CN102070877B - Low-intensity magnetic field-induced ordered carbon nanotube/epoxy resin composite material and preparation method thereof - Google Patents
Low-intensity magnetic field-induced ordered carbon nanotube/epoxy resin composite material and preparation method thereof Download PDFInfo
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- CN102070877B CN102070877B CN201010614797A CN201010614797A CN102070877B CN 102070877 B CN102070877 B CN 102070877B CN 201010614797 A CN201010614797 A CN 201010614797A CN 201010614797 A CN201010614797 A CN 201010614797A CN 102070877 B CN102070877 B CN 102070877B
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Abstract
The invention provides an ordered carbon nanotube/epoxy resin composite material and a preparation method thereof. The composite material and the preparation method thereof are characterized in that: an adopted carbon nanotube at least loads one of iron nano particles, cobalt nano particles, nickel nano particles and ferroferric oxide nano particles. The preparation method comprises the following steps of: dispersing 1 to 15 mass parts of carbon nanotube into 100 mass parts of epoxy resin in the presence of a solvent by using mechanical stirring and ultrasonic methods, performing heating to remove the solvent, adding 10 to 50 mass parts of amine curing agent for further uniform mixing, performing vacuum defoaming, pouring the mixture into a mould in a magnetic field with the intensity of 0.15 to 1.0 tesla, curing the poured mixture at room temperature for 0.5 to 1 hour, taking the mould out of the magnetic field, and finally continuously curing the mixture at the room temperature to 120 DEG C for 4 to 24 hours. The preparation method provided by the invention is simple, and ensures high efficiency and low cost; and the obtained product ordered carbon nanotube/epoxy resin composite material has high comprehensive performance.
Description
Technical field
The invention belongs to nano material technology processing and applied technical field.Be particularly related to a kind of low-intensity magnetic field inductive ordering carbon nano tube/epoxy resin matrix material of preparation.
Background technology
In the nearest more than ten years; Because functional performances such as the mechanical property of particular structure, excellence and light, electricity, heat; Carbon nanotube (CNTs) obtains important breakthrough in using in a lot of fields; Also showing more potential in many high-tech areas simultaneously uses; Like fields such as biotechnology, Materials science, catalytic chemistry, physical chemistry, biological chemistries, so the ideal that CNTs is considered to the novel nano matrix material adds phase, and becomes a new focus in the nano science research.Carbon nanotube has very high major diameter and stronger Van der Waals force is arranged each other and assembles easily and reunite; Causing it in polymeric matrix, to lack well disperses; How making carbon nanotube obtain the excellent comprehensive performance in the polymeric matrix good distribution is one of this hot research fields, also is the main contents of existing research and technology.CNTs that it should be noted that free random orientation on the other hand is filled into and does not give full play of the ideal effect in the polymkeric substance.Compare with the CNTs of random orientation; Arrange performance and functional performance that orderly carbon nanotube can show a lot of excellences; As can form excellent more conductive network passage, can realize good load transmission, thereby further improve the performance of CNTs/ polymer composites greatly.Thereby the research that carbon nanotube carries out oriented more and more received the attention of people's height, and certain progress has been arranged, but still be in the preliminary stage.
In order to prepare ordered arrangement CNTs/ polymer composites; Prior art has proposed some methods, mainly contains: 1. template, promptly under the geometrical constraint of template; Through methods such as chemical vapour deposition, galvanic deposit or spin coatings one in polymkeric substance and the nanophase implanted another phase mutually; Form nano composite material, there are problems such as technical matters process complicacy, preparation cost height in this method owing to will use conditions such as special template, rare gas element and high temperature.Prior art (CN200610042684, CN200710119224, CN200580021228.8) all is the preparation of Carbon Nanotube Array at present, does not also relate to the related polymer matrix material.2. arrange in the field of force, and the fused polymkeric substance is applied coaxial shearing, the carbon nanotube of stochastic distribution will be under the rubbing effect of melt arranged in co-axial alignment, but at present domestic also do not see relate to the patent that arrange in the field of force.3. electric field is arranged, and utilizes the features of response of nano particle to electric field, and the directed dipolar interaction of generation is impelled particle to attract each other and arranged.The particle that can respond electric field is ferroelectricity material or suitable/contrary electrically material (under highfield) often.Patent CN200610028956 provides a kind of method for preparing oriented arrange carbon nanotube composite material of arranging with electric field; They adopt a kind of oriented arrange carbon nanotube composite material high-speed preparation device, it is made up of pore on vibratory screening apparatus, cable, vibrating motor, foundation trench, insulator foot, HV generator, sealed insulation shell, the sealed insulation shell and sealed insulation cover.Patent CN200610076246 provides a kind of composite material and preparation method thereof of electric field controls carbon nanotube dispersed arrangement, it is characterized in that carbon nanotube is applied interchange or DC electric field, and carbon nanotube is arranged along electric field line.This kind method is had relatively high expectations to appointed condition, and exists pollution heavily to wait negative impact.
A kind of new method that obtains showing great attention to recently is the induced by magnetic field ranking method.Magnetic field is and temperature, the same important physical parameter high-intensity magnetic field of the pressure particular electrical magnetic field form as a kind of extreme condition; Can high-intensity energy contactlessly be delivered to the atomic scale of material; Change the behaviors such as arrangement, coupling and migration of atom and molecule; Thereby tissue and performance to material produce huge and deep effect, a kind of important technical of magnetic field processing having become development of new material.Patent CN200910154049 provides the method for a kind of magnetic induced multi-wall carbon nano tubes ordered arrangement in chitosan basal body; This kind method through the early stage a series of Processing of Preparation carbon nanotube/chitosan acetic acid mixed solution; Place permanent magnet in both mold ends at last, again mixing solutions is filled with mould.This kind method is simple, control easily, with low cost, be convenient to suitability for industrialized production, be a kind of method that big application potential is arranged.
Summary of the invention
The purpose of this invention is to provide that a kind of high-level efficiency, technology are simple, with low cost, excellent combination property, broad-spectrum ordering carbon nano tube/epoxy resin matrix material and preparation method thereof.
A kind of low-intensity magnetic field inductive of the present invention ordering carbon nano tube/epoxy resin matrix material; Be that the use carbon nanotube is that load at least has wherein a kind of carbon nanotube of iron, cobalt, nickel and ferriferrous oxide nano-particle; Earlier with mechanical stirring and ultrasonic method with the particular carbon nanotube of 1 ~ 15 mass parts by solvent dispersion in the epoxy resin of 100 mass parts; Heating is removed the amine curing agent that adds 10 ~ 50 mass parts behind the solvent again and is further mixed; After the froth in vacuum mixture is poured into that to place intensity be the mould in the magnetic field of 0.15 ~ 1.0 tesla; After at room temperature solidifying 0.5 ~ 1h, mould is taken out from magnetic field, ℃ continuation curing a 4 ~ 24h makes in room temperature ~ 120 at last.Its preparation method comprises the steps:
(1) with the epoxy resin of 100 mass parts, the carbon nanotube of 1 ~ 15 mass parts and the solvent of 20 ~ 200 mass parts, machinery stirs 5 ~ 30min, ultrasonic then aid dispersion 0.5 ~ 24h earlier;
(2) successively adopt the method for heating and underpressure distillation to remove the solvent in the mixture that step (1) obtains;
(3) join the amine curing agent of 10 ~ 50 mass parts in the carbon nano tube/epoxy resin mixture that step (2) obtains and carry out mechanical stirring 5 ~ 15min, vacuum froth breaking then;
(4) the carbon nano tube/epoxy resin mixed solution that step (3) is obtained is poured into and is placed on intensity is in the mould in 0.15 ~ 1.0T magnetic field; After at room temperature solidifying 0.5 ~ 4h; Mould is taken out from magnetic field, and ℃ continuation curing a 4 ~ 24h promptly obtains a kind of ordering carbon nano tube/epoxy resin matrix material in room temperature ~ 120 more at last.
The described epoxy resin of step (1) is bisphenol A-type, and epoxy equivalent (weight) is in 145 ~ 350g/mol scope.
The described carbon nanotube of step (1) adheres to or is enclosed with at least a in nickel, iron, cobalt, the Z 250 particle, and is at least a in multi-walled carbon nano-tubes, the SWCN.
The described solvent of step (1) is at least a in ethanol, acetone, trichloromethane, methylene dichloride or the pimelinketone.
The described amine curing agent of step (3) is at least a in m-xylene diamine, TEPA, the isophorone diamine.
The described magnetic field of step (4) is the stationary magnetic field that permanent magnet or electro-magnet provide.
A kind of low-intensity magnetic field inductive ordering carbon nano tube/epoxy resin matrix material provided by the present invention and preparation method thereof its advantage is: it is matrix that (1) the present invention adopts epoxy resin; It is a kind of thermosetting resin of excellence; Of many uses, its processing fluidity is good, helps the magnetic field ordered arrangement of carbon nanotube; And curing process is simpler, and efficient is higher.Prepared ordering carbon nano tube/epoxy resin matrix material has the excellent comprehensive performance, and Application Areas is more extensive; (2) carbon nanotube obtains to be more prone to, and is not limited to the carbon nanotube of load Z 250 particle, can also adopt the carbon nanotube of load iron, cobalt, nickel particles; (3) the magnetic field acquisition is more convenient, is not limited to permanent magnet, can also adopt dc electromagnetic field, and magneticstrength is regulated convenient; (4) because magneticstrength required for the present invention is lower, low for equipment requirements, technology is simple, and is with low cost.
Description of drawings:
Fig. 1 is a action of a magnetic field specimen preparation synoptic diagram.
Fig. 2 is the optical transmission microphotograph of the random orientation carbon nano tube/epoxy resin matrix material that do not obtain through induced by magnetic field.
Fig. 3 is the optical transmission microphotograph of the ordering carbon nano tube/epoxy resin matrix material for preparing among all embodiment.
Fig. 4 is the different content ordering of embodiment 1 method preparation and the volume specific resistance of disordering carbon nano tube/epoxy resin matrix material.This figure shows electroconductibility the improving a lot than disordering carbon nano tube/epoxy resin matrix material of ordering carbon nano tube/epoxy resin matrix material.
Fig. 5 is the ordering of embodiment 1 method preparation and the second-order transition temperature curve of disordering carbon nano tube/epoxy resin matrix material and pure epoxy resin, the pure EP of a.; B. ordering CNTs (3wt%)/EP matrix material; C. disordering CNTs (3wt%)/EP matrix material.This figure shows second-order transition temperature the improving a lot than disordering carbon nano tube/epoxy resin matrix material of ordering carbon nano tube/epoxy resin matrix material.
Embodiment:
Following embodiment further specifies of the present invention, rather than to qualification of the present invention.
Embodiment 1:
A kind of preparation method of low-intensity magnetic field inductive ordering carbon nano tube/epoxy resin matrix material comprises the steps:
(1) be that the bisphenol A type epoxy resin of 192g/mol, the multi-walled carbon nano-tubes of 3 mass parts nickel particles loads and the acetone solvent of 200 mass parts mix with 100 mass parts oxirane values, machinery stirs 5min, ultrasonic then aid dispersion 0.5h earlier;
(2) successively adopt the method for heating and underpressure distillation to remove the acetone in the mixture that step (1) obtains.
(3) join the TEPA solidifying agent of 15 mass parts in the carbon nano tube/epoxy resin mixture that step (2) obtains and carry out mechanical stirring 5min, vacuum froth breaking then.
(4) the carbon nano tube/epoxy resin mixed solution that step (3) is obtained is poured in the mould that is placed in the permanent magnetic field that intensity is 0.25T; After at room temperature solidifying 0.5h; Mould is taken out from magnetic field, continue to solidify 24h in room temperature more at last and promptly obtain a kind of ordering carbon nano tube/epoxy resin matrix material.
Embodiment 2:
A kind of preparation method of low-intensity magnetic field inductive ordering carbon nano tube/epoxy resin matrix material comprises the steps:
(1) be the bisphenol A type epoxy resin of 192g/mol, the SWCN of 3 mass parts iron particle loads and the trichloromethane solvent of 200 mass parts with 100 mass parts oxirane values, machinery stirs 15min, ultrasonic then aid dispersion 2h earlier;
(2) successively adopt the method for heating and underpressure distillation to remove the trichloromethane in the mixture that step (1) obtains;
(3) join the m-xylene diamine solidifying agent of 20 mass parts in the carbon nano tube/epoxy resin mixture that step (2) obtains and carry out mechanical stirring 10min, vacuum froth breaking then;
(4) the carbon nano tube/epoxy resin mixed solution that step (3) is obtained is poured in the mould that is placed in the constant EM field that intensity is 0.35T; After at room temperature solidifying 0.5h; Mould is taken out from magnetic field, continue to solidify 12h at 80 ℃ more at last and promptly obtain a kind of ordering carbon nano tube/epoxy resin matrix material.
Embodiment 3:
A kind of preparation method of low-intensity magnetic field inductive ordering carbon nano tube/epoxy resin matrix material comprises the steps:
(1) be the bisphenol A type epoxy resin of 145g/mol with 100 mass parts oxirane values, the multi-walled carbon nano-tubes of 15 mass parts cobalt particle loads and the dichloromethane solvent of 100 mass parts mix, and machinery stirs 30min, ultrasonic then aid dispersion 12h earlier.
(2) successively adopt the method for heating and underpressure distillation to remove the dichloromethane solvent in the mixture that step (1) obtains.
(3) join the isophorone diamine solidifying agent of 50 mass parts in the carbon nano tube/epoxy resin mixture that step (2) obtains and carry out mechanical stirring 5min, vacuum froth breaking then.
(4) the carbon nano tube/epoxy resin mixed solution that step (3) is obtained is poured into and is placed on intensity is in the mould in the constant EM field of 1.0T; After at room temperature solidifying 4h; Mould is taken out from magnetic field, continue to solidify 8h at 120 ℃ more at last and promptly obtain a kind of ordering carbon nano tube/epoxy resin matrix material.
Embodiment 4:
A kind of preparation method of low-intensity magnetic field inductive ordering carbon nano tube/epoxy resin matrix material comprises the steps:
(1) be that the bisphenol A type epoxy resin epoxy resin of 350g/mol, the Z 250 particle SWCN of 1 mass parts and the alcohol solvent of 200 mass parts mix with 100 mass parts oxirane values, machinery stirs 30min, ultrasonic then aid dispersion 2h earlier.
(2) successively adopt the method for heating and underpressure distillation to remove the alcohol solvent in the mixture that step (1) obtains.
(3) join the m-xylene diamine solidifying agent of 10 mass parts in the carbon nano tube/epoxy resin mixture that step (2) obtains and carry out mechanical stirring 15min, vacuum froth breaking then.
(4) the carbon nano tube/epoxy resin mixed solution that step (3) is obtained is poured into and is placed on intensity is in the mould in the constant EM field of 0.5T; After at room temperature solidifying 0.5h; Mould is taken out from magnetic field, continue to solidify 24h in room temperature more at last and promptly obtain a kind of ordering carbon nano tube/epoxy resin matrix material.
Embodiment 5:
A kind of preparation method of low-intensity magnetic field inductive ordering carbon nano tube/epoxy resin matrix material comprises the steps:
(1) be that the bisphenol A type epoxy resin epoxy resin of 194g/mol, the Z 250 particle multi-walled carbon nano-tubes of 5 mass parts and the cyclohexanone solvent of 100 mass parts mix with 100 mass parts oxirane values, machinery stirs 30min, ultrasonic then aid dispersion 2h earlier.
(2) successively adopt the method for heating and underpressure distillation to remove the cyclohexanone solvent in the mixture that step (1) obtains.
(3) join the m-xylene diamine solidifying agent of 17 mass parts in the carbon nano tube/epoxy resin mixture that step (2) obtains and carry out mechanical stirring 15min, vacuum froth breaking then.
(4) the carbon nano tube/epoxy resin mixed solution that step (3) is obtained is poured into and is placed on intensity is in the mould in the 0.3T permanent magnetic field; After at room temperature solidifying 0.5h; Mould is taken out from magnetic field, continue to solidify 12h at 80 ℃ more at last and promptly obtain a kind of ordering carbon nano tube/epoxy resin matrix material.
Claims (6)
1. the preparation method of a low-intensity magnetic field inductive ordering carbon nano tube/epoxy resin matrix material is characterized in that: comprise the steps:
(1) with the epoxy resin of 100 mass parts, the carbon nanotube of 1-15 mass parts and the solvent of 20-200 mass parts, machinery stirs 5-30min, ultrasonic then aid dispersion 0.5-24h earlier; Described carbon nanotube adheres to or is enclosed with at least a in nickel, iron, cobalt, the Z 250 particle, and is at least a in multi-walled carbon nano-tubes, the SWCN;
(2) successively adopt the method for heating and underpressure distillation to remove the solvent in the mixture that step (1) obtains;
(3) join the amine curing agent of 10-50 mass parts in the carbon nano tube/epoxy resin mixture that step (2) obtains and carry out mechanical stirring 5-15min, vacuum froth breaking then;
(4) the carbon nano tube/epoxy resin mixed solution that step (3) is obtained is poured into and is placed on intensity is in the mould in the 0.15-1.0T magnetic field; After at room temperature solidifying 0.5-4h; Mould is taken out from magnetic field, solidify 4-24h in room temperature-120 a ℃ continuation more at last and promptly obtain a kind of ordering carbon nano tube/epoxy resin matrix material.
2. preparation method according to claim 1 is characterized in that: the described epoxy resin of step (1) is bisphenol A-type, and epoxy equivalent (weight) is in the 145-350g/mol scope.
3. preparation method according to claim 1 is characterized in that: the described solvent of step (1) is at least a in ethanol, acetone, trichloromethane, methylene dichloride or the pimelinketone.
4. preparation method according to claim 1 is characterized in that: the described amine curing agent of step (3) is at least a in m-xylene diamine, TEPA, the isophorone diamine.
5. preparation method according to claim 1 is characterized in that: the described magnetic field of step (4) is the stationary magnetic field that permanent magnet or electro-magnet provide.
6. with any ordering carbon nano tube/epoxy resin matrix material that described preparation method prepares among the claim 1-5.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103059514B (en) * | 2012-12-05 | 2015-05-20 | 哈尔滨工业大学 | Preparation method of magnetic lyophoby type carbon nano tube base nanochannel damping plate and damper |
| CN104387768B (en) * | 2014-08-27 | 2017-02-15 | 汕头大学 | Electric-conduction wear-resistance composite material molded by using magnetic-orienting ice-templating method |
| CN105462167A (en) * | 2014-09-25 | 2016-04-06 | 倪伟华 | Preparation method of carbon nanotube epoxy resin spectacle frame composite material |
| CN107938432A (en) * | 2017-10-19 | 2018-04-20 | 周夕和 | A kind of preparation method of carbon nanometer paper composites |
| CN107828344B (en) * | 2017-11-21 | 2020-11-03 | 桂林电子科技大学 | One-dimensional micro-nano particle/epoxy resin composite adhesive film arranged along Z direction and preparation method thereof |
| CN109385906B (en) * | 2018-10-10 | 2021-03-19 | 河海大学 | Preparation method of magnetic-orientation carbon nanotube-reinforced glass fiber epoxy composite material |
| CN109749093A (en) * | 2018-12-17 | 2019-05-14 | 长沙理工大学 | A kind of forming method improving epoxide resin material surface abrasion resistance |
| CN114854176A (en) * | 2022-06-20 | 2022-08-05 | 苏州圣杰特种树脂有限公司 | High Tg temperature epoxy resin for aviation and production process thereof |
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| CN101604555A (en) * | 2009-06-30 | 2009-12-16 | 哈尔滨工业大学 | The preparation method of composite film stealth material of magnetic orientation carbon nano tube |
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Non-Patent Citations (2)
| Title |
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| Ma C. G.et al..Electrical and thermal properties of carbon nanotubes/PMMA composites induced by low magnetic fields.《PLASTICS, RUBBER AND COMPOSITES》.2010,第39卷(第2期),第49-53页. * |
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