CN101428789B - Method for processing barometric pressure, normal-temperature plasma modification on carbon nano-tube surface - Google Patents
Method for processing barometric pressure, normal-temperature plasma modification on carbon nano-tube surface Download PDFInfo
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- CN101428789B CN101428789B CN 200810204059 CN200810204059A CN101428789B CN 101428789 B CN101428789 B CN 101428789B CN 200810204059 CN200810204059 CN 200810204059 CN 200810204059 A CN200810204059 A CN 200810204059A CN 101428789 B CN101428789 B CN 101428789B
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Abstract
The invention relates to a processing method for modifying atmospheric pressure on the surface of a carbon nanometer tube and a normal temperature plasma, which comprises the following steps: placing the carbon nanometer tube on a special transmission device of a plasma processing device; spraying the e plasma to the surface of the carbon nanometer tube under the atmospheric pressure and the open environment, so that the carbon nanometer tube moves in the atmosphere of the plasma, wherein the processing power is 10W to 5000W and the time is 0.01s to 6000s; and then generating the surface modification of the carbon nanometer tube. The invention can directly improve the surface property, the structure and the shape of the carbon nanometer tube for one step under the atmospheric pressure and the normal temperature, and has the advantages of strong process controllability, simple replacement process and less environmental pollution by adopting the dry process. The effect of isosexual repulsion is generated on the particle surface of the carbon nanometer tube, so that the possibility on the reunion of nanometer particles is reduced.
Description
Technical field
The invention belongs to the modification preparation field of carbon nano-tube material, particularly relate to the treatment process of carbon nano tube surface normal atmosphere, normal-temperature plasma modification.
Background technology
Because nano material has the characteristics such as dimensional effect, surface effects, quantum effect, macro quanta tunnel effect, thereby shows the notable feature that is different from general macroscopic material at aspects such as optics, mechanics, electricity, magnetics, is developed rapidly in recent years.
Carbon nanotube has unique topological framework, and the heat conductivility that specific tenacity is high, the axial expansion coefficient is low, unique and conductivity etc. are considered to a kind of new function material and structured material of excellent performance, carbon nanotube has unique structure, electricity, optics, magnetics and mechanical property, has broad application prospects in fields such as battery, Scanning Probe Microscopy, nanoelectronic device, flat field emission device and molecular computers.The method of synthesizing carbon nanotubes is a lot of at present, but the carbon nanotube of which kind of method preparation all is attended by the impurity such as decolorizing carbon particle, amorphous carbon fiber and graphite granule, these impurity and carbon nano tube hybrid are together, and chemical property is close, not only affect the performance of gained matrix material, and make its performance test be subject to very large obstruction.Therefore, carbon nanotube is carried out effective surface modification and become the prerequisite that carbon nanotube is used.
Mainly containing following two difficult problems aspect the exploitation high-performance carbon nanotube nano composite material at present:
(1) can be in matrix the Uniform Dispersion carbon nanotube;
(2) how to strengthen interface interaction power between carbon nanotube and matrix in order to load is transferred to carbon nanotube from matrix effectively.
Under the effect that does not have chemical bond, but the load transfer between carbon nanotube and matrix mainly relies on the interaction of electrostatic interaction and Van der Waals force to realize. and the carbon nanotube of functionalization and the chemical bond between the polymer matrix connect can more effectively realize load transfer.
Carry out chemical modification in carbon nano tube surface three kinds of diverse ways arranged:
(1) adds functional group at the carbon nanotube wall;
(2) carry out functionalization at rejected region.
(3) carbon nanotube carries out acid treatment, and soon carbon nanotube refluxes in nitric acid or with its ultrasonic concussion in the mixture of sulfuric acid and nitric acid, carboxyl introduced carbon nanotube.Carbon nanotube and SOC12 reaction with carboxyl are converted into acyl chlorides with carboxyl; Acyl chlorides further reacts with amino or oxy-compound again, generates new modified carbon nano-tube.
The technology such as normal temperature, atmospheric plasma body chemical vapor phase growing, ion implantation, sputter, plasma spraying, chemical polymerization, anodic oxidation obtain widespread use in the fields such as aerospace, electronics, machinery.This new process for treating surface is being brought into play increasing effect in the nanometer engineering technology in recent years.
Normal temperature, atmospheric plasma refer to part or all of Ionized gas, comprise electronics, ion, also comprise the high energy activeconstituentss such as free radical and photon.Normal temperature, atmospheric plasma have high energy, at a high speed, highly active advantage.Equilibrium relationship in nonequilibrium state normal temperature, the atmospheric plasma between electronic temp and ion temperature is false, and normal temperature, atmospheric plasma can have both effectively to be excited molecule, atom and preserve the characteristic that the material substrate molecule is not damaged; In the material surface improved performance, substrate performance is unaffected; Form gaseous species and the plasma chemistry condition of plasma body by suitable selection. can carry out the modification of extraordinary purpose to chemical structure and the physical structure of bill of material surface layer, and can realize the irrealizable reaction of traditional chemical reaction.
The using plasma treatment technology carries out study on the modification to carbon nano tube surface provides scientific basic and strong technical support for next step application of carbon nanotube.In plasma treatment procedure, acceleration electronics, ion and the free radical and the carbon that produce are received.The mitron surface bumps and interacts, and must exert an influence to its pattern.Before being untreated, carbon nano tube surface has the decolorizing carbon of some random arrangement, and through after the Cement Composite Treated by Plasma, surperficial decolorizing carbon is assembled the formation pencil gradually, and along with treatment time prolongation fascircular texture is more obvious.Simultaneously, find to be stained with particulate material at sidewall.In argon plasma, find that also plasma body is to the caused morphology change of the etching effect of carbon nanotube [13].Argon ion constantly bombards carbon nanotube, etches away some decolorizing carbon particle and granules of catalyst, and carbon nanotube is fractureed, and length diminishes, and has played the purpose of certain cleaning carbon nano tube surface.In the high-temperature hydrogen plasma body [13～15,17], find that volumetric expansion can occur carbon nanotube, " onion " (onion shape) structure appears in the top.In high temperature H2 plasma body, multi-walled carbon nano-tubes can undergo phase transition, generate the nanometer diamond crystal, and along with the increase of time, in plasma treatment procedure, acceleration electronics, ion and the free radical and the carbon nano tube surface that produce bump and interact, and must exert an influence to its pattern.Before being untreated, carbon nano tube surface has the decolorizing carbon of some random arrangement, and through after the Cement Composite Treated by Plasma, surperficial decolorizing carbon is assembled the formation pencil gradually, and along with treatment time prolongation fascircular texture is more obvious.Simultaneously, find to be stained with particulate material at sidewall.But utilize normal atmosphere, normal-temperature plasma that the technology of surface modification of carbon nanotube is had no patent report.
Summary of the invention
Technical problem to be solved by this invention provides the treatment process of carbon nano tube surface normal atmosphere, normal-temperature plasma modification, present method is dry method modification, can the directly modification on acquisition carbon nano tube surface of a step under normal atmosphere and room temperature, open environment.
The treatment process of carbon nano tube surface normal atmosphere of the present invention, normal-temperature plasma modification comprises:
Carbon nanotube is placed on the dedicated transmissions device of apparatus for processing plasma, at normal atmosphere, under the open environment, directly plasma jet is arrived carbon nano tube surface, carbon nanotube is moved in plasma atmosphere, processing power is 10W-5000W, and the time is 0.01s-6000s, produces surface modification of carbon nanotube.
Described carbon nanotube is commercially available commodity.
Described plasma body is selected from one or more in helium, argon gas or the functional gas, and wherein helium, argon gas mol ratio are 50%-99.99%, and functional gas is 0.001～30%, and the plasma body of flowing through simultaneously forms the district and forms plasma atmosphere.
The purity of described helium or argon gas is 99.99%.
Described functional gas is SO
2, ammonia, oxygen, hydrogen, nitrogen, tetrafluoro-methane, carbonic acid gas, methane (CH
4), ethane (C
2H
6), propane (C
3H
8), butane (C
4H
10), pentane (C
5H
12), hexane (C
6H
14), heptane (C
7H
16), octane (C
8H
18), nonane (C
9H
20), decane (C
10H
22), undecane (C
11H
24), dodecane (C
12H
26), tridecane (C
13H
28), ethene (C
2H
4), propylene (C
3H
6), butylene (C
4H
8), amylene (C
5H
10), hexene (C
6H
12), propadiene (C
3H
4), divinyl (C
4H
6), isoprene (C
5H
8), hexatriene (C
6H
8), acetylene (C
2H
2), propine (C
3H
4), butine (C
4H
6), pentyne (C
5H
8), hexin (C
6H
10), heptyne (C
7H
12), octyne (C
8H
14), n-heptylacetylene (C
9H
16), decine (C
10H
18), undecyne (C
11H
20), tetrafluoroethylene and silane, various siloxane gas, vinylformic acid, the steam of methacrylic acid or their composition gas.
Describedly under jet plasma atmosphere prerequisite, carbon nano tube surface is carried out surface modification by the demand of difference requirement.
Described modified carbon nano-tube is applied to polymer modification, polymer composite modification and fiber.
Improve in the system of carbon nano tube surface performance in the treatment process of normal atmosphere, normal-temperature plasma modification, mainly comprise by plasma generation high energy active particle, carbon nano tube surface is etched or activation, grafting etc. make carbon nano tube surface produce the effect of two like magnetic poles repel each other.Under jet plasma atmosphere prerequisite, form free radical and cause thus carbon nano tube surface that further free radical causes to form the free radical grafting reaction under certain condition with other materials and component and the surface modification of carbon nanotube that obtains, and because the radical polymerization that the carbon nano tube surface free radical of plasma body initiation causes is plasma body Atom Transfer Radical Polymerization (ATRP).The plasma body surface modification of carbon nanotube is dry method modification, mainly adopts above-described gas and their mixed gas, and the plasma body that utilizes normal atmosphere, normal-temperature plasma equipment to produce carries out surface treatment to carbon nanotube.A common step of plasma surface modifying method finishes, and can realize the raising to the consistency of different physical property materials by adjusting the gaseous fraction, the proportioning that form plasma body.
Beneficial effect
(1) the inventive method process controllability is strong, and change technique is simple, technical process is short, need not aftertreatment, and level of automation is high, and energy consumption is low, continuous operations, easily realizes large-scale industrialization production and little to the pollution of environment;
(2) gained carbon nano tube surface of the present invention produces the effect of two like magnetic poles repel each other, reaches the possibility that reduces nanoparticle agglomerates;
(3) gained carbon nanotube particulate internal structure of the present invention is not destroyed, and its nano crystal particles uniformity coefficient and particle size distribution range narrow down, and the dispersiveness in associated materials improves, and improves with corresponding high molecular bonding properties.
Description of drawings
The transmission electron microscope photo of Fig. 1 gained sample;
Fig. 2 is that the water-sol (0.5/1000 nano powder/water) of gained sample leaves standstill 24 hours contrast experiment's photos.No. 1 is the former powder helium plasma treatment of commodity carbon nanotube sample, and No. 2 is the former powder oxygen plasma treatment of commodity carbon nanotube sample, and No. 3 is the former powder of commodity carbon nanotube;
Fig. 3 is carbon nano tube surface plasma modification device schematic diagram, 1 plasma body carrier gas (helium or argon gas), 2 functional gases, 3 plasma body generation control systems, 4 plasma generators and shower nozzle, 5 nano-powder e Foerderanlages, 6 surface treating nano powders not, 7 surface-treated nano-powders.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
Get on the dedicated transmissions device that a certain amount of commercialization carbon nanotube is placed on apparatus for processing plasma.Schematic diagram such as Fig. 3 passage of plasma nozzle (or install additional), this container or carrier place 2 centimetres of the spout below specific ranges of normal pressure, normal-temperature plasma jet apparatus with interior (design of nozzle segment passage is by particular requirement), nano-powder lay thickness is by 5 millimeters thickness laies, under the prerequisite of opening normal pressure, room-temperature plasma, container or carrier are done the motion of specific speed. realize that carbon nanotube is processed under helium plasma atmosphere, 40 watts of power and 5 second time.Transmission electron microscope photo such as Fig. 1 of this sample.The water-sol (0.5/1000 nano powder/water) that is formed by this sample leaves standstill 24 hours contrast experiment's photos such as Fig. 2-No. 1 sample.
Get on the dedicated transmissions device that a certain amount of commercialization carbon nanotube is placed on apparatus for processing plasma.Schematic diagram such as Fig. 3 passage of plasma nozzle (or install additional), this container or carrier place 2 centimetres of the spout below specific ranges of normal pressure, normal-temperature plasma jet apparatus with interior (design of nozzle segment passage is by particular requirement), nano-powder lay thickness is pressed 2-9 millimeter thickness lay, under the prerequisite of opening normal pressure, room-temperature plasma, container or carrier are done the motion of specific speed. realize that carbon nanotube is processed under oxygen gas plasma atmosphere, 40 watts of power and 5 second time.Transmission electron microscope photo such as Fig. 1 of this sample.The water-sol (0.5/1000 nano powder/water) that is formed by this sample leaves standstill 24 hours contrast experiment's photos such as Fig. 2-No. 2 sample.
Claims (4)
1. the treatment process of carbon nano tube surface normal atmosphere, normal-temperature plasma modification comprises:
Carbon nanotube is placed on the dedicated transmissions device of apparatus for processing plasma, at normal atmosphere, under the open environment, directly plasma jet is arrived carbon nano tube surface, carbon nanotube is moved in plasma atmosphere, processing power is 10W-5000W, and the time is 0.01s-6000s, produces surface modification of carbon nanotube; Wherein, described plasma body is helium or argon gas.
2. the treatment process of carbon nano tube surface normal atmosphere according to claim 1, normal-temperature plasma modification, it is characterized in that: the purity of described helium or argon gas is 99.99%.
3. the described method of arbitrary claim according to claim 1-2 is characterized in that: under jet plasma atmosphere prerequisite carbon nano tube surface is carried out surface modification by the demand of difference requirement.
4. the described method of arbitrary claim according to claim 1-2, it is characterized in that: described modified carbon nano-tube is applied to polymer modification, polymer composite modification and fiber.
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| CN101559936B (en) * | 2009-05-27 | 2012-09-26 | 天津大学 | Carbon nano-tube modified by in-situ polymerization based on plasma initiation and preparation method thereof |
| CN101830456B (en) * | 2010-05-12 | 2012-01-04 | 中国科学院上海应用物理研究所 | Method for improving electric conductivity of carbon nano tube network |
| CN102380133B (en) * | 2011-10-20 | 2013-09-11 | 天津师范大学 | Multi-walled carbon nanotube injected with carboxyl ions, preparation method and application thereof |
| EP2788433A1 (en) * | 2011-12-05 | 2014-10-15 | Solvay SA | Use of atmospheric plasma for the surface of inorganic particles and inorganic particles comprising an organic fluorine-containing surface modification |
| CN102557005B (en) * | 2011-12-28 | 2013-09-18 | 温州医学院 | Modification method for reducing cytotoxicity of carbon nanotubes |
| CN103241724B (en) * | 2013-05-09 | 2015-06-10 | 上海应用技术学院 | Fluorine-containing polymer functionalized carbon nanotube and preparation method thereof |
| CN105350130A (en) * | 2015-09-28 | 2016-02-24 | 复旦大学 | Water-driven multistage tube carbon nanotube fibers and method for preparing same |
| US10920085B2 (en) | 2016-01-20 | 2021-02-16 | Honda Motor Co., Ltd. | Alteration of carbon fiber surface properties via growing of carbon nanotubes |
| CN108383102B (en) * | 2018-04-10 | 2020-04-24 | 浙江工商大学 | Method and device for preparing carbon nano material by plasma in open environment |
| CN109148240B (en) * | 2018-07-06 | 2020-05-01 | 健康力（北京）医疗科技有限公司 | Metal ceramic tube shell for CT bulb tube and preparation method thereof |
| CN110302770A (en) * | 2019-05-28 | 2019-10-08 | 高化学（江苏）化工新材料有限责任公司 | A kind of method of modifying of carbon nano-tube catalyst and its application |
| KR102441127B1 (en) * | 2020-07-01 | 2022-09-07 | 한국핵융합에너지연구원 | Method for enhance water-dispersibility of conductivity carbon powder and method for colloidal solution of conductivity carbon powder |
| CN111733589B (en) * | 2020-07-15 | 2022-06-21 | 安徽工业大学 | Carbon fiber monofilament micro-plasma surface micro-area processing device and using method |
| CN115069168B (en) * | 2022-06-14 | 2023-09-22 | 西安交通大学 | Carbon nanotube material fluorination device based on plasma and application method thereof |
| CN115594887B (en) * | 2022-12-13 | 2023-04-07 | 广东粤港澳大湾区黄埔材料研究院 | Preparation method of modified carbon nanotube and application of modified carbon nanotube in tire tread rubber |
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| CN101220166A (en) * | 2008-01-28 | 2008-07-16 | 南京航空航天大学 | Process for producing carbon nano-tube/polymer high dielectric constant compound film |
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