CN106283623A - A kind of surface size processing method of CNT - Google Patents
A kind of surface size processing method of CNT Download PDFInfo
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- CN106283623A CN106283623A CN201510237417.4A CN201510237417A CN106283623A CN 106283623 A CN106283623 A CN 106283623A CN 201510237417 A CN201510237417 A CN 201510237417A CN 106283623 A CN106283623 A CN 106283623A
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Abstract
The invention belongs to technical field of nano material, the process processed particularly to a kind of carbon nano tube surface starching, the CNT through starching process can be used as the reinforcement of all kinds of epoxy resin composite materials of amine curing agent solidification.The present invention includes techniques below step.Step I: the CNT of surface amino groups functionalization is added in preferred sizing agent solution, obtains uniform liquefied mixture through ball milling；Step II: step I gained mixture is through filtering off except unnecessary sizing agent solution, and is vacuum dried；Step III: dried CNT is carried out secondary ball milling, the CNT rotor-vibrating screen after ball milling sieves, and obtains the CNT that the starching of different-grain diameter processes.CNT after starching is easily dispersed in epoxy resin-base, and beneficially the surface infiltration of epoxy resin, has, to the epoxy resin-base of amine curing agent solidification, the effect of being remarkably reinforced.Present invention process is easy, it is easy to actual production and application.
Description
Technical field:
The invention belongs to technical field of nano material, the process processed particularly to a kind of carbon nano tube surface starching, the CNT through starching process can be used as the nanometer reinforcement of all kinds of epoxy resin composite materials of amine curing agent solidification.
Background technology:
Since Japanese Scientists in 1991 finds CNT, because of nanometer grade diameter, the high length-diameter ratio of its uniqueness, and the mechanical property of excellence, it is expected to become the preferable reinforcement of advanced composite material.In recent years, all conduct extensive research around being prepared on a large scale of CNT with commercial Application.Owing to CNT has bigger draw ratio and specific surface area, it is susceptible to reunite, is difficult in resin matrix dispersed.Meanwhile, the surface inertness of CNT makes the interface binding power between itself and matrix more weak, and under plus load effect, stress can not effectively transmit between matrix and CNT.For these shortcomings of CNT, solution currently mainly is that CNT carries out surface physics modification and chemical modification.The method of physical modification mainly carries out physical absorption with surfactant and organic polymer in carbon nano tube surface, and the existence of adsorption layer can improve the dispersibility of CNT, but the adhesion of physical absorption is more weak, thus can not effectively improve interface cohesion.Chemical modification method mainly introduces chemical functional group or graft polymers on the surface of CNT, it is sterically hindered that the existence of chemical graft thing increases between CNT, the functional group being simultaneously grafted can improve the compatibility between epoxy molecule chain, thus the dispersion and interface cohesion to CNT can be improved effect.Such as Niu Mei etc. (patent publication No. CN102219925A) use p-phthalic acid and ethylene glycol surface modifying multiwall carbon nano-tube, good with the multiple chemical substance compatibility, but general to the reinforced effects of polymer matrix composites.CNT is stirred by Zhao Fujun etc. (patent publication No. CN1667040) with coupling agent, dispersant and organic solvent, and carries out ultrasonic Treatment, and CNT can be made to be easily dispersed in the epoxy, combines for composite material interface and there is no improvement.In epoxy resin composite material preparation process, aminated carbon nano tube is widely used as nanoreinforcement material, but owing to the amino group polarity on aminated carbon nano tube surface is bigger, with in epoxy resin mixed process, epoxy resin is poor to the wellability of aminated carbon nano tube, the amino group reactivity of carbon nano tube surface is relatively low simultaneously, thus can not fully improve the dispersibility of CNT, and plays its potentiation.
It is known that carbon fiber is before dispatching from the factory, it is required for processing, at one layer of sizing agent of its surface-coated, to improve the interface compatibility of itself and resin matrix through starching.Owing to CNT has the highest draw ratio, can be regarded as a kind of quasi-continuous nanofiber, and CNT inert for surface chemistry, also should carry out starching process on its surface, to improve its dispersion in resin matrix and reinforced effects.Because form and the surface chemical property of CNT with traditional carbon fibres differ greatly, its sizing process also should be different.
Summary of the invention:
It is an object of the invention to for the existing state of the art, solve the deficiency of existing surface modification of carbon nanotube method, more effectively improve interface cohesion and the mechanical property of composite, the surface of aminated carbon nano tube is carried out starching process, improve the epoxy resin wellability to CNT, and make CNT have good dispersibility in epoxy resin-base, effectively play the CNT potentiation to resin matrix.
The present invention realizes the concrete technical scheme that above-mentioned purpose used:
The process that a kind of carbon nano tube surface starching processes, it is characterised in that include following components and step:
Component 1: preferably sizing agent, is dissolved in the mixed solvent of methyl iso-butyl ketone (MIBK) and isophorone for benzyl glycidyl ether or lauryl diglycidyl ether, and solution concentration is 50-80wt%, and methyl iso-butyl ketone (MIBK) is 1:2 ~ 2:1 with the volume ratio of isophorone.
Step I: the CNT of aminofunctional is added in component 1, obtains uniform liquefied mixture through ball milling.Wherein CNT and sizing agent solution quality are than for 1:2 ~ 1:8, and rotational speed of ball-mill is 150-300 r/min, and Ball-milling Time is 2-5 h.The multi-walled carbon nano-tubes of aminofunctional can be obtained through chloride and amidized chemical treatment by functionalized multi-wall carbonnanotubes, and this technique belongs to the known mature technology of this area.
Step II: step I gained mixture is through filtering off except unnecessary sizing agent solution, and heat drying under vacuum conditions；
Step III: dried CNT is carried out secondary ball milling, rotational speed of ball-mill is 50-100 r/min, and Ball-milling Time is 0.5-1 h.CNT rotor-vibrating screen after ball milling sieves, and can get, according to the mesh number of vibrosieve used, the CNT that the starching of different-grain diameter processes.
By the enforcement of technique scheme, the surface of aminated carbon nano tube is carried out starching process, it is added in all kinds of epoxy resin composite materials of amine curing agent solidification, can be obviously improved the epoxy resin wellability to CNT, CNT has good dispersibility in epoxy resin-base.Contrast the aminated carbon nano tube that non-starching processes, CNT after starching processes can be obviously improved the interface cohesion with epoxy resin-base, improving tensile property and the bending property of epoxy resin, wherein hot strength and stretch modulus promote amplitude >=10%, bending strength and bending modulus and promote amplitude >=15%.CNT after starching processes can be as the nanometer reinforcement of a kind of effective epoxy resin composite material.The technology of the present invention is easy and simple to handle, it is easy to popularization and application in actual production.
Accompanying drawing explanation
Fig. 1 is the HRTEM photo of the CNT in embodiment 1 after surface size process
Detailed description of the invention
By following example, the present invention is described in detail.
In each embodiment, epoxy resin poured body bending property and tensile property are tested according to GB/T2567-2008.
Embodiment 1
Component 1: benzyl glycidyl ether is dissolved in methyl iso-butyl ketone (MIBK)/isophorone mixed solvent, and solution concentration is 50wt%, methyl iso-butyl ketone (MIBK) is 1:2 with the volume ratio of isophorone.Benzyl glycidyl ether, methyl iso-butyl ketone (MIBK) and isophorone are produced by Aldrich Chemical Co., Ltd., and purity is 98%.Step I: the multi-walled carbon nano-tubes of ethylenediamine surface grafting is added in component 1, obtains uniform liquefied mixture through ball milling.The wherein multi-walled carbon nano-tubes of ethylenediamine surface grafting, the TNMC3 functionalized multi-wall carbonnanotubes that in Chengdu, epoch nanometer company of section produces is used to process obtain through chloride, amination, ethylenediamine is produced by Zhengzhou Zhi Yi chemical products company limited, CNT external diameter is 10 ~ 30nm, average length 5 μm, the surface grafting rate of amino is 2.5wt%.CNT and sizing agent solution quality are than for 1:2, and rotational speed of ball-mill is 300 r/min, and Ball-milling Time is 5 h.Step II: step I gained mixture is through filtering off except unnecessary sizing agent solution, and heat drying under vacuum conditions；Step III: dried CNT is carried out secondary ball milling, rotational speed of ball-mill is 100r/min, and Ball-milling Time is 0.5h.CNT after ball milling sieves with 200 mesh rotor-vibrating screens, obtains the CNT of the starching process of uniform particle sizes, average length 2.5 μm.
CNT before and after starching being processed is separately added in EPON 828 epoxy resin-base that Shell Co. Ltd produces, 2h is stirred at 60 DEG C, add the 4 of Huifeng Synthetic Material Co., Ltd., Jiangyin's production again, 4 '-MDA firming agent, 50 DEG C of stirring 1h, each component proportion is: CNT/EPON 828 epoxy resin/4,4 '-MDA firming agent=1/100/30(mass ratio).Being cast in steel die by mixture after deaeration, heating cure in vacuum drying oven, curing process program is 90 DEG C/1h+130 DEG C/3h+180 DEG C/2h.Resin-cast body hot strength prepared by non-starching CNT is 80MPa, and stretch modulus is 2.4GPa, and bending strength is 128MPa, and bending modulus is 3.1GPa；Resin-cast body hot strength prepared by the CNT containing sizing agent is 89MPa, and stretch modulus is 2.7Gpa, and bending strength is 148MPa, and bending modulus is 3.6GPa.
Embodiment 2
Component 1: lauryl diglycidyl ether is dissolved in methyl iso-butyl ketone (MIBK)/isophorone mixed solvent, and solution concentration is 70wt%, methyl iso-butyl ketone (MIBK) is 1:1 with the volume ratio of isophorone.Lauryl diglycidyl ether, methyl iso-butyl ketone (MIBK) and isophorone are produced by Aldrich Chemical Co., Ltd., and purity is 98%.Step I: the multi-walled carbon nano-tubes of diethylenetriamine surface grafting is added in component 1, obtains uniform liquefied mixture through ball milling.The wherein multi-walled carbon nano-tubes of diethylenetriamine surface grafting, the TNMC3 functionalized multi-wall carbonnanotubes that in Chengdu, epoch nanometer company of section produces is used to process obtain through chloride, amination, diethylenetriamine is produced by Beijing Hua Ye whole world Chemical Co., Ltd., CNT external diameter is 10 ~ 30nm, average length 5 μm, the surface grafting rate of amino is 2.3wt%.CNT and sizing agent solution quality are than for 1:5, and rotational speed of ball-mill is 250 r/min, and Ball-milling Time is 3h.Step II: step I gained mixture is through filtering off except unnecessary sizing agent solution, and heat drying under vacuum conditions；Step III: dried CNT is carried out secondary ball milling, rotational speed of ball-mill is 80r/min, and Ball-milling Time is 0.75h.CNT after ball milling sieves with 200 mesh rotor-vibrating screens, obtains the CNT of the starching process of uniform particle sizes, average length 3 μm.
CNT before and after starching being processed is separately added in EPON 828 epoxy resin-base that Shell Co. Ltd produces, 2h is stirred at 60 DEG C, add the 4 of Huifeng Synthetic Material Co., Ltd., Jiangyin's production again, 4 '-MDA firming agent, 50 DEG C of stirring 1h, each component proportion is: CNT/EPON 828 epoxy resin/4,4 '-MDA firming agent=1/100/30(mass ratio).Being cast in steel die by mixture after deaeration, heating cure in vacuum drying oven, curing process program is 90 DEG C/1h+130 DEG C/3h+180 DEG C/2h.Resin-cast body hot strength prepared by non-starching CNT is 80MPa, and stretch modulus is 2.4GPa, and bending strength is 128MPa, and bending modulus is 3.1GPa；Resin-cast body hot strength prepared by the CNT containing sizing agent is 88MPa, and stretch modulus is 2.8Gpa, and bending strength is 151MPa, and bending modulus is 3.7GPa.
Embodiment 3
Component 1: benzyl glycidyl ether is dissolved in methyl iso-butyl ketone (MIBK)/isophorone mixed solvent, and solution concentration is 80wt%, methyl iso-butyl ketone (MIBK) is 2:1 with the volume ratio of isophorone.Benzyl glycidyl ether, methyl iso-butyl ketone (MIBK) and isophorone are produced by Aldrich Chemical Co., Ltd., and purity is 98%.Benzyl glycidyl ether is produced by Aldrich Chemical Co., Ltd., and purity is 98%.Step I: the multi-walled carbon nano-tubes of ethylenediamine surface grafting is added in component 1, obtains uniform liquefied mixture through ball milling.The wherein multi-walled carbon nano-tubes of ethylenediamine surface grafting, the TNMC3 functionalized multi-wall carbonnanotubes that in Chengdu, epoch nanometer company of section produces is used to process obtain through chloride, amination, ethylenediamine is produced by Zhengzhou Zhi Yi chemical products company limited, CNT external diameter is 10 ~ 30nm, average length 5 μm, the surface grafting rate of amino is 2.5wt%.CNT and sizing agent solution quality are than for 1:5, and rotational speed of ball-mill is 200 r/min, and Ball-milling Time is 3 h.Step II: step I gained mixture is through filtering off except unnecessary sizing agent solution, and heat drying under vacuum conditions；Step III: dried CNT is carried out secondary ball milling, rotational speed of ball-mill is 80r/min, and Ball-milling Time is 0.5h.CNT after ball milling sieves with 200 mesh rotor-vibrating screens, obtains the CNT of the starching process of uniform particle sizes, average length 2.5 μm.
CNT before and after starching being processed is separately added in the TDE-85 epoxy resin-base that Jindong Chemical Factory, Tianjin produces, 2h is stirred at 60 DEG C, add the 4 of the production of Suzhou Yin Sheng Chemical Co., Ltd. again, 4 '-DADPS firming agent, 50 DEG C of stirring 1h, each component proportion is: CNT/TDE-85 epoxy resin/DDS firming agent=1/100/30(mass ratio).Being cast in steel die by mixture after deaeration, heating cure in vacuum drying oven, curing process program is 80 DEG C/1h+120 DEG C/2h+150 DEG C/3h+180 DEG C/3h.Resin-cast body hot strength prepared by non-starching CNT is 75MPa, and stretch modulus is 3.0GPa, and bending strength is 148MPa, and bending modulus is 3.9GPa；Resin-cast body hot strength prepared by the CNT containing sizing agent is 83MPa, and stretch modulus is 3.4Gpa, and bending strength is 172MPa, and bending modulus is 4.5GPa.
Embodiment 4
Component 1: lauryl diglycidyl ether is dissolved in methyl iso-butyl ketone (MIBK)/isophorone mixed solvent, and solution concentration is 50wt%, methyl iso-butyl ketone (MIBK) is 1:1 with the volume ratio of isophorone.Lauryl diglycidyl ether, methyl iso-butyl ketone (MIBK) and isophorone are produced by Aldrich Chemical Co., Ltd., and purity is 98%.Step I: the multi-walled carbon nano-tubes of ethylenediamine surface grafting is added in component 1, obtains uniform liquefied mixture through ball milling.The wherein multi-walled carbon nano-tubes of ethylenediamine surface grafting, the TNMC3 functionalized multi-wall carbonnanotubes that in Chengdu, epoch nanometer company of section produces is used to process obtain through chloride, amination, diethylenetriamine is produced by Beijing Hua Ye whole world Chemical Co., Ltd., CNT external diameter is 10 ~ 30nm, average length 5 μm, the surface grafting rate of amino is 2.3wt%.CNT and sizing agent solution quality are than for 1:8, and rotational speed of ball-mill is 150r/min, and Ball-milling Time is 2 h.Step II: step I gained mixture is through filtering off except unnecessary sizing agent solution, and heat drying under vacuum conditions；Step III: dried CNT is carried out secondary ball milling, rotational speed of ball-mill is 50r/min, and Ball-milling Time is 1h.CNT after ball milling sieves with 200 mesh rotor-vibrating screens, obtains the CNT of the starching process of uniform particle sizes, average length 2.5 μm.
CNT before and after starching being processed is separately added in the TDE-85 epoxy resin-base that Jindong Chemical Factory, Tianjin produces, 2h is stirred at 60 DEG C, add the 4 of the production of Suzhou Yin Sheng Chemical Co., Ltd. again, 4 '-DADPS firming agent, 50 DEG C of stirring 1h, each component proportion is: CNT/TDE-85 epoxy resin/DDS firming agent=1/100/30(mass ratio).Being cast in steel die by mixture after deaeration, heating cure in vacuum drying oven, curing process program is 80 DEG C/1h+120 DEG C/2h+150 DEG C/3h+180 DEG C/3h.Resin-cast body hot strength prepared by non-starching CNT is 75MPa, and stretch modulus is 3.0GPa, and bending strength is 148MPa, and bending modulus is 3.9GPa；Resin-cast body hot strength prepared by the CNT containing sizing agent is 85MPa, and stretch modulus is 3.4Gpa, and bending strength is 175MPa, and bending modulus is 4.6GPa.
Claims (7)
1. the process that a carbon nano tube surface starching processes, it is characterised in that include following components and step:
Component 1: preferably sizing agent.
2. step I: the CNT of aminofunctional is added in component 1, obtains uniform liquefied mixture through ball milling.
Wherein CNT and sizing agent solution quality are than for 1:2 ~ 1:8, and rotational speed of ball-mill is 150-300 r/min, and Ball-milling Time is 2-5 h.
4. the multi-walled carbon nano-tubes of aminofunctional can be obtained through chloride and amidized chemical treatment by functionalized multi-wall carbonnanotubes, and this technique belongs to the known mature technology of this area.
5. step II: step I gained mixture is through filtering off except unnecessary sizing agent solution, and heat drying under vacuum conditions；
Step III: dried CNT is carried out secondary ball milling, rotational speed of ball-mill is 50-100 r/min, and Ball-milling Time is 0.5-1 h.
6. the CNT rotor-vibrating screen after ball milling sieves, and can get, according to the mesh number of vibrosieve used, the CNT that the starching of different-grain diameter processes.
The process that a kind of carbon nano tube surface starching the most according to claim 1 processes, wherein, preferred sizing agent described in component 1 is benzyl glycidyl ether or lauryl diglycidyl ether is dissolved in the mixed solvent of methyl iso-butyl ketone (MIBK) and isophorone, solution concentration is 50-80wt%, and methyl iso-butyl ketone (MIBK) is 1:2 ~ 2:1 with the volume ratio of isophorone.
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| CN104513404A (en) * | 2013-10-01 | 2015-04-15 | 北京化工大学 | Preparation of epoxy compound coated carbon nano-tube electrostatic spraying carbon fiber prepreg |
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| CN104513404A (en) * | 2013-10-01 | 2015-04-15 | 北京化工大学 | Preparation of epoxy compound coated carbon nano-tube electrostatic spraying carbon fiber prepreg |
Non-Patent Citations (2)
| Title |
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| 李卓: "反应性碳纳米管的制备及其对环氧树脂力学性能的影响", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 沈青: "《分子酸碱化学》", 31 March 2012 * |
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