CN112677602B - Toughening material for prepreg, high-toughness composite material and preparation method thereof - Google Patents
Toughening material for prepreg, high-toughness composite material and preparation method thereof Download PDFInfo
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- CN112677602B CN112677602B CN201910987787.8A CN201910987787A CN112677602B CN 112677602 B CN112677602 B CN 112677602B CN 201910987787 A CN201910987787 A CN 201910987787A CN 112677602 B CN112677602 B CN 112677602B
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 19
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- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 23
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 22
- 239000004917 carbon fiber Substances 0.000 claims abstract description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims description 91
- 239000011347 resin Substances 0.000 claims description 91
- 239000011159 matrix material Substances 0.000 claims description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- 229910021389 graphene Inorganic materials 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 239000004695 Polyether sulfone Substances 0.000 claims description 13
- 229920006393 polyether sulfone Polymers 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000012783 reinforcing fiber Substances 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 5
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 2
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- 229920001601 polyetherimide Polymers 0.000 claims description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 238000005470 impregnation Methods 0.000 abstract description 17
- 238000009830 intercalation Methods 0.000 abstract description 5
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- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 4
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- 239000004966 Carbon aerogel Substances 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a toughening material for prepreg, a high-toughness composite material and a preparation method thereof. The toughening material comprises carbon material aerogel and thermoplastic resin, wherein the mass ratio of the carbon material aerogel to the thermoplastic resin is 1: (0.5-40). The carbon material aerogel and the thermoplastic resin are compounded and pressed to obtain a toughening layer of the toughening material, then the prepreg is subjected to intercalation toughening, the compression strength of the obtained composite material laminated board after impact is obviously improved, and meanwhile, the carbon material aerogel structure in the toughening layer is beneficial to maintaining the rigidity of the composite material. The method is also beneficial to improving the process operability and the carbon fiber impregnation effect.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a toughening material for prepreg, a high-toughness composite material and a preparation method thereof.
Background
The advanced resin matrix composite has the performance characteristics of high specific modulus, high specific strength, fatigue resistance, corrosion resistance, strong designability and the like, is widely applied, is one of the light-weight and high-performance materials preferred by main bearing structural members of aerospace aircrafts, is widely applied in various fields of aerospace, military industry, automobile light weight and the like, and has increasingly larger application specific gravity. The carbon fiber resin matrix composite material has a 50% duty cycle in boeing 787 and 52% duty cycle in poder 350. Advanced resin matrix composite materials are divided into three generations according to the toughness. Since the first generation of composite materials exhibit brittle material performance characteristics, the performance of the laminate is sensitive to damage caused by impact load, particularly delamination damage, and for this reason, development of measures such as toughening of epoxy resin matrix and improvement of fiber reinforcement mode are required to improve the impact resistance. The second generation composite material is a toughened and modified resin matrix composite material, the matrix resin used is a thermoplastic resin toughening system such as 977, 6376, 5260 and the like, and the reinforcing fibers are represented by middle-mode high-strength carbon fibers in T800H of Tooli company and IM7 of Hercules company. Typical applications are the tail wing of boeing B777 aircraft, as well as the wings, fuselage, horizontal tail, floor beams, hatches, fairings, transmitter blades, etc. of other aircraft. As a candidate scheme for reducing the weight of the civil aircraft body structure, boeing company provides an index for improving the performance of carbon fibers and formulates a standard BMS8-17 of carbon fiber reinforced materials, middle-modulus high-strength yarns and fabrics. The 5 month boeing company in 1990 also provides a high-toughness carbon fiber epoxy prepreg standard (BMS 8-276), a technical index system suitable for composite materials for civil aircraft main bearing structures is provided, the third generation high-toughness resin matrix composite materials are produced, the interlayer toughening or intercalation toughening technology of the resin-rich resin is adopted, the compression strength (CAI) after impact is greatly improved, the representative matrix resins are Toray 3900, hexcel8552 and the like, and the representative Dongli high-toughness T800/3900 prepreg is mainly used for the composite materials of the B787 main bearing structure of the boeing company.
High CAI requires high toughness for composite materials, while the main approach to toughness improvement is matrix resin toughening and interlaminar toughening. The matrix resin is toughened by preferentially adopting thermoplastic resin as a toughening agent, so that the toughness is improved, and the heat resistance of the composite material is not reduced. Hexcel corporation patent EP2607411 uses polyether sulfone (PES) resin and Polyamide (PA) particles to carry out composite toughening modification on an epoxy resin matrix, PES exists in the epoxy resin in a completely dissolved mode, PA particles exist in the epoxy resin in a dispersed state, and the CAI of the carbon fiber prepreg prepared by using the toughened resin matrix can reach 350MPa. Because the content of the thermoplastic resin is close to 30 weight percent, the viscosity of the toughened resin matrix is very high, and the requirements on the mixing process of the resin matrix and the subsequent coating and presoaking processes are very high. The technology of "ex-situ toughening" (CN 200610099381.9) is proposed by Yixiaosu and the like to solve a series of process problems caused by direct dissolution or dispersion of high-content thermoplastic resin in a resin matrix. The "ex-situ toughening" technology places thermoplastic resin in the form of film, powder, etc. between two carbon fiber layers impregnated with low viscosity resin matrix, and increases the interlayer toughness of the composite material in a targeted manner, thereby significantly increasing the CAI of the composite material. Chinese patent CN104842619a provides a manufacturing process of a prepreg with a high-toughness multilayer structure, and one or more toughening layers are added on the basis of a three-layer structure of a resin layer-a fiber layer-a resin layer, wherein the toughening layers exist in the form of a film, powder or fabric, and the CAI of the toughened composite material reaches 260MPa. Although the above toughening technique achieves a good toughening effect, other problems are brought at the same time, such as loss of interlayer rigidity caused by "off-site toughening", and further influence on the mechanical strength of the composite material.
Disclosure of Invention
The invention aims to solve the technical problems of high system viscosity, high preparation difficulty and poor impregnation effect caused by toughening a resin matrix by using thermoplastic resin in the prior art, and provides a toughening material for a prepreg, wherein a toughening layer of the toughening material is obtained by compounding and pressing carbon material aerogel and thermoplastic resin, the prepreg is subjected to intercalation toughening, the compression strength of a composite material laminated board after impact is obviously improved, and meanwhile, the carbon material aerogel structure in the toughening layer is beneficial to maintaining the rigidity of the composite material.
One of the purposes of the invention is to provide a toughening material for a prepreg, which comprises carbon material aerogel and thermoplastic resin, wherein the mass ratio of the carbon material aerogel to the thermoplastic resin is 1: (0.5 to 40), preferably 1: (2-10).
In the above technical solution, the carbon material aerogel is at least one selected from graphene aerogel and carbon nanotube aerogel.
In the above embodiments, the thermoplastic resin is at least one selected from the group consisting of, but not limited to, thermoplastic resins such as polyetherketone, polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, polyphenylene sulfide, polyphenylene oxide, and polyamide, and modified products thereof.
The second object of the present invention is to provide a method for preparing the toughening material for prepregs, which comprises compacting raw materials including the carbon aerogel and thermoplastic resin.
Preferably, the preparation method of the toughening material comprises the steps of dissolving the thermoplastic resin in an organic solvent, immersing the carbon material aerogel in the thermoplastic resin solution, removing the organic solvent, and then pressing to obtain the toughening material.
In the above technical scheme, the organic solvent is a good solvent of the thermoplastic resin, preferably at least one of tetrahydrofuran, dichloroethane, tetrachloroethane, dichloromethane, chloroform, N-dimethylformamide, N-dimethylacetamide or N, N-dimethylpyrrolidone.
In the above technical solution, the method for removing the organic solvent may be selected from methods generally used in the art, preferably heating and vacuumizing to remove the organic solvent, and the temperature may be 50-150 ℃.
In the technical scheme, high-temperature pressing is preferred, and the temperature during pressing is 50-150 ℃.
In the above technical solution, the toughening material is preferably pressed into a film.
In the above technical solution, the density and shape of the carbon material aerogel are not particularly limited, and the toughened materials with different thicknesses or areas can be obtained by adjusting the density and shape of the carbon material aerogel and the content of the thermoplastic resin.
The invention further provides a high-toughness composite material, which comprises a prepreg and a toughening layer, wherein the toughening layer is paved between the prepreg layers, the toughening layer is made of the toughening material for the prepreg, and the prepreg comprises a resin matrix and reinforcing fibers.
The high-toughness composite material comprises the following components in percentage by weight:
20 to 40wt% of a resin matrix, preferably 25 to 35wt%;
50 to 80wt% of reinforcing fibers, preferably 60 to 70wt%;
the toughening layer is 0.5 to 30wt%, preferably 2 to 20wt%.
In the technical scheme, the resin matrix and the reinforcing fibers form the prepreg, the toughening layer is formed by compounding and pressing carbon material aerogel and thermoplastic resin, and the toughening layer is paved between the layers of the prepreg for intercalation toughening.
In the above technical solution, the resin matrix may be a resin matrix common in the art, preferably an epoxy resin system, a bismaleimide resin system, a phenolic resin system or a cyanate resin system. The composition of the resin matrix is not particularly limited, and a usual auxiliary agent may be added to the resin matrix, and the components and the amounts thereof are all usual components and usual amounts in the art, or may be adjusted according to the actual situation.
In the above technical solution, the reinforcing fiber may be at least one fiber in the field, preferably carbon fiber, aramid fiber, glass fiber, basalt fiber, etc. The reinforcing fibers may be in the form of continuous unidirectional fibers or fabrics.
In the above technical scheme, the preferable thickness of the toughening layer is 5-200 μm, preferably 10-30 μm, and the thickness and area of the toughening layer can be adjusted by the density and shape of the carbon material aerogel and the content of the thermoplastic resin.
The fourth object of the invention is to provide a preparation method of the high-toughness composite material, which comprises the steps of paving the toughening layer between the layers of the prepreg and curing to obtain the high-toughness composite material.
In the above technical scheme, the layering sequence can be designed according to the requirement, the toughening layers are paved between two layers of prepregs, the number of the used toughening layers can be adjusted according to the requirement, and for example, one toughening layer can be inserted into every other two layers of prepregs.
In the above technical solution, the prepreg is obtained by impregnating reinforcing fibers with a resin matrix. The impregnation method is a method generally known in the art.
In the above technical solution, the curing process and curing conditions may be the processes and conditions generally used in the prior art. The equipment used is also equipment in the processing of resin matrix composite materials in the prior art, such as a film coater, a presoaking machine, an autoclave and the like.
Preferably, the curing temperature is 120-180 ℃, and the heating rate is 2-10 ℃/min.
Specifically, the preparation method may include the steps of:
a) Preparing a resin adhesive film: uniformly coating a resin matrix on the surface of release paper on a hot-melting coating machine;
b) Preparing a prepreg: and (3) finishing the impregnation of the resin adhesive film on the reinforced fiber on a presoaking machine provided with a plurality of groups of winding and unwinding stations, covering the PE film, and winding.
c) Preparing a toughening layer: the method comprises the steps of dissolving thermoplastic resin in an organic solvent to form a thermoplastic resin solution, immersing carbon material aerogel in the thermoplastic resin solution, and then removing the organic solvent for pressing.
d) Preparing a high-toughness composite material:
and paving the toughening layer film between the prepreg layers, and curing to obtain the high-toughness composite material.
The invention has the following beneficial effects:
1) The prepreg is toughened by layers through the toughening layer formed by compounding and pressing the carbon material aerogel and the plastic resin, so that the addition of toughening components in the prepreg resin matrix is avoided, the system viscosity is low, and the process operability and the carbon fiber impregnation effect are improved.
2) The toughening layer is formed by compounding and pressing carbon material aerogel and plastic resin, the toughness of the composite material can be obviously improved through a synergistic effect, and the influence on the mechanical property of the composite material is reduced.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The raw materials used in the specific embodiment of the present invention are commercially available.
[ example 1 ]
Preparation of prepreg by using Toray T700X 12k carbon fiber, and controlling fiber surface density to be 100g/m 2 。
The resin matrix comprises the following components:
bisphenol a epoxy resin: 100 parts of
4,4' -diaminodiphenyl sulfone: 45 parts of
1) Preparing a resin adhesive film: pouring the resin matrix into a resin tank of a film coating machine, and uniformly coating the resin matrix on release paper at the coating temperature of 90 ℃. The surface density of the resin adhesive film is 20g/m 2 。
2) Preparing a prepreg: and respectively placing the two rolls of resin adhesive films on an upper unreeling station and a lower unreeling station at the front end of the presoaking machine, and finishing the impregnation of unidirectionally arranged carbon fibers by the upper resin adhesive film and the lower resin adhesive film at the first heating roller, the second heating roller and the heating plate. And cooling by a cooling plate, rolling the upper release paper, covering the PE film, and finally finishing the rolling of the prepreg.
3) Preparing a toughening layer: 10 parts of polyethersulfone resin are dissolved in 100 parts of N, N-dimethylformamide, 0.2 part of polyethersulfone resin are dissolved in 100 parts of N, N-dimethylformamide, and the surface density is 1.0g/m 2 The layered graphene aerogel is placed in the solution for full impregnation, heated to 80 ℃ and vacuumized to remove the solvent, then placed in the solution again for impregnation, heated to 80 ℃ again and vacuumized to remove the solvent until the mass ratio of the graphene aerogel to the polyether sulfone resin attached to the graphene aerogel reaches 1:9, heated to 100 ℃ and pressed to obtain the graphene aerogel and thermoplastic resin composite film, namely a toughening layer, wherein the density of the toughening layer surface is 10g/m 2 The thickness was 20. Mu.m.
4) Preparation and performance evaluation of the high-toughness composite laminate:
cutting the prepreg and the toughening layer into proper sizes according to the GB/T21239-2007 standard requirement, paving the layers, wherein the layering sequence of the prepreg is [45/0/-45/90] S, the toughening layer is intercalated between every two layers of prepregs, placing the prepregs into an autoclave for curing, the curing process is 120 ℃/1h+180 ℃/2h, the heating rate is 2 ℃/min, and cutting the cured laminated board to obtain a test sample plate with the size of 150mm multiplied by 100mm multiplied by 5 mm. The panels were tested for compressive strength after impact according to GB/T21239-2007 standard.
Examples 2 to 3
The prepreg method was the same as in example 1, except that the toughening layer was prepared, the areal density of the graphene aerogel of example 2 was 0.2g/m 2 The density of the obtained toughened layer is 2g/m 2 The thickness was 5. Mu.m. Example 3 graphene aerogel having an areal density of 4g/m 2 The density of the obtained toughened layer is 40g/m 2 The thickness was 60. Mu.m.
Examples 4 to 5
The prepreg process was the same as in example 1 except that during the preparation of the toughening layer, the aerogel used in example 3 had an areal density of 1.0g/m at 0.2 parts 2 The mass ratio of the layered carbon nanotube aerogel to the polyether sulfone resin attached to the layered carbon nanotube aerogel is 1:9, and the density of the obtained toughened layer is 10g/m 2 Thickness is 23 μm; the aerogel used in example 4 had an areal density of 0.2 parts of 1.0g/m 2 The mass ratio of the lamellar graphene carbon nano tube doped aerogel to the polyether sulfone resin is 1:9, and the density of the obtained toughened layer is 10g/m 2 The thickness was 21. Mu.m.
Examples 6 to 7
The prepreg method was the same as in example 1, except that in the preparation of the toughening layer, the laminar graphene aerogel used in example 6 had an areal density of 2g/m 2 The mass ratio of the graphene aerogel to the polyether sulfone resin attached to the graphene aerogel reaches 1:1, and the density of the toughening layer surface is 4g/m 2 The thickness was 13. Mu.m. Example 7 the layered graphene aerogel used had an areal density of 2g/m 2 The mass ratio of the graphene aerogel to the polyether sulfone resin attached to the graphene aerogel reaches 1:29, and the density of the toughening layer surface is 60g/m 2 The thickness was 120. Mu.m.
[ example 8 ]
Preparation of prepreg by using Toray T700X 12k carbon fiber, and controlling fiber surface density to be 100g/m 2 。
The resin matrix comprises the following components:
bisphenol a epoxy resin: 100 parts of
4,4' -diaminodiphenyl sulfone: 45 parts of
1) Preparing a resin adhesive film: pouring the resin matrix into a resin tank of a film coating machine, and uniformly coating the resin matrix on release paper at the coating temperature of 90 ℃. The surface density of the resin adhesive film is 20g/m 2 。
2) Preparing a prepreg: and respectively placing the two rolls of resin adhesive films on an upper unreeling station and a lower unreeling station at the front end of the presoaking machine, and finishing the impregnation of unidirectionally arranged carbon fibers by the upper resin adhesive film and the lower resin adhesive film at the first heating roller, the second heating roller and the heating plate. And cooling by a cooling plate, rolling the upper release paper, covering the PE film, and finally finishing the rolling of the prepreg.
3) Preparing a toughening layer: 10 parts of polysulfone resin are dissolved in 100 parts of dichloroethane, 0.2 part of the polysulfone resin is used to prepare a polymer having an areal density of 1.0g/m 2 The layered graphene aerogel is placed in the solution for full impregnation, heated to 80 ℃ and vacuumized to remove the solvent, then placed in the solution again for impregnation, heated to 80 ℃ again and vacuumized to remove the solvent until the mass ratio of the graphene aerogel to polysulfone resin attached to the graphene aerogel reaches 1:9, heated to 100 ℃ and pressed to obtain the graphene aerogel and thermoplastic resin composite film, namely a toughening layer, wherein the density of the toughening layer surface is 10g/m 2 The thickness was 22. Mu.m.
4) Preparation and performance evaluation of the high-toughness composite laminate:
cutting the prepreg and the toughening layer into proper sizes according to the GB/T21239-2007 standard requirement, paving the layers, wherein the layering sequence of the prepreg is [45/0/-45/90] S, the toughening layer is intercalated between every two layers of prepregs, placing the prepregs into an autoclave for curing, the curing process is 120 ℃/1h+180 ℃/2h, the heating rate is 2 ℃/min, and cutting the cured laminated board to obtain a test sample plate with the size of 150mm multiplied by 100mm multiplied by 5 mm. The panels were tested for compressive strength after impact according to GB/T21239-2007 standard.
[ example 9 ]
Preparation of prepreg by using Toray T700X 12k carbon fiber, and controlling fiber surface density to be 100g/m 2 。
The resin matrix comprises the following components:
bisphenol a epoxy resin: 100 parts of
4,4' -diaminodiphenyl sulfone: 45 parts of
1) Preparing a resin adhesive film: pouring the resin matrix into a resin tank of a film coating machine, and uniformly coating the resin matrix on release paper at the coating temperature of 90 ℃. The surface density of the resin adhesive film is 20g/m 2 。
2) Preparing a prepreg: and respectively placing the two rolls of resin adhesive films on an upper unreeling station and a lower unreeling station at the front end of the presoaking machine, and finishing the impregnation of unidirectionally arranged carbon fibers by the upper resin adhesive film and the lower resin adhesive film at the first heating roller, the second heating roller and the heating plate. And cooling by a cooling plate, rolling the upper release paper, covering the PE film, and finally finishing the rolling of the prepreg.
3) Preparing a toughening layer: 10 parts of polyetherketone are dissolved in 100 parts of N, N-dimethylformamide, 0.2 part of polyetherketone are added to a surface density of 1.0g/m 2 The layered graphene aerogel is placed in the solution for full impregnation, heated to 80 ℃ and vacuumized to remove the solvent, then placed in the solution again for impregnation, heated to 80 ℃ again and vacuumized to remove the solvent until the mass ratio of the graphene aerogel to the polyether ketone resin attached to the graphene aerogel reaches 1:9, heated to 100 ℃ and pressed to obtain the graphene aerogel and thermoplastic resin composite film, namely a toughening layer, wherein the density of the toughening layer surface is 10g/m 2 The thickness was 21. Mu.m.
4) Preparation and performance evaluation of the high-toughness composite laminate:
cutting the prepreg and the toughening layer into proper sizes according to the GB/T21239-2007 standard requirement, paving the layers, wherein the layering sequence of the prepreg is [45/0/-45/90] S, the toughening layer is intercalated between every two layers of prepregs, placing the prepregs into an autoclave for curing, the curing process is 120 ℃/1h+180 ℃/2h, the heating rate is 2 ℃/min, and cutting the cured laminated board to obtain a test sample plate with the size of 150mm multiplied by 100mm multiplied by 5 mm. The panels were tested for compressive strength after impact according to GB/T21239-2007 standard.
[ example 10 ]
Preparation of prepreg by using Toray T700X 12k carbon fiber, and controlling fiber surface density to be 100g/m 2 。
The resin matrix comprises the following components:
tetrafunctional epoxy resin: 30 parts of
Trifunctional epoxy resins: 30 parts of
Bisphenol a epoxy resin: 40 parts of
4,4' -diaminodiphenyl sulfone: 65 parts of
1) Preparing a resin adhesive film: pouring the resin matrix into a resin tank of a film coating machine, and uniformly coating the resin matrix on release paper at the coating temperature of 90 ℃. The surface density of the resin adhesive film is 20g/m 2 。
2) Preparing a prepreg: and respectively placing the two rolls of resin adhesive films on an upper unreeling station and a lower unreeling station at the front end of the presoaking machine, and finishing the impregnation of unidirectionally arranged carbon fibers by the upper resin adhesive film and the lower resin adhesive film at the first heating roller, the second heating roller and the heating plate. And cooling by a cooling plate, rolling the upper release paper, covering the PE film, and finally finishing the rolling of the prepreg.
3) Preparing a toughening layer: 10 parts of polyethersulfone resin are dissolved in 100 parts of N, N-dimethylformamide, 0.2 part of polyethersulfone resin are dissolved in 100 parts of N, N-dimethylformamide, and the surface density is 1.0g/m 2 The layered graphene aerogel is placed in the solution for full impregnation, heated to 80 ℃ and vacuumized to remove the solvent, then placed in the solution again for impregnation, heated to 80 ℃ again and vacuumized to remove the solvent until the mass ratio of the graphene aerogel to the polyether sulfone resin attached to the graphene aerogel reaches 1:9, heated to 100 ℃ and pressed to obtain the graphene aerogel and thermoplastic resin composite film, namely a toughening layer, wherein the density of the toughening layer surface is 10g/m 2 The thickness was 20. Mu.m.
4) Preparation and performance evaluation of the high-toughness composite laminate:
cutting the prepreg and the toughening layer into proper sizes according to the GB/T21239-2007 standard requirement, paving the layers, wherein the layering sequence of the prepreg is [45/0/-45/90] S, the toughening layer is intercalated between every two layers of prepregs, placing the prepregs into an autoclave for curing, the curing process is 120 ℃/1h+180 ℃/2h, the heating rate is 2 ℃/min, and cutting the cured laminated board to obtain a test sample plate with the size of 150mm multiplied by 100mm multiplied by 5 mm. The panels were tested for compressive strength after impact according to GB/T21239-2007 standard.
Examples 11 to 12
The prepreg method was the same as in example 10, except that carbon fibers were used, namely Toray T300×12k carbon fibers and Toray T800h×12k carbon fibers, respectively.
[ comparative example 1 ]
The prepreg process was the same as in example 1 except that no toughening layer was prepared and no intercalation toughening was performed during the preparation of the laminate.
[ comparative example 2 ]
The prepreg process was the same as in example 1, except that the toughening layer was graphene aerogel only, and no thermoplastic resin was included.
The results of the compressive strength test after impact for the composite laminates of examples and comparative examples are shown in table 1.
Table 1 results of test for compressive strength after impact of laminate
| Compression strength after impact (MPa) | |
| Example 1 | 258 |
| Example 2 | 247 |
| Example 3 | 231 |
| Example 4 | 230 |
| Example 5 | 266 |
| Example 6 | 251 |
| Example 7 | 228 |
| Example 8 | 247 |
| Example 9 | 255 |
| Example 10 | 260 |
| Example 11 | 229 |
| Example 12 | 311 |
| Comparative example 1 | 175 |
| Comparative example 2 | 237 |
The composite laminate compositions of the examples and comparative examples are shown in table 2 below.
Table 2 example and comparative composite laminate compositions
Claims (11)
1. A toughening material for a prepreg, the toughening material comprising a carbon material aerogel and a thermoplastic resin, wherein the mass ratio of the carbon material aerogel to the thermoplastic resin is 1: (0.5-10); the toughening material is prepared by dissolving the thermoplastic resin in an organic solvent, immersing carbon material aerogel in the thermoplastic resin solution, removing the organic solvent, and then pressing, wherein the thickness of the obtained toughening material is 10-30 mu m.
2. The toughening material of claim 1 wherein:
the thermoplastic resin is at least one selected from polyether ketone, polyether ether ketone, polyether imide, polysulfone, polyether sulfone, polyphenylene sulfide, polyphenyl ether, polyamide or modified products thereof; and/or the number of the groups of groups,
the carbon material aerogel is at least one selected from graphene aerogel or carbon nanotube aerogel.
3. The toughening material of claim 1 wherein:
the mass ratio of the carbon material aerogel to the thermoplastic resin is 1: (2-10).
4. A method of producing a toughening material according to any one of claims 1 to 3, comprising the steps of:
and dissolving the thermoplastic resin in an organic solvent, soaking the carbon material aerogel in the thermoplastic resin solution, removing the organic solvent, and then pressing to obtain the toughening material.
5. The method for producing a toughening material according to claim 4, wherein:
the organic solvent is at least one of tetrahydrofuran, dichloroethane, tetrachloroethane, dichloromethane, trichloromethane, N-dimethylformamide, N-dimethylacetamide or N, N-dimethylpyrrolidone.
6. A high toughness composite material comprising a prepreg and a toughening layer, wherein the prepreg is interlaminar with the toughening layer, the toughening layer is made of the toughening material for the prepreg according to any one of claims 1 to 3, and the prepreg comprises a resin matrix and reinforcing fibers.
7. The high toughness composite according to claim 6, comprising the following components in weight percent:
20-40 wt% of a resin matrix;
50-80 wt% of reinforcing fiber;
0.5 to 30 weight percent of toughening layer.
8. The high toughness composite according to claim 7, wherein:
25-35 wt% of a resin matrix;
60-70 wt% of reinforcing fiber;
2-20wt% of toughening layer.
9. The high toughness composite according to claim 6, wherein:
the resin matrix is an epoxy resin system, a bismaleimide resin system, a phenolic resin system or a cyanate resin system; and/or the number of the groups of groups,
the reinforcing fiber is at least one selected from carbon fiber, aramid fiber, glass fiber and basalt fiber.
10. The high toughness composite according to claim 6, wherein:
the thickness of the toughening layer is 10-30 mu m.
11. A method of preparing a high toughness composite according to any one of claims 6 to 10, comprising laying the toughening layer between layers of prepreg, curing to obtain the high toughness composite.
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