CN106280246A - The carbon fiber of a kind of galapectite deposition and polymer matrix composites preparation method thereof - Google Patents
The carbon fiber of a kind of galapectite deposition and polymer matrix composites preparation method thereof Download PDFInfo
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- CN106280246A CN106280246A CN201510238972.9A CN201510238972A CN106280246A CN 106280246 A CN106280246 A CN 106280246A CN 201510238972 A CN201510238972 A CN 201510238972A CN 106280246 A CN106280246 A CN 106280246A
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Abstract
The present invention relates to carbon fiber and the polymer matrix composites preparation method thereof of a kind of surface deposition halloysite nanotubes, belong to field of compound material.Feature of present invention is to use the halloysite nanotubes being easily dispersed to be deposited on carbon fiber surface, builds transition enhancement layer structure in the composite.The present invention includes techniques below step.Step I: by halloysite nanotubes ultrasonic disperse in deionized water, make the aqueous dispersions of halloysite nanotubes；Step II: by carbon fiber with the certain speed aqueous dispersions by halloysite nanotubes, halloysite nanotubes is deposited on carbon fiber surface, carbon fiber bundle rolling after drying；Step III: having the carbon fiber of halloysite nanotubes to prepare polymer matrix composites by surface deposition, halloysite nanotubes forms transition enhancement layer structure between carbon fiber and resin matrix.Present invention process is simple, and the interface performance of the carbon fiber resin matrix composite of preparation is excellent, it is easy to popularization and application in actual production.
Description
Technical field
The invention belongs to field of compound material, particularly to carbon fiber and the polymer matrix composites preparation method thereof of a kind of surface deposition halloysite nanotubes.
Background technology
Carbon fiber composite layer plywood is widely used in having in the structural member of loss of weight requirement, and this just requires that these laminate materials have specific strength, specific stiffness in the face of excellence.But the defect of the performance such as interlaminar strength outside these carbon fiber composite layer plywood faces limits again the application of these polymer matrix composites.Research in recent years shows, the factor controlling fiber parameter material interlaminar strength includes the performance such as the interface cohesion between carbon fiber-resin matrix and the modulus of resin matrix itself, toughness.In order to improve the interlaminar strength of carbon fiber resin matrix composite, the structure of the design multidirectional orientation of fiber is a kind of effective method.But this can not solve material problem substantially, the essence of solution carbon fiber layer condensation material interlaminar strength is also intended to the intrinsic performance such as the modulus of the interface between fiber-resin matrix and resin matrix itself and sets about.
One of key influence factor of interface performance of carbon fiber resin matrix composite is the modulus of fiber and resin matrix.If the modulus difference of the modulus of resin matrix and composite material interface layer is bigger, boundary layer will seem relatively weak, the interface shear strength that thus can cause material is relatively low, in this case, during material damage, crackle longitudinally develops mainly along fiber in boundary layer, causing the complete unsticking of fiber-resin basal body interface, section part fiber surface is smooth；If if the modulus of the modulus of resin matrix and composite material interface layer is more or less the same, time the most quite, the boundary layer performance of composite reaches unanimity with resin matrix performance, thus can bring higher interface shear strength, in this case, during material damage, crackle can be suppressed along the fiber longitudinally development in boundary layer, the broken interfacial detachment caused of matrix near failure mode between fiber-resin matrix predominantly boundary layer, section part fiber surface is substantially stained with the resin matrix of residual.
The cementing agent of fiber surface can form transition zone between fiber and resin matrix, and being formed of this transition zone beneficially improves the compatibility between fiber and resin matrix.In recent years it is theoretical that the understanding about the boundary layer in composite also exists two kinds of theories, i.e. Deformation Bedding opinion and inhibition layer.The former think the boundary layer of composite under stress effect owing to plastic deformation can be produced, thus the stress applied can be had relexation；It is more higher modulus than resin matrix that the latter then thinks that the boundary layer of composite has, the generation of high-modulus makes the molecular stuffing at boundary layer more closely knit mainly due to molecular resin at fiber surface Preferential adsorption, and the modulus that boundary layer is higher is conducive to stress dispersed and transmission between fiber and resin matrix.
In sum, reduce the modulus gap between carbon fiber and resin matrix, improve the effective ways that composite material interface layer modulus is raising composite overall performance, and the interface enhancement layer structure that nanoreinforcement material is incorporated into fiber surface structure this method existing is real effective way.
At present carbon nanomaterial such as CNT etc. is incorporated into carbon fiber surface and strengthens boundary layer in composite material shaping process by most researcheres, but CNT is easily reunited and is difficult to scattered feature and makes its more difficult extensive moulding process being applied to composite.
Halloysite nanotubes is a kind of 1-dimention nano clay material, and cheap, abundance ,-Si-OH-group is contained on surface.Research worker is existing in terms of halloysite nanotubes is as the reinforcement of polymer matrix composite is attempted, and illustrates potential using value.Halloysite nanotubes is easily dispersed in organic solvent and polymeric matrix, can strengthen the interface structure of composite if depositing to carbon fiber surface.
Summary of the invention
It is an object of the invention to for the existing state of the art, develop the preparation method of a kind of carbon fiber resin matrix composite with transition enhancing structure, by halloysite nanotubes by the diffusion carbon fiber surface to resin matrix in composite solidification process, improve composite material interface performance, there is the using value of reality.
The present invention realizes the concrete technical scheme that above-mentioned purpose used:
The carbon fiber of a kind of surface deposition halloysite nanotubes and polymer matrix composites preparation method thereof, is characterized by, comprise the following steps:
Step I: by halloysite nanotubes ultrasonic disperse in deionized water, make the aqueous dispersions of halloysite nanotubes, halloysite nanotubes content in deionized water is 0.05-0.1wt%；
Step II: by carbon fiber continuously and slowly through the aqueous dispersions of halloysite nanotubes, carbon fiber rolling after drying；
Step III: using surface deposition to have the carbon fiber of halloysite nanotubes to prepare polymer matrix composites, halloysite nanotubes forms transition enhancement layer structure between carbon fiber and resin matrix.
Wherein, in step I, halloysite nanotubes is halloysite nanotubes or the halloysite nanotubes of surface modification of non-modified, the halloysite nanotubes of surface modification includes silane coupler process, surface grafting carboxyl functional group or amido functional group, and this technique belongs to the known mature technology of this area.In step II, carbon fiber passes through the speed controlling of halloysite nanotubes aqueous dispersions at 0.05-0.2m/min.Carbon fiber described in step II and step III includes business-like high-strength and high model carbon fiber.Resin matrix described in step III is the epoxy resin of various chemical constitution, and carbon fiber volume content in the composite is 60%-70%.
By the enforcement of technique scheme, halloysite nanotubes is incorporated into carbon fiber surface and strengthens the boundary layer of composite, while regulation and control resin matrix modulus is mated with carbon fiber boundary layer modulus, build the modulus transition zone that halloysite nanotubes strengthens, and then realize the activeness and quietness effect that composite micro-/ nano is multiple dimensioned.Contrast does not deposits the carbon fibre composite of halloysite nanotubes, the deposition of halloysite nanotubes can be obviously improved the interface cohesion of carbon fiber and epoxy resin-base, and the bending strength of unidirectional carbon fiber reinforced plastics promotes amplitude >=10%, interlaminar shear strength promotes amplitude >=10%.The halloysite nanotubes deposition carbon fiber surface technique related in the present invention is simple, it is easy to popularization and application in actual production.
Detailed description of the invention
By following example, the present invention is described in detail.
In each embodiment, unidirectional carbon fiber reinforced plastics bending property is tested according to GB/T 3356-2014, and unidirectional carbon fiber reinforced plastics interlaminar shear strength is tested according to JC/T 773-2010.
Embodiment 1
Step I: by the halloysite nanotubes of non-modified ultrasonic disperse in deionized water, make the aqueous dispersions of halloysite nanotubes, halloysite nanotubes content in deionized water is 0.05wt%.Halloysite nanotubes is produced by Dongming Tian He high-temperature material company limited, purity 95%.Step II: by Toray®T700-12K high-strength continuous carbon fibre passes through halloysite nanotubes aqueous dispersions with 0.05m/min speed, carbon fiber rolling after 100 DEG C of vacuum drying.Step III: EPON 828 epoxy resin that carbon fiber step II obtained produces with Shell Co. Ltd is prepared as unidirectional composite material, firming agent is 4 that Huifeng Synthetic Material Co., Ltd., Jiangyin produces, 4 '-MDA.Each component proportion is: EPON 828 epoxy resin/4,4 '-MDA=100/30(mass ratio).Carbon fiber volume content in the composite is 70%.Composite is heating cure in vacuum drying oven, and curing process program is 90 DEG C/1h+130 DEG C/3h+180 DEG C/2h.Unidirectional carbon fiber reinforced plastics bending strength is 1400MPa, and interlaminar shear strength is 68MPa.As a comparison, preparing the carbon fiber one-way composite not depositing halloysite nanotubes under similarity condition, its bending strength is 1270MPa, and interlaminar shear strength is 61MPa.
Embodiment 2
Step I: put into by 10 grams of halloysite nanotubes in 200 milliliters of ethanol solution, adds Silane coupling agent KH550 and 2 milliliters of acetic acid, the supersound process 0.5 hour of 6 milliliters, then reacts 24 hours under 80 DEG C of mechanical agitation.After reaction terminates, carry out cyclic washing with deionized water, obtain the halloysite nanotubes of surface grafting Silane coupling agent KH550 after drying.The halloysite nanotubes in deionized water ultrasonic disperse modified by Silane coupling agent KH550, makes the aqueous dispersions of halloysite nanotubes, and halloysite nanotubes content in deionized water is 0.07wt%.Halloysite nanotubes is produced by Dongming Tian He high-temperature material company limited, purity 95%.Silane coupling agent KH550 is produced by Nanjing Chen Gong organosilicon material company limited.Step II: by Toray T700-12K high-strength continuous carbon fibre with 0.1m/min speed by halloysite nanotubes aqueous dispersions, carbon fiber rolling after 100 DEG C of vacuum drying；Step III: the TDE-85 epoxy resin that carbon fiber step II obtained produces with Jindong Chemical Factory, Tianjin is prepared as unidirectional composite material, firming agent is 4 that Huifeng Synthetic Material Co., Ltd., Jiangyin produces, 4 '-MDA.Each component proportion is: TDE-85 epoxy resin/4,4 '-MDA=100/30(mass ratio).Carbon fiber volume content in the composite is 65%.Composite is heating cure in vacuum drying oven, and curing process program is 90 DEG C/1h+130 DEG C/3h+180 DEG C/2h.Unidirectional carbon fiber reinforced plastics bending strength is 1520MPa, and interlaminar shear strength is 85MPa.As a comparison, preparing the carbon fiber one-way composite not depositing halloysite nanotubes under similarity condition, its bending strength is 1380MPa, and interlaminar shear strength is 77MPa.
Embodiment 3
Step I: 10 grams of halloysite nanotubes are put in concentrated sulphuric acid (98%)/concentrated nitric acid (68%) mixed liquor that 200 milliliters of volume ratios are 3:1, react 2 hours under 80 C, it is washed with deionized water to neutrality, obtaining the halloysite nanotubes of surface grafting carboxyl after drying, the surface grafting rate of carboxyl is 3wt%.The halloysite nanotubes ultrasonic disperse in deionized water of carboxyl by surface grafting, makes the aqueous dispersions of halloysite nanotubes, and halloysite nanotubes content in deionized water is 0.1wt%.Halloysite nanotubes is produced by Dongming Tian He high-temperature material company limited, purity 95%.Step II: by Toray®M40-12K height model continuous carbon fibre passes through halloysite nanotubes aqueous dispersions with 0.1m/min speed, carbon fiber rolling after 100 DEG C of vacuum drying.Step III: EPON 828 epoxy resin that carbon fiber step II obtained produces with Shell Co. Ltd is prepared as unidirectional composite material, firming agent is the DDS that Suzhou Yin Sheng Chemical Co., Ltd. produces.Each component proportion is: EPON 828 epoxy resin/4,4 '-DADPS=100/30(mass ratio).Carbon fiber volume content in the composite is 65%.Composite is heating cure in vacuum drying oven, and curing process program is 80 DEG C/1h+120 DEG C/2h+150 DEG C/3h+180 DEG C/3h.Unidirectional carbon fiber reinforced plastics bending strength is 1450MPa, and interlaminar shear strength is 73MPa.As a comparison, preparing the carbon fiber one-way composite not depositing halloysite nanotubes under similarity condition, its bending strength is 1310MPa, and interlaminar shear strength is 65MPa.
Embodiment 4
Step I: 10 grams of halloysite nanotubes are put in concentrated sulphuric acid (98%)/concentrated nitric acid (68%) mixed liquor that 200 milliliters of volume ratios are 3:1, react 2 hours under 80 C, it is washed with deionized water to neutrality, obtains the halloysite nanotubes of surface grafting carboxyl after drying.Being dissolved in by the halloysite nanotubes of surface grafting carboxyl in thionyl chloride/DMF solution that volume ratio is 20:1, temperature rises to 70 C and stirs 24 hours, and washs with THF, obtains the halloysite nanotubes of chloride after drying.Being mixed with ethylenediamine by chloride halloysite nanotubes, react 48 hours in 100 C under nitrogen protection, product washs, obtains after drying the halloysite nanotubes of surface grafting amino through oxolane.By the halloysite nanotubes ultrasonic disperse in deionized water of surface grafting amino, making the aqueous dispersions of halloysite nanotubes, halloysite nanotubes content in deionized water is 0.05wt%；Step II: by Toray®M40-12K height model continuous carbon fibre passes through halloysite nanotubes aqueous dispersions with 0.2m/min speed, carbon fiber rolling after 100 DEG C of vacuum drying；Step III: the TDE-85 epoxy resin that carbon fiber step II obtained produces with Jindong Chemical Factory, Tianjin is prepared as unidirectional composite material, firming agent is the DDS that Suzhou Yin Sheng Chemical Co., Ltd. produces.Each component proportion is: EPON 828 epoxy resin/4,4 '-DADPS=100/30(mass ratio).Carbon fiber volume content in the composite is 60%.Composite is heating cure in vacuum drying oven, and curing process program is 80 DEG C/1h+120 DEG C/2h+150 DEG C/3h+180 DEG C/3h.Unidirectional carbon fiber reinforced plastics bending strength is 1490MPa, and interlaminar shear strength is 76MPa.As a comparison, preparing the carbon fiber one-way composite not depositing halloysite nanotubes under similarity condition, its bending strength is 1350MPa, and interlaminar shear strength is 68MPa.
Claims (5)
1. surface deposits carbon fiber and a polymer matrix composites preparation method thereof for halloysite nanotubes, it is characterized by, comprises the following steps:
Step I: by halloysite nanotubes ultrasonic disperse in deionized water, make the aqueous dispersions of halloysite nanotubes, halloysite nanotubes content in deionized water is 0.05-0.1wt%；
Step II: by carbon fiber continuously and slowly through the aqueous dispersions of halloysite nanotubes, carbon fiber rolling after drying；
Step III: using surface deposition to have the carbon fiber of halloysite nanotubes to prepare polymer matrix composites, halloysite nanotubes forms transition enhancement layer structure between carbon fiber and resin matrix.
The carbon fiber of a kind of surface the most according to claim 1 deposition halloysite nanotubes and polymer matrix composites preparation method thereof, wherein, in step I, halloysite nanotubes is halloysite nanotubes or the halloysite nanotubes of surface modification of non-modified, and the halloysite nanotubes of surface modification includes silane coupler process, surface grafting carboxyl functional group or amido functional group.
The carbon fiber of a kind of surface the most according to claim 1 deposition halloysite nanotubes and polymer matrix composites preparation method thereof, wherein, in step II, carbon fiber passes through the speed controlling of halloysite nanotubes aqueous dispersions at 0.05-0.2m/min.
The carbon fiber of a kind of surface the most according to claim 1 deposition halloysite nanotubes and polymer matrix composites preparation method thereof, wherein, the carbon fiber described in step II and step III includes business-like high-strength and high model carbon fiber.
The carbon fiber of a kind of surface the most according to claim 1 deposition halloysite nanotubes and polymer matrix composites preparation method thereof, wherein, resin matrix described in step III is the epoxy resin of various chemical structural type, and carbon fiber volume content in the composite is 60%-70%.
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Cited By (2)
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| CN108299826A (en) * | 2018-02-01 | 2018-07-20 | 广州市新稀冶金化工有限公司 | Porous filamentous nanocarbon/special engineering plastics composite material and preparation method |
| CN109504036A (en) * | 2018-11-16 | 2019-03-22 | 南昌航空大学 | A kind of micro-nano graphite flake epoxy resin-matrix/modified carbon fiber composite material and preparation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108299826A (en) * | 2018-02-01 | 2018-07-20 | 广州市新稀冶金化工有限公司 | Porous filamentous nanocarbon/special engineering plastics composite material and preparation method |
| CN109504036A (en) * | 2018-11-16 | 2019-03-22 | 南昌航空大学 | A kind of micro-nano graphite flake epoxy resin-matrix/modified carbon fiber composite material and preparation method |
| CN109504036B (en) * | 2018-11-16 | 2021-03-12 | 南昌航空大学 | Micro-nano graphite sheet epoxy resin-based/modified carbon fiber composite material and preparation method thereof |
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