CN103172049A - Functionalized carbon nano-tube paper and preparation method of composite material thereof - Google Patents
Functionalized carbon nano-tube paper and preparation method of composite material thereof Download PDFInfo
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Abstract
The invention relates to functionalized carbon nano-tube paper and a preparation method of a composite material thereof. According to the invention, prepared functionalized carbon nano-tube paper and thermoset resin are processed through a resin pre-impregnation process, a prepreg hot-pressing forming process or a powder forming process, such that a functionalized carbon nano-tube paper composite material is prepared. The material has excellent comprehensive performances especially mechanical strength. The material also has the advantages of environment friendliness, wide applicability, low production cost, and the like. Therefore, development requirements of environment-friendly material under continuously increased environment-protection awareness can be satisfied. The material has great application prospect in the field of structural and functional composite materials.
Description
Technical field
The present invention relates to a kind of functionalized carbon nanotubes paper and composite manufacture method thereof, belong to chemical technology field.
Background technology
Carbon nanotube paper is (also referred to as Buckypaper, Buckie paper) be a kind of carbon nanotube by mutual winding, paper shape thin layer by the formation of the Van der Waals force between tube and tube, the self supporting structure of its uniqueness is given its outstanding mechanics, electricity and thermal property, thereby has broad application prospects in fields such as stopper, sensor, electrical condenser, electrode, fuel cell, Field Emission Display, structure and functional composite materials.
In order to give full play to and utilize the over-all properties of carbon nanotube paper excellence, carbon nanotube paper has been become one of important channel that promotes the carbon nanotube paper application development as the compound research of strongthener and macromolecular material, caused material scholar and engineering technical personnel's extensive attention.especially it is worth mentioning that, a large amount of achievements in research is verified, because carbon nanotube paper can be when overcoming the carbon nano tube compound material high viscosity and realizing the carbon nanotube high filler loading capacity, can guarantee that carbon nanotube disperses equably in polymkeric substance, thereby it and macromolecular material compound can realize mechanical property between carbon nanotube paper and macromolecular material non-linear add and, and obtain high performance composite (QF Cheng with superpower physical strength, JW Bao, etal. Advanced Functional Materials, 2009, 19, 3219-3225, JW Bao, ZY Liang, etal. US 2010/0227155 Al, Bao Jianwen. the Chinese material progress, 2009,28,19-27).Yet, understand from the angle that organic/inorganic is compound, the tensile strength of single-root carbon nano-tube is 11 ~ 130GPa, Young's modulus is 1000 ~ 1800GPa, and the tensile strength of existing carbon nanotube paper/macromolecular material matrix material is only 0.2 ~ 2.1GPa, Young's modulus is 33 ~ 170GPa, obviously still embodies far away the superiority of organic/inorganic composite means on collaborative strongthener mechanical property, the potentiality that its physical strength still is significantly increased.Therefore, research still need look for another way based on the high performance of carbon nanotube paper and matrix material thereof, explores new thinking of development.
Matrix material mainly is comprised of resin, strongthener and interfacial phase, and as a rule, interfacial phase is the deciding factor of composite property quality.With regard to carbon nanotube paper/polymer composites, the shared ratio of its interfacial phase is farther far above conventional matrix material, thereby how to give its excellent interfacial adhesion strength and have very important effect for the high performance of carbon nanotube paper/polymer composites and the application in structure and functional composite material field thereof.Combination between carbon nanotube and resin mainly contains Intermolecular Forces, mechanical snap and chemical bonds etc., wherein, chemical bonding is to pretend firmly, mechanical snap power and Intermolecular Forces a little less than.In order to give matrix material high interface binding intensity, often by the method for chemistry or physics, carbon nanotube is carried out functionalized surfaces and process, thereby increase the interface interaction power of itself and polymkeric substance, realize the purpose of matrix material high performance.At present, although the preparation research of functionalized carbon nanotubes paper has been obtained some breakthroughs, but its application in structure and functional composite material still faces many difficulties and challenge, be mainly manifested in: 1) adopt at present the standby carbon nanotube paper of CVD legal system all to be difficult to form effective chemical bond between resin and carbon nanotube, thereby be unfavorable for stress in effective transmission at interface, finally cause the enhancing modified effect of carbon nanotube excellence to be embodied fully.2) existing research work mainly adopts the suspension suction method to prepare functionalized carbon nanotubes paper, namely first adopt tensio-active agent or high polar solvent that functionalized carbon nanotubes is dispersed in and form suspension in liquid solvent, then obtain functionalized carbon nanotubes paper by suction filtration.Yet, the former can't be under the prerequisite of destroying carbon nanometer tube surface functional group not, remove remaining tensio-active agent, and remaining tensio-active agent forms effective Chemical bonding not only bad for the phase interface of matrix material, and as impurity, the high performance of matrix material is had serious negative effect on the contrary in the matrix material body; The latter adopts a large amount of high boiling points, poisonous organic solvent as solvent, and its complicated process of preparation is unfavorable for commercial scale production, and uses poisonous organic solvent to be not suitable with the constantly development of the environmental friendliness shaped material of enhancing of environmental consciousness because need are a large amount of.Therefore, the preparation method who how to explore novel functionalized carbon nanotubes paper is one of key subject that carbon nanotube paper/the polymer composites high performance needs to be resolved hurrily.
For existing carbon nanotube paper/existing problem of polymer composites high performance, a kind of functionalized carbon nanotubes paper and composite manufacture method thereof are provided, and this preparation method is simple, suitability is wide, with low cost, thereby can solve the key subject that carbon nanotube paper/the polymer composites high performance needs to be resolved hurrily, have very important using value and academic significance.
Summary of the invention
The deficiency that exists in order to overcome prior art, the object of the present invention is to provide a kind of functionalized carbon nanotubes paper and composite manufacture method thereof, and this preparation method is simple, suitability is wide, with low cost, thereby can solve the key subject that carbon nanotube paper/the polymer composites high performance needs to be resolved hurrily.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of preparation method of functionalized carbon nanotubes paper is provided, and its feature comprises in step:
1) under-10 ~ 140 ℃, carbon nanotube is added oleum in intercalation 0.1 ~ 96h, then temperature be under-10 ~ 60 ℃, agitation condition after nitric acid oxidation is processed 0.1h ~ 480h, filter with centrifugation or nanofiltration membrane, to neutral, namely get functionalized carbon nanotubes through deionized water wash.
2) functionalized carbon nanotubes freely is scattered in solvent, namely gets functionalized carbon nanotubes paper through suction filtration.
The diameter of described Single Walled Carbon Nanotube is 0.5 ~ 5nm; The diameter of described double-walled carbon nano-tube is 1.0 ~ 10nm; The diameter of described multi-walled carbon nano-tubes is 1.5 ~ 15nm; The thickness of described carbon nanotube paper is 5 ~ 200um.
SO in described oleum
3Concentration be 2wt% ~ 50wt%; The concentration of described nitric acid is 30 ~ 68wt%; Described solvent is the organic solvents such as ketone, alcohols, heterocyclic, ester class, water, or their combination.
The preparation method of described functionalized carbon nanotubes paper composites realizes thermosetting resin and functionalized carbon nanotubes paper by resin prepreg technique, prepreg hot press forming technology or powder technology; Described resin prepreg technique is first thermosetting resin liquid to be applied or thermosetting resin membrane is positioned over the carbon nanotube paper surface, prepares the carbon nanotube paper composites at vacuum/antivacuum auxiliary lower heat-pressure curing; Described prepreg hot press forming technology is first carbon nanotube paper to be immersed in to obtain the carbon nanotube prepreg in the thermosetting resin organic solvent solution, prepares the carbon nanotube paper composites at vacuum/antivacuum auxiliary lower heat-pressure curing; Described powder technology is first thermosetting powders to be sprayed at the carbon nanotube paper surface, prepares the carbon nanotube paper composites at vacuum/antivacuum auxiliary lower heat-pressure curing.
Described thermosetting resin is a kind of in resol, epoxy resin, bimaleimide resin, benzoxazine colophony, cyanate ester resin, urethane resin, unsaturated polyester, or their combination.
Described Heating temperature is less than 400 ℃; Described pressure is 1 ~ 400kN; The described dwell time is 10 ~ 800 minutes; Described relative vacuum degree is less than-0.01MPa; Described organic solvent is a kind of in ethanol, methyl alcohol, acetone, tetrahydrofuran (THF) and ethyl acetate, perhaps their combination.
Described heating unit comprises hot-plate, thermocompressor, compression molding instrument, autoclave or baking oven.
Compared with prior art, the beneficial effect obtained of the present invention is:
1. the technical program adopts the standby functionalized carbon nanotubes paper of strong acid legal system, content by regulation and control carbon nano tube surface functional group, not only can be under the prerequisite that keeps the original high length-diameter ratio of carbon nanotube, form effective chemical bond between resin matrix and carbon nanotube, thereby make stress can access effective transmission at phase interface, and not extra introducing the 3rd component (as tensio-active agent etc.), therefore, resulting carbon nanotube paper composites shows excellent over-all properties.
2. technical scheme provided by the present invention need not the extra poisonous organic solvent of interpolation high boiling point, therefore, has the advantages such as environmental friendliness, suitability are wide, low production cost, can satisfy the demand for development of the environmental friendliness shaped material that environmental consciousness constantly strengthens.
Description of drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the carbon nanotube paper that provides of the embodiment of the present invention 1;
Fig. 2 is the infrared spectrogram of the carbon nanotube paper that provides of the embodiment of the present invention 1.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
1. the preparation of functionalized carbon nanotubes paper
1) be that the Single Walled Carbon Nanotube of 0.5nm adds SO with mean diameter under 25 ℃
3Concentration is intercalation 3h in the oleum of 20wt%, then temperature be under 25 ℃, agitation condition after the nitric acid oxidation that concentration is 68wt% is processed 120h, use centrifugation, to neutrality, namely get functionalized carbon nanotubes through deionized water wash.
2) functionalized carbon nanotubes freely is scattered in water, namely gets through suction filtration the functionalized carbon nanotubes paper that thickness is 5um.
2. the functionalized carbon nanotubes paper that step 1 is prepared is immersed in the acetone solution of epoxy resin, obtains the prefabricated body of functionalized carbon nanotubes paper/epoxy resin after the acetone volatilization.
3. the heating and pressurizing moulding of the prefabricated body of functionalized carbon nanotubes paper/epoxy resin
1) the prefabricated body of functionalized carbon nanotubes paper/epoxy resin with one deck is positioned in mould;
2) this mould is positioned in thermocompressor, this mould is applied the pressure of 10kN, after heating made this mould be warming up to 120 ℃ simultaneously, pressurize was 120 minutes under air atmosphere;
3) after the demoulding, namely obtain functionalized carbon nanotubes paper/epoxy resin composite material.
The scanning electron microscope of this functionalized carbon nanotubes paper and infrared spectrogram are seen Fig. 1 and Fig. 2.
Embodiment 2
1. the preparation of functionalized carbon nanotubes paper
1) be that the double-walled carbon nano-tube of 1.0nm adds SO with mean diameter under-10 ℃
3Concentration is intercalation 96h in the oleum of 50wt%, then temperature be under 60 ℃, agitation condition after the nitric acid oxidation that concentration is 30wt% is processed 0.1h, use centrifugation, to neutrality, namely get the functionalized carbon nanotubes that thickness is 20um through deionized water wash.
2) functionalized carbon nanotubes freely is scattered in ethanol, namely gets through suction filtration the functionalized carbon nanotubes paper that thickness is 25um.
2. the functionalized carbon nanotubes paper that step 1 is prepared is immersed in the ethanol of resol, obtains the prefabricated body of functionalized carbon nanotubes paper/resol after the ethanol volatilization.
3. the heating and pressurizing moulding of the prefabricated body of functionalized carbon nanotubes paper/resol
1) the two-layer prefabricated body of functionalized carbon nanotubes paper/resol is positioned in mould;
2) this mould is positioned in the compression molding instrument, this mould is applied the pressure of 400kN, simultaneously
The heating make this mould be warming up to 170 ℃ after, vacuum (the relative vacuum degree less than-0.01MPa)
Lower pressurize 800 minutes;
3) after the demoulding, namely obtain functionalized carbon nanotubes paper/phenolic resin composite.
Embodiment 3
1. the preparation of functionalized carbon nanotubes paper
1) be that the multi-walled carbon nano-tubes of 1.5nm adds SO with mean diameter under 140 ℃
3Concentration is intercalation 480h in the oleum of 2wt%, then temperature be under 110 ℃, agitation condition after the nitric acid oxidation that concentration is 50wt% is processed 480h, use centrifugation, to neutrality, namely get functionalized carbon nanotubes through deionized water wash.
2) functionalized carbon nanotubes freely is scattered in tetrahydrofuran (THF), namely gets through suction filtration the functionalized carbon nanotubes paper that thickness is 50um.
2. the bismaleimides powder is sprayed in the prepared functionalized carbon nanotubes paper of step 1, obtains functionalized carbon nanotubes paper/pair bismaleimide resin precast body.
3. the heating and pressurizing moulding of functionalized carbon nanotubes paper/pair bismaleimide resin precast body
1) the functionalized carbon nanotubes paper of one deck/pair bismaleimide resin precast body is positioned in mould;
2) this mould is positioned in the compression molding instrument, this mould is applied the pressure of 1kN, add simultaneously
After heat made this mould be warming up to 280 ℃, pressurize was 200 minutes under air atmosphere;
3) after the demoulding, namely obtain functionalized carbon nanotubes paper/pair bismaleimide resin matrix material.
Embodiment 4
1. the preparation of functionalized carbon nanotubes paper
1) be that the Single Walled Carbon Nanotube of 1.0nm adds SO with mean diameter under 30 ℃
3Concentration is intercalation 4h in the oleum of 25wt%, then temperature be under 35 ℃, agitation condition after the nitric acid oxidation that concentration is 65wt% is processed 240h, use centrifugation, to neutrality, namely get functionalized carbon nanotubes through deionized water wash.
2) functionalized carbon nanotubes freely is scattered in ethyl acetate, namely gets through suction filtration the functionalized carbon nanotubes paper that thickness is 20um.
2. unsaturated polyester is coated in the prepared functionalized carbon nanotubes paper of step 1, obtains functionalized carbon nanotubes paper/unsaturated polyester precast body.
3. the heating and pressurizing moulding of functionalized carbon nanotubes paper/unsaturated polyester precast body
1) the functionalized carbon nanotubes paper of one deck/unsaturated polyester precast body is positioned in mould;
2) this mould is positioned in autoclave, this mould is applied the pressure of 120kN, simultaneously heating
After making this mould be warming up to 100 ℃, pressurize is 150 minutes under air atmosphere;
3) after the demoulding, namely obtain functionalized carbon nanotubes paper/unsaturated polyester composite.
Embodiment 5
1. the preparation of functionalized carbon nanotubes paper
1) be that the double-walled carbon nano-tube of 2.0nm adds SO with mean diameter under 30 ℃
3Concentration is intercalation 2h in the oleum of 30wt%, then temperature be under 40 ℃, agitation condition after the nitric acid oxidation that concentration is 65wt% is processed 120h, use centrifugation, to neutrality, namely get functionalized carbon nanotubes through deionized water wash.
2) functionalized carbon nanotubes freely is scattered in water, namely gets through suction filtration the functionalized carbon nanotubes paper that thickness is 40um.
2. the benzoxazine film is placed in the prepared functionalized carbon nanotubes paper of step 1, obtains functionalized carbon nanotubes paper/benzoxazine precast body.
3. the heating and pressurizing moulding of functionalized carbon nanotubes paper/benzoxazine precast body
1) the functionalized carbon nanotubes paper of one deck/benzoxazine precast body is positioned in mould;
2) this mould is positioned in hot-plate, this mould is applied the pressure of 150kN, simultaneously heating
After making this mould be warming up to 180 ℃, (the relative vacuum degree is less than-0.01MPa) lower guarantor in vacuum
Pressed 200 minutes;
3) after the demoulding, namely obtain functionalized carbon nanotubes paper/benzoxazine matrix material.
Embodiment 6
1. the preparation of functionalized carbon nanotubes paper
1) be that the multi-walled carbon nano-tubes of 2.5nm adds SO with mean diameter under 30 ℃
3Concentration is intercalation 3h in the oleum of 30wt%, then temperature be under 50 ℃, agitation condition after the nitric acid oxidation that concentration is 65wt% is processed 24h, use centrifugation, to neutrality, namely get functionalized carbon nanotubes through deionized water wash.
2) functionalized carbon nanotubes freely is scattered in water, namely gets through suction filtration the functionalized carbon nanotubes paper that thickness is 55um.
2. urethane resin is coated in the prepared functionalized carbon nanotubes paper of step 1, obtains functionalized carbon nanotubes paper/urethane resin precast body.
3. the heating and pressurizing moulding of functionalized carbon nanotubes paper/urethane resin precast body
1) the functionalized carbon nanotubes paper of one deck/urethane resin precast body is positioned in mould;
2) this mould is positioned in baking oven, this mould is applied the pressure of 20kN, heating simultaneously makes this
After mould was warming up to 80 ℃, pressurize was 10 minutes under air atmosphere;
3) after the demoulding, namely obtain functionalized carbon nanotubes paper/urethane resin matrix material.
Embodiment 7
1. the preparation of functionalized carbon nanotubes paper
1) be that the Single Walled Carbon Nanotube of 5nm adds SO with mean diameter under 30 ℃
3Concentration is intercalation 3h in the oleum of 30wt%, then temperature be under 50 ℃, agitation condition after the nitric acid oxidation that concentration is 50wt% is processed 240h, use centrifugation, to neutrality, namely get functionalized carbon nanotubes through deionized water wash.
2) functionalized carbon nanotubes freely is scattered in water, namely gets through suction filtration the functionalized carbon nanotubes paper that thickness is 30um.
2. cyanate ester resin is sprayed in the prepared functionalized carbon nanotubes paper of step 1, obtains functionalized carbon nanotubes paper/cyanate ester resin precast body.
3. the heating and pressurizing moulding of functionalized carbon nanotubes paper/cyanate ester resin precast body
1) the functionalized carbon nanotubes paper of one deck/cyanate ester resin precast body is positioned in mould;
2) this mould is positioned in baking oven, this mould is applied the pressure of 200kN, heating simultaneously makes
After this mould was warming up to 220 ℃, pressurize was 240 minutes under air atmosphere;
3) after the demoulding, namely obtain functionalized carbon nanotubes paper/cyanate ester resin composite material.
Embodiment 8
1. the preparation of functionalized carbon nanotubes paper
1) be that the double-walled carbon nano-tube of 10nm adds SO with mean diameter under 25 ℃
3Concentration is intercalation 5 in the oleum of 20wt%, then temperature be under 25 ℃, agitation condition after the nitric acid oxidation that concentration is 68wt% is processed 120h, use centrifugation, to neutrality, namely get functionalized carbon nanotubes through deionized water wash.
2) functionalized carbon nanotubes freely is scattered in water, namely gets through suction filtration the sense that thickness is 50um
Carbon nano tube paper.
2. the functionalized carbon nanotubes paper that step 1 is prepared is immersed in the acetone solution of epoxy resin, obtains the prefabricated body of functionalized carbon nanotubes paper/epoxy resin after the acetone volatilization.
3. the heating and pressurizing moulding of the prefabricated body of functionalized carbon nanotubes paper/epoxy resin
1) the prefabricated body of functionalized carbon nanotubes paper/epoxy resin with one deck is positioned in mould;
2) this mould is positioned in thermocompressor, this mould is applied the pressure of 140kN, after heating made this mould be warming up to 120 ℃ simultaneously, pressurize was 240 minutes under air atmosphere;
3) after the demoulding, namely obtain functionalized carbon nanotubes paper/epoxy resin composite material.
Embodiment 9
1. the preparation of functionalized carbon nanotubes paper
1) be that the multi-walled carbon nano-tubes of 15nm adds SO with mean diameter under 30 ℃
3Concentration is intercalation 3h in the oleum of 25wt%, then be 45 in temperature, under agitation condition after the nitric acid oxidation that concentration is 50wt% is processed 240h, use centrifugation, to neutrality, namely get functionalized carbon nanotubes through deionized water wash.
2) functionalized carbon nanotubes freely is scattered in water, namely gets through suction filtration the functionalized carbon nanotubes paper that thickness is 200um.
2. cyanate ester resin is sprayed in the prepared functionalized carbon nanotubes paper of step 1, obtains functionalized carbon nanotubes paper/cyanate ester resin precast body.
3. the heating and pressurizing moulding of functionalized carbon nanotubes paper/cyanate ester resin precast body
1) the functionalized carbon nanotubes paper of one deck/cyanate ester resin precast body is positioned in mould;
2) this mould is positioned in baking oven, this mould is applied the pressure of 250kN, heating simultaneously makes
After this mould was warming up to 220 ℃, (the relative vacuum degree was less than-0.01MPa) lower pressurize in vacuum
240 minutes;
3) after the demoulding, namely obtain functionalized carbon nanotubes paper/cyanate ester resin composite material.
Referring to Fig. 1, it is the scanning electron microscope (SEM) photograph of the functionalized carbon nanotubes paper that provides of the embodiment of the present invention 1; It is the infrared spectrogram of the functionalized carbon nanotubes paper that provides of the embodiment of the present invention 1 referring to Fig. 2.Can be found out by Fig. 1 and Fig. 2, after the strong acid oxide treatment, functionalized carbon nanotubes paper has been introduced a large amount of functional groups under the prerequisite that keeps high length-diameter ratio.
Claims (7)
1. the preparation method of a functionalized carbon nanotubes paper, its feature comprises in step:
1) under-10 ~ 140 ℃, carbon nanotube is added oleum in intercalation 0.1 ~ 96h, then temperature be under-10 ~ 60 ℃, agitation condition after nitric acid oxidation is processed 0.1h ~ 480h, filter with centrifugation or nanofiltration membrane, to neutral, namely get functionalized carbon nanotubes through deionized water wash;
2) functionalized carbon nanotubes freely is scattered in solvent, namely gets functionalized carbon nanotubes paper through suction filtration.
2. the preparation method of functionalized carbon nanotubes paper according to claim 1, it is characterized in that: the diameter of described Single Walled Carbon Nanotube is 0.5 ~ 5nm; The diameter of described double-walled carbon nano-tube is 1.0 ~ 10nm; The diameter of described multi-walled carbon nano-tubes is 1.5 ~ 15nm; The thickness of described carbon nanotube paper is 5 ~ 200um.
3. the preparation method of functionalized carbon nanotubes paper according to claim 1, is characterized in that: SO in described oleum
3Concentration be 2wt% ~ 50wt%; The concentration of described nitric acid is 30 ~ 68wt%; Described solvent is the organic solvents such as ketone, alcohols, heterocyclic, ester class, water, or their combination.
4. the preparation method of a functionalized carbon nanotubes paper composites is characterized in that: the preparation method system of described functionalized carbon nanotubes paper composites realizes thermosetting resin and functionalized carbon nanotubes paper by resin prepreg technique, prepreg hot press forming technology or powder technology; Described resin prepreg technique is first thermosetting resin liquid to be applied or thermosetting resin membrane is positioned over the carbon nanotube paper surface, prepares the carbon nanotube paper composites at vacuum/antivacuum auxiliary lower heat-pressure curing; Described prepreg hot press forming technology is first carbon nanotube paper to be immersed in to obtain the carbon nanotube prepreg in the thermosetting resin organic solvent solution, prepares the carbon nanotube paper composites at vacuum/antivacuum auxiliary lower heat-pressure curing; Described powder technology is first thermosetting powders to be sprayed at the carbon nanotube paper surface, prepares the carbon nanotube paper composites at vacuum/antivacuum auxiliary lower heat-pressure curing.
5. composite manufacture method according to claim 4, it is characterized in that: described thermosetting resin is a kind of in resol, epoxy resin, bimaleimide resin, benzoxazine colophony, cyanate ester resin, urethane resin, unsaturated polyester, or their combination.
6. composite manufacture method according to claim 4, it is characterized in that: described Heating temperature is less than 400 ℃; Described pressure is 1 ~ 400kN; The described dwell time is 10 ~ 800 minutes; Described relative vacuum degree is less than-0.01MPa; Described organic solvent is a kind of in ethanol, methyl alcohol, acetone, tetrahydrofuran (THF) and ethyl acetate, perhaps their combination.
7. composite manufacture method according to claim 4, it is characterized in that: described heating unit comprises hot-plate, thermocompressor, compression molding instrument, autoclave or baking oven.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103346291A (en) * | 2013-07-10 | 2013-10-09 | 肖辉 | Carbon nano-paper-based in-situ loaded ferroferric oxide lithium-ion battery negative electrode and preparation method thereof |
| CN107630386A (en) * | 2017-09-26 | 2018-01-26 | 成都新柯力化工科技有限公司 | One kind electromagnetic shielding paper and preparation method thereof |
| CN108084661A (en) * | 2017-12-27 | 2018-05-29 | 张万虎 | A kind of preparation method of carbon nano tube compound material |
| CN112080753A (en) * | 2020-09-15 | 2020-12-15 | 西北矿冶研究院 | Carbon anode plate for fluorine preparation by impregnation method and tail gas treatment process |
| CN114181494A (en) * | 2020-09-14 | 2022-03-15 | 中国科学院福建物质结构研究所 | Preparation method of anti-delamination high-conductivity polymer matrix composite material prepared by carbon nano tube bucky paper in-situ deposition of carbon fibers |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1475437A (en) * | 2003-07-31 | 2004-02-18 | 清华大学 | Manufacturing method of carbon nano tube paper |
| CN101177254A (en) * | 2006-11-10 | 2008-05-14 | 同济大学 | Hydrophilicity carbon nanometer-tube and preparation method thereof |
| US20100227155A1 (en) * | 2009-01-20 | 2010-09-09 | Florida State University Research Foundation | Nanoscale fiber films, composites, and methods for alignment of nanoscale fibers by mechanical stretching |
| CN102350234A (en) * | 2011-06-30 | 2012-02-15 | 中国科学院金属研究所 | Dispersion method for carbon nanotubes |
| CN102351165A (en) * | 2011-06-23 | 2012-02-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | Large-area freestanding carbon nanotube paper and preparation method thereof |
| CN102642825A (en) * | 2012-04-16 | 2012-08-22 | 天津师范大学 | Histidine-functionalized carbon nanotube and preparation method and application thereof |
-
2013
- 2013-03-04 CN CN2013100697891A patent/CN103172049A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1475437A (en) * | 2003-07-31 | 2004-02-18 | 清华大学 | Manufacturing method of carbon nano tube paper |
| CN101177254A (en) * | 2006-11-10 | 2008-05-14 | 同济大学 | Hydrophilicity carbon nanometer-tube and preparation method thereof |
| US20100227155A1 (en) * | 2009-01-20 | 2010-09-09 | Florida State University Research Foundation | Nanoscale fiber films, composites, and methods for alignment of nanoscale fibers by mechanical stretching |
| CN102351165A (en) * | 2011-06-23 | 2012-02-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | Large-area freestanding carbon nanotube paper and preparation method thereof |
| CN102350234A (en) * | 2011-06-30 | 2012-02-15 | 中国科学院金属研究所 | Dispersion method for carbon nanotubes |
| CN102642825A (en) * | 2012-04-16 | 2012-08-22 | 天津师范大学 | Histidine-functionalized carbon nanotube and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘妍等: "多壁巴基纸／环氧复合材料拉伸性能的影响因素", 《复合材料学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103346291A (en) * | 2013-07-10 | 2013-10-09 | 肖辉 | Carbon nano-paper-based in-situ loaded ferroferric oxide lithium-ion battery negative electrode and preparation method thereof |
| CN103346291B (en) * | 2013-07-10 | 2015-12-02 | 昆明纳太能源科技有限公司 | Lithium ion battery negative of a kind of carbon nanometer paper substrate original position load tri-iron tetroxide and preparation method thereof |
| CN107630386A (en) * | 2017-09-26 | 2018-01-26 | 成都新柯力化工科技有限公司 | One kind electromagnetic shielding paper and preparation method thereof |
| CN108084661A (en) * | 2017-12-27 | 2018-05-29 | 张万虎 | A kind of preparation method of carbon nano tube compound material |
| CN114181494A (en) * | 2020-09-14 | 2022-03-15 | 中国科学院福建物质结构研究所 | Preparation method of anti-delamination high-conductivity polymer matrix composite material prepared by carbon nano tube bucky paper in-situ deposition of carbon fibers |
| CN114181494B (en) * | 2020-09-14 | 2023-03-28 | 中国科学院福建物质结构研究所 | Preparation method of anti-layering high-conductivity polymer matrix composite material prepared by in-situ deposition of carbon fibers on carbon nanotube base paper |
| CN112080753A (en) * | 2020-09-15 | 2020-12-15 | 西北矿冶研究院 | Carbon anode plate for fluorine preparation by impregnation method and tail gas treatment process |
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