic treatments 3min under 0.6A current strength, Electrochemical surface modification process is carried out to carbon fiber, washing, drying.
By impregnated carbon fiber after surface treatment in 0.2mol/L cobalt nitrate solution, dipping 45min, room temperature is dried.
The carbon fiber of loading catalyst is placed in CVD stove, passes into high pure nitrogen, drain air, be warming up to 450 DEG C, close nitrogen, change logical high-purity hydrogen, constant temperature 45min.
Close hydrogen, change logical nitrogen, be warming up to 750 DEG C, then pass into hydrogen, ethene.Carbon-source gas: hydrogen=1:2.5(flow-rate ratio), constant temperature 15min.Stop heating, close ethene and hydrogen, be down to after room temperature until furnace temperature, close nitrogen, take out sample, namely obtain CNTs-CF complex.
This CNTs-CF complex CNTs is evenly distributed, densification, the diameter 80-120nm of CNTs, length 300-600nm, and multifilament TENSILE STRENGTH is 4.36GPa, declines 8.6% before more untreated.
embodiment 6
Process 2h under beautiful for east T700 carbon fiber is placed in 500 DEG C of nitrogen atmospheres, remove fiber surface sizing agent.
Carbon fiber is placed in 5wt% carbonic hydroammonium electrolyte, electrolytic treatments 8min under 1.2A current strength, Electrochemical surface modification process is carried out to carbon fiber, washing, drying.
By impregnated carbon fiber after surface treatment in 0.17mol/L nickel nitrate solution, dipping 60min, room temperature is dried.
The carbon fiber of loading catalyst is placed in CVD stove, passes into high pure nitrogen, drain air, be warming up to 375 DEG C, close nitrogen, change logical high-purity hydrogen, constant temperature 65min.
Close hydrogen, change logical nitrogen, be warming up to 500 DEG C, then pass into hydrogen, ethene.Carbon-source gas: hydrogen=1:4(flow-rate ratio), constant temperature 20min.Stop heating, close ethene and hydrogen, be down to after room temperature until furnace temperature, close nitrogen, take out sample, namely obtain CNTs-CF complex.
This CNTs-CF complex CNTs is evenly distributed, the diameter 70-150nm of CNTs, length 500-800nm, and multifilament TENSILE STRENGTH is 4.62GPa, declines 5.7% before more untreated.The high-strength high-toughness epoxy polymer matrix composites interlaminar shear strength adopting this CNTs-CF to strengthen is 103.9MPa, improves 11.2% before more untreated.
embodiment 7
Process 2.5h under beautiful for east T700 carbon fiber is placed in 500 DEG C of nitrogen atmospheres, remove fiber surface sizing agent.
Carbon fiber is placed in 1wt% NaOH electrolyte, electrolytic treatments 15min under 0.4A current strength, Electrochemical surface modification process is carried out to carbon fiber, washing, drying.
By impregnated carbon fiber after surface treatment in 0.15mol/L iron nitrate solution, dipping 40min, room temperature is dried.
The carbon fiber of loading catalyst is placed in CVD stove, passes into high pure nitrogen, drain air, be warming up to 525 DEG C, close nitrogen, change logical high-purity hydrogen, constant temperature 35min.
Close hydrogen, change logical nitrogen, be warming up to 800 DEG C, then pass into hydrogen, acetylene.Carbon-source gas: hydrogen=1:7(flow-rate ratio), constant temperature 3min.Stop heating, close acetylene and hydrogen, be down to after room temperature until furnace temperature, close nitrogen, take out sample, namely obtain CNTs-CF complex.
This CNTs-CF complex CNTs is evenly distributed, densification, the diameter 90-200nm of CNTs, length 200-500nm, and multifilament TENSILE STRENGTH is 4.49GPa, declines 8.4% before more untreated.
embodiment 8
Is produced from Yangzhou T300 grade carbon fiber and be placed in 8wt% ammonium nitrate electrolyte, electrolytic treatments 7min under 0.7A current strength, Electrochemical surface modification process is carried out to carbon fiber, washing, drying.
By impregnated carbon fiber after surface treatment in 0.08mol/L cobalt nitrate solution, dipping 20min, room temperature is dried.
The carbon fiber of loading catalyst is placed in CVD stove, passes into high pure nitrogen, drain air, be warming up to 420 DEG C, close nitrogen, change logical high-purity hydrogen, constant temperature 40min.
Close hydrogen, change logical nitrogen, then be warming up to 550 DEG C, then pass into hydrogen, acetylene.Carbon-source gas: hydrogen=1:5(flow-rate ratio), constant temperature 10min.Stop heating, close acetylene and hydrogen, be down to after room temperature until furnace temperature, close nitrogen, take out sample, namely obtain CNTs-CF complex.
This CNTs-CF complex CNTs is evenly distributed, densification, the diameter 80-150nm of CNTs, length 300-500m, and multifilament TENSILE STRENGTH is 3.32GPa, declines 7.3% before more untreated.The high-strength high-toughness epoxy polymer matrix composites interlaminar shear strength adopting this CNTs-CF to strengthen is 98.6MPa, improves 12.9% before more untreated.
embodiment 9
By beautiful for east T700 carbon fiber under nitrogen protection, pass into 220V electricity, except glue 2min.
Carbon fiber is placed in 6wt% ammonium dihydrogen phosphate (ADP) electrolyte, electrolytic treatments 10min under 0.2A current strength, Electrochemical surface modification process is carried out to carbon fiber, washing, drying.
By impregnated carbon fiber after surface treatment in 0.13mol/L nickel nitrate solution, dipping 5min, room temperature is dried.
The carbon fiber of loading catalyst is placed in CVD stove, passes into high pure nitrogen, drain air, be warming up to 560 DEG C, close nitrogen, change logical high-purity hydrogen, constant temperature 50min.
Close hydrogen, change logical nitrogen, then be warming up to 750 DEG C, then pass into hydrogen, natural gas.Carbon-source gas: hydrogen=1:1(flow-rate ratio), constant temperature 5min.Stop heating, close natural gas and hydrogen, be down to after room temperature until furnace temperature, close nitrogen, take out sample, namely obtain CNTs-CF complex.
This CNTs-CF complex CNTs is evenly distributed, densification, the diameter 80-170nm of CNTs, length 400-600nm, and multifilament TENSILE STRENGTH is 4.62GPa, declines 5.7% before more untreated.
embodiment 10
Process 3h under middle simple T700 grade carbon fiber is placed in 400 DEG C of nitrogen atmospheres, remove fiber surface sizing agent.
Carbon fiber is placed in 5wt% sulfuric acid electrolyte, electrolytic treatments 4min under 0.6A current strength, Electrochemical surface modification process is carried out to carbon fiber, washing, drying.
By impregnated carbon fiber after surface treatment in 0.25mol/L iron nitrate solution, dipping 35min, room temperature is dried.
The carbon fiber of loading catalyst is placed in CVD stove, passes into high pure nitrogen, drain air, be warming up to 500 DEG C, close nitrogen, change logical high-purity hydrogen, constant temperature 70min.
Close hydrogen, change logical nitrogen, then be warming up to 550 DEG C, then pass into hydrogen, acetylene and ethene mist (acetylene: ethene=1:1).Carbon-source gas: hydrogen=1:1.5(flow-rate ratio), constant temperature 120min.Stop heating, close acetylene, ethene and hydrogen, be down to after room temperature until furnace temperature, close nitrogen, take out sample, namely obtain CNTs-CF complex.
This CNTs-CF complex CNTs is evenly distributed, densification, the diameter 120-300nm of CNTs, length 1-2 μm, and multifilament TENSILE STRENGTH is 4.42GPa, declines 7.9% before more untreated.The high-strength high-toughness epoxy polymer matrix composites interlaminar shear strength adopting this CNTs-CF to strengthen is 102.7MPa, improves 13.4% before more untreated.
embodiment 11
Weihai is expanded under T300 grade carbon fiber is placed in 450 DEG C of nitrogen atmospheres and process 2.5h, remove fiber surface sizing agent.
Carbon fiber is placed in 7wt% ammonium sulfate electrolyte, electrolytic treatments 5min under 0.5A current strength, Electrochemical surface modification process is carried out to carbon fiber, washing, drying.
By impregnated carbon fiber after surface treatment in 0.06mol/L cobalt nitrate solution, dipping 40min, room temperature is dried.
The carbon fiber of loading catalyst is placed in CVD stove, passes into high pure nitrogen, drain air, be warming up to 520 DEG C, close nitrogen, change logical high-purity hydrogen, constant temperature 25min.
Close hydrogen, change logical nitrogen, be warming up to 700 DEG C, then pass into hydrogen, acetylene and ethene mist (acetylene: ethene=1:2).Carbon-source gas: hydrogen=1:3(flow-rate ratio), constant temperature 35min.Stop heating, close acetylene, ethene and hydrogen, be down to after room temperature until furnace temperature, close nitrogen, take out sample, namely obtain CNTs-CF complex.
This CNTs-CF complex CNTs is evenly distributed, densification, the diameter 90-180nm of CNTs, length 700nm-1 μm, and multifilament TENSILE STRENGTH is 3.48GPa, declines 5.9% before more untreated.
embodiment 12
Process 3h under beautiful for east T700 grade carbon fiber is placed in 500 DEG C of nitrogen atmospheres, remove fiber surface sizing agent.
Carbon fiber is placed in 3wt% carbonic hydroammonium electrolyte, electrolytic treatments 9min under 0.1A current strength, Electrochemical surface modification process is carried out to carbon fiber, washing, drying.
By impregnated carbon fiber after surface treatment in 0.01mol/L nickel nitrate solution, dipping 15min, room temperature is dried.
The carbon fiber of loading catalyst is placed in CVD stove, passes into high pure nitrogen, drain air, be warming up to 400 DEG C, close nitrogen, change logical high-purity hydrogen, constant temperature 80min.
Close hydrogen, change logical nitrogen, then be warming up to 625 DEG C, then pass into hydrogen, acetylene and ethene mist (acetylene: ethene=1:3).Carbon-source gas: hydrogen=1:4.5(flow-rate ratio), constant temperature 50min.Stop heating, close acetylene, ethene and hydrogen, be down to after room temperature until furnace temperature, close nitrogen, take out sample, namely obtain CNTs-CF complex.
This CNTs-CF complex CNTs is evenly distributed, densification, the diameter 90-200nm of CNTs, length 800nm-1.5 μm, and multifilament TENSILE STRENGTH is 4.72GPa, declines 4.6% before more untreated.
embodiment 13
T300 grade carbon fiber (without sizing agent) will be made by oneself and be placed in 2wt% ammonium nitrate electrolyte, electrolytic treatments 2min under 0.9A current strength, Electrochemical surface modification process will be carried out to carbon fiber, washing, drying.
By impregnated carbon fiber after surface treatment in 0.12mol/L iron nitrate solution, dipping 35min, room temperature is dried.
The carbon fiber of loading catalyst is placed in CVD stove, passes into high pure nitrogen, drain air, be warming up to 445 DEG C, close nitrogen, change logical high-purity hydrogen, constant temperature 55min.
Close hydrogen, change logical nitrogen, be warming up to 700 DEG C, then pass into hydrogen, methane.Carbon-source gas: hydrogen=1:8(flow-rate ratio), constant temperature 8min.Stop heating, close methane and hydrogen, be down to after room temperature until furnace temperature, close nitrogen, take out sample, namely obtain CNTs-CF complex.
This CNTs-CF complex CNTs is evenly distributed, densification, the diameter 150-500nm of CNTs, length 500-700nm, and multifilament TENSILE STRENGTH is 3.56GPa, declines 6.7% before more untreated.The high-strength high-toughness epoxy polymer matrix composites interlaminar shear strength adopting this CNTs-CF to strengthen is 98.5MPa, improves 13.6% before more untreated.
embodiment 14
Process 1.5h under beautiful for east T700 carbon fiber is placed in 450 DEG C of nitrogen atmospheres, remove fiber surface sizing agent.
Carbon fiber is placed in 8wt% NaOH electrolyte, electrolytic treatments 3min under 1.5A current strength, Electrochemical surface modification process is carried out to carbon fiber, washing, drying.
By impregnated carbon fiber after surface treatment in 0.35mol/L cobalt nitrate solution, dipping 25min, room temperature is dried.
The carbon fiber of loading catalyst is placed in CVD stove, passes into high pure nitrogen, drain air, be warming up to 450 DEG C, close nitrogen, change logical high-purity hydrogen, constant temperature 40min.
Close hydrogen, change logical nitrogen, then be warming up to 650 DEG C, then pass into hydrogen, acetylene.Carbon-source gas: hydrogen=1:2(flow-rate ratio), constant temperature 25min.Stop heating, close acetylene and hydrogen, be down to after room temperature until furnace temperature, close nitrogen, take out sample, namely obtain CNTs-CF complex.
This CNTs-CF complex CNTs is evenly distributed, densification, the diameter 120-300nm of CNTs, length 600-900nm, and multifilament TENSILE STRENGTH is 4.69GPa, declines 4.8% before more untreated.
embodiment 15
Process 3h under beautiful for east T700 carbon fiber is placed in 400 DEG C of nitrogen atmospheres, remove fiber surface sizing agent.
Carbon fiber is placed in 10wt% carbonic hydroammonium electrolyte, electrolytic treatments 9min under 0.4A current strength, Electrochemical surface modification process is carried out to carbon fiber, washing, drying.
By impregnated carbon fiber after surface treatment in 0.5mol/L nickel nitrate solution, dipping 50min, room temperature is dried.
The carbon fiber of loading catalyst is placed in CVD stove, passes into high pure nitrogen, drain air, be warming up to 530 DEG C, close nitrogen, change logical high-purity hydrogen, constant temperature 20min.
Close hydrogen, change logical nitrogen, then be warming up to 600 DEG C, then pass into hydrogen, propylene.Carbon-source gas: hydrogen=1:9(flow-rate ratio), constant temperature 18min.Stop heating, close ethene and hydrogen, be down to after room temperature until furnace temperature, close nitrogen, take out sample, namely obtain CNTs-CF complex.
This CNTs-CF complex CNTs is evenly distributed, densification, the diameter 120-400nm of CNTs, length 800nm-1.2 μm, and multifilament TENSILE STRENGTH is 4.61GPa, declines 5.9% before more untreated.
Claims (6)
1. the method for a carbon fiber surface growth in situ CNTs, comprise surface treatment of carbon fibers, catalyst loading, catalyst reduction and CNTs and grow operation, it is characterized in that: described surface treatment of carbon fibers adopts electrochemical oxidation process, and electrolytic condition is: concentration of electrolyte is 1-10wt.%; Faradaic current 0.1-1.5A, electrolysis time 1-15min; Described electrolyte is the one in sulfuric acid, NaOH, ammonium salt aqueous solution.
2. the method for carbon fiber surface growth in situ CNTs according to claim 1, comprise surface treatment of carbon fibers, catalyst loading, catalyst reduction and CNTs and grow operation, it is characterized in that: described electrolytic condition is: electrolyte is the ammonium salt solution of 3 ~ 8wt.%, Faradaic current 0.2 ~ 1.2A, electrolysis time 1-10min.
3. the method for carbon fiber surface growth in situ CNTs according to claim 1, comprise surface treatment of carbon fibers, catalyst loading, catalyst reduction and CNTs and grow operation, it is characterized in that: described catalyst loading procedure complex catalyst precursor bulk concentration is not less than 0.01mol/L, dip time 5-60min.
4. the method for carbon fiber surface growth in situ CNTs according to claim 3, comprises surface treatment of carbon fibers, catalyst loading, catalyst reduction and CNTs and grows operation, it is characterized in that: described complex catalyst precursor bulk concentration 0.05 ~ 0.2mol/L.
5. the method for the carbon fiber surface growth in situ CNTs according to claim 1,2,3 or 4, comprise surface treatment of carbon fibers, catalyst loading, catalyst reduction and CNTs and grow operation, it is characterized in that: described catalyst reduction condition for heat up under inert gas shielding, at 300-650 DEG C, high-purity hydrogen constant temperature reduction 0-120min; Described CNTs growth heats up under inert gas shielding, constant temperature growth 3-120min under 400-850 DEG C of condition.
6. the method for carbon fiber surface growth in situ CNTs according to claim 1, comprises surface treatment of carbon fibers, catalyst loading, catalyst reduction and CNTs and grows operation, it is characterized in that:
(1) carbon fiber surface electrochemical treatments: electrolyte is the ammonium salt solution of 3 ~ 8wt.%, Faradaic current 0.2 ~ 1.2A, electrolysis time 1-10min;
(2) catalyst loads: adopt solution dipping method to load, complex catalyst precursor bulk concentration is 0.05 ~ 0.2mol/L, and dip time is 5-60min; A kind of or wherein several combination in the ethanolic solution of the salt of catalyst precursor chosen from Fe, cobalt, nickel;
(3) catalyst reduction: heat up under nitrogen atmosphere protection, 400-550 DEG C of constant temperature reductase 12 0-60min;
(4) CNTs growth: heat up under nitrogen atmosphere protection, 500-750 DEG C of constant temperature 5-30min; Carbon-source gas is acetylene, ethene or its combination, and the flow-rate ratio of carbon-source gas and hydrogen is 1:(1 ~ 6).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781843A (en) * | 2009-12-25 | 2010-07-21 | 北京化工大学 | Surface treatment method of mid-high-strength carbon fiber |
| CN102002847A (en) * | 2010-11-15 | 2011-04-06 | 四川城际轨道交通材料有限责任公司 | Electrochemical CF (Carbon Fiber) surface modification method |
| CN102351166A (en) * | 2011-06-30 | 2012-02-15 | 中国科学院上海硅酸盐研究所 | Method for directly growing carbon nanotube on surface of carbon fiber |
| CN104310371A (en) * | 2014-09-30 | 2015-01-28 | 张映波 | Method for growing carbon nano tube in situ on surface of fiber |
-
2015
- 2015-01-29 CN CN201510044981.4A patent/CN104532548A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781843A (en) * | 2009-12-25 | 2010-07-21 | 北京化工大学 | Surface treatment method of mid-high-strength carbon fiber |
| CN102002847A (en) * | 2010-11-15 | 2011-04-06 | 四川城际轨道交通材料有限责任公司 | Electrochemical CF (Carbon Fiber) surface modification method |
| CN102351166A (en) * | 2011-06-30 | 2012-02-15 | 中国科学院上海硅酸盐研究所 | Method for directly growing carbon nanotube on surface of carbon fiber |
| CN104310371A (en) * | 2014-09-30 | 2015-01-28 | 张映波 | Method for growing carbon nano tube in situ on surface of fiber |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN105047423A (en) * | 2015-08-07 | 2015-11-11 | 华中师范大学 | Flexible symmetrical pseudocapacitance super capacitor and preparation method thereof |
| CN105645393A (en) * | 2016-01-14 | 2016-06-08 | 山东科技大学 | Preparing method for in-situ growth of graphene on graphite fibers |
| CN105645393B (en) * | 2016-01-14 | 2017-12-01 | 山东科技大学 | A kind of preparation method of the growth in situ graphene on graphite fibre |
| CN106319933B (en) * | 2016-08-17 | 2019-06-07 | 山东大学 | Carbon fiber electrically chemical treatment method for surface growth carbon nanotube |
| CN106319933A (en) * | 2016-08-17 | 2017-01-11 | 山东大学 | Carbon fiber electrochemical processing method for surface growth carbon nanotube |
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