CN101007443B - Preparation method of nanofiber toughening carbon fiber reinforced composite - Google Patents
Preparation method of nanofiber toughening carbon fiber reinforced composite Download PDFInfo
- Publication number
- CN101007443B CN101007443B CN200710063099XA CN200710063099A CN101007443B CN 101007443 B CN101007443 B CN 101007443B CN 200710063099X A CN200710063099X A CN 200710063099XA CN 200710063099 A CN200710063099 A CN 200710063099A CN 101007443 B CN101007443 B CN 101007443B
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- nanofiber
- resin
- preform
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 75
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 75
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000002121 nanofiber Substances 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 53
- 239000011347 resin Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 50
- 230000008569 process Effects 0.000 claims abstract description 33
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 26
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 26
- 229920006351 engineering plastic Polymers 0.000 claims abstract description 18
- 239000011229 interlayer Substances 0.000 claims abstract description 9
- 238000009987 spinning Methods 0.000 claims abstract description 9
- 238000001523 electrospinning Methods 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 50
- 239000011159 matrix material Substances 0.000 claims description 36
- 229920002492 poly(sulfone) Polymers 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 14
- 239000003822 epoxy resin Substances 0.000 claims description 13
- 229920000647 polyepoxide Polymers 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000010041 electrostatic spinning Methods 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 230000003014 reinforcing effect Effects 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004697 Polyetherimide Substances 0.000 claims description 5
- 229920001601 polyetherimide Polymers 0.000 claims description 5
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical class CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004643 cyanate ester Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000009719 polyimide resin Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 38
- 239000012528 membrane Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000805 composite resin Substances 0.000 abstract 3
- 230000005611 electricity Effects 0.000 abstract 1
- 238000007493 shaping process Methods 0.000 abstract 1
- 230000003068 static effect Effects 0.000 abstract 1
- 239000004744 fabric Substances 0.000 description 65
- 238000005452 bending Methods 0.000 description 40
- 239000000243 solution Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 21
- 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 18
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 18
- 238000001291 vacuum drying Methods 0.000 description 15
- 208000037656 Respiratory Sounds Diseases 0.000 description 11
- 239000000835 fiber Substances 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 10
- -1 poly tetrafluoroethylene Polymers 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 10
- 230000000930 thermomechanical effect Effects 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 229910015900 BF3 Inorganic materials 0.000 description 9
- FAUAZXVRLVIARB-UHFFFAOYSA-N 4-[[4-[bis(oxiran-2-ylmethyl)amino]phenyl]methyl]-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC(CC=2C=CC(=CC=2)N(CC2OC2)CC2OC2)=CC=1)CC1CO1 FAUAZXVRLVIARB-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000013557 residual solvent Substances 0.000 description 4
- 239000011157 advanced composite material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002480 polybenzimidazole Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 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 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 230000003176 fibrotic effect Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Images
Abstract
A nano-fiber toughened carbon fiber resin-based composite material preparation method belongs to composite material field. It is characterized by using the nano-fiber felt or membrane of thermoplastic engineering plastics as the toughening components. The preparation method is: using the carbon fiber pre-forming body as the negative pole receiver of static electricity spinning, directly spinning the thermoplastic engineering plastics nano-fiber felt or membrane on the pre-forming body, compared with the resin base of carbon fiber pre-forming body, the spinned nano-fiber felt or membrane has weight ratio; ballasting the pre-forming body of carbon fiber which contains nano-fiber felt or membrane, preparing the carbon fiber pre-forming body containing nano-fiber interlayer structure; curing in accordance with the composite materials molding process, preparing the toughened carbon fiber resin-based composite material. Compared with traditional toughening method, the invention has simpler shaping process, the fracture toughness property of carbon fiber resin-based composite material is significantly increased with less toughening component content, the yield rate of electrospinning is higher, it is easy to spread and application in actual production.
Description
Technical field
The present invention relates to a kind of preparation method of nanofiber toughening carbon fiber reinforced composite, belong to field of compound material.
Background technology
The preform of carbon fiber/resin matrix has been widely used in the advanced composite material field, and the resin matrix of current advanced composite material just develops towards high-ductility, direction high-strength, high temperature.Yet the toughness reinforcing of composite is a difficult point always, thermoplastic is blended into the resin matrix of composite, the intensity and the heat resistance that can in toughness reinforcing, keep composite, but owing to viscosity sharply increases the processing and forming difficulty that causes composite.In actual application, method for toughening need be complementary with the moulding process of advanced composite material, could solve the toughness problem of fibre reinforced composites and have its actual application value.The mode that traditional interlayer toughened method adopts thermoplastic particle or solvent method film shop layer to add more, and about addition reaches 15%, just can obtain reasonable toughening effect.But the toughness of thermoplastic itself makes it be difficult to be processed into micro-size particles, and the preparation process of solvent method film is more complicated then, and its difficult dissolubility will influence the flowability and the permeability of resin matrix, has therefore limited its practical application.
Electrostatic spinning has almost been included all polymer even organic-inorganic hybrid composite system as realizing one of Fibrotic method few in number of nano material.Nanofiber non-woven mat or film are collected the receiver of metal material usually, because carbon fiber has excellent conducting performance, the preform of carbon fiber/resin matrix can be used as the receiver of electrostatic spinning.Preform is that body is driven in the centre of preparation composite, be easy to processing and forming, if directly as the receiver of electrostatic spinning, can simplify nanofiber non-woven mat or the operability of film in actual application greatly with the preform of carbon fiber/resin matrix.
The diameter of nanofiber is generally between tens nanometers～one micron, and the hole dimension of non-woven mat is between several～hundreds of micron, and (specific area as the nanofiber of diameter 100nm is 1000m to have the specific area of superelevation
2About/g) and big porosity.United States Patent (USP) (6265333) with polybenzimidazoles (PBI) nanofiber of electrostatic spinning as time fortifying fibre, be incorporated into the prepreg surface of main fortifying fibre/resin matrix, under the prerequisite of the performance that does not reduce laminate and its weight of increase, realized the interlayer toughened of certain effect, improved with the interface of resin matrix and combine but its reason mainly is a time fortifying fibre.Chinese patent (200510027914) is distributed to the function nano particle in the polymer solution, prepared nano fiber non-woven fabric by electrostatic spinning, substantially do not influencing under the situation of thickness of composite material and weight, certain thickness nano fibrous membrane is inserted into the interface layer of composite, has prepared a kind of functional interlayer composite.Based on applying of glass fibre non-woven mat, the technology diversity and the performance of glass fiber reinforced plastics composite material have been promoted, its principle is to have utilized the loose structure of glass fibre non-woven mat to be beneficial to characteristics such as the infiltration of resin matrix and mechanical strength isotropic, and has improved manufacturability and adaptability greatly.If thermoplastic is prepared into the non-woven mat or the film of nanofiber, and has mass ratio with respect to the resin matrix in the preform, toughening effect can be reached, a new application of nanofiber mats or film can be opened up simultaneously structural composite material.
Summary of the invention
The technical problem to be solved in the present invention is the toughness reinforcing difficult problem that performance behind the composite material toughening and two aspects of method for toughening really solve fibre reinforced composites, a kind of preparation method of nanofiber toughening carbon fiber reinforced composite is provided, when increasing toughness, guaranteed that also modulus and heat resistance do not reduce, solve the difficult matching of general method for toughening and composite material process planning, and had actual using value.
The preparation method of nanofiber toughening carbon fiber reinforced composite of the present invention adopts the nanofiber mats of thermoplastic engineering plastic or film as toughness reinforcing component, be layed in the interlayer of the carbon fiber preform that contains resin matrix, reaction induced being separated by nanofiber mats or film in the resin matrix solidification process of preform realized toughening effect, prepares the carbon fiber resin matrix composite that a kind of toughness improves.
The toughening effect of described toughening composition is not that the form with nanofiber exists, but the little dissolubility that has improved in resin matrix of the diameter of nanofiber, the bigger serface of nanofiber and high porosity, improved resin matrix in the permeability of composite interlayer with to the wellability of fortifying fibre, and the thermoplastic realization response is induced be separated, the thermoplastic phase microballoon that is finally converted into diameter and is micro-meter scale is realized.
Fortifying fibre is a carbon fiber in the described toughening composition, and the electric conductivity of utilizing carbon fiber is continuous or directly be received in gap on the preform of carbon fiber/resin matrix with the nanofiber mats of thermoplastic engineering plastic or symphysis.
The preparation method of nanofiber toughening carbon fiber reinforced composite of the present invention comprises the following steps:
1) adopt electrospinning process to prepare the nanofiber of thermoplastic engineering plastic, with the preform of carbon fiber/resin matrix receiver as electrostatic spinning, directly with the nanofiber spinning on preform, form one deck nanofiber mats or film; The nanofiber mats of thermoplastic engineering plastic or film are 1.0%～5.0% with respect to the mass ratio of resin matrix in the carbon fiber preform; The diameter of nanofiber is between the 100-1000nm;
2) repeat above step 1), obtain carbon fiber preform that above-mentioned multilayer contains nanofiber mats or film after, the shop layer, preparation contains the carbon fiber preform of nanofiber sandwich structure;
3) moulding process according to composite solidifies, and is prepared into toughness reinforcing carbon fiber resin matrix composite.
Described step 1) adopts electrospinning process to prepare the nanofiber of thermoplastic engineering plastic, and wherein thermoplastic engineering plastic is one or several of polyether sulfone, polysulfones, PEI, polyether-ketone, polyester, Polyamide Engineering Plastic; Thermoplastic engineering plastic is dissolved in dimethyl formamide, dimethylacetylamide, acetone, carrene, trichloroethanes, dimethyl sulfoxide (DMSO), one or more solvents of oxolane, makes electrostatic spinning behind the solution.
The preform of described carbon fiber/resin matrix is the prepreg of carbon fiber; Carbon fibre fabric cloth; The carbon fiber needle punched fabric; Through change, weft-knitted and axial, multidirectional enhancing knitted fabric; Two dimension two is a kind of to, two-dimentional three-dimensional braid.
Contain resin matrix in the described carbon fiber preform, resin matrix is one of epoxy resin, bimaleimide resin, unsaturated-resin, polyimide resin, phenolic resins, cyanate ester resin, vinyl ester resin, and the volume content of carbon fiber is 50%-70% in the preform.
Advantage of the present invention:
The present invention utilizes the carbon fiber good electrical conductivity, with the preform of carbon fiber/resin matrix receiver as electrostatic spinning, directly with the nanofiber spinning on preform, by spreading the interlayer that layer promptly is layed in nanofiber carbon fiber resin matrix composite easily, more traditional method for toughening moulding process is simple.The little dissolubility that has improved in resin matrix of the diameter of nanofiber, the bigger serface of nanofiber and high porosity, improved resin matrix in the permeability of composite interlayer with to the wellability of fortifying fibre, therefore the thermoplastic realization response being induced is separated, the fracture toughness of carbon fiber resin matrix composite significantly improves under less toughness reinforcing constituent content, and the yield of electrospinning silk is higher, is easy to apply in actual production.Importantly the present invention has opened up a new application of nanofiber mats or film.
In addition, except that having the fracture toughness that significantly improves, the not high-modulus and the high-fire resistance of toughened system have also been kept by nanofiber toughened carbon fiber resin matrix composite.Adopt among the present invention the nanofiber toughened hot setting of polysulfones carbon fiber/epoxy resin preimpregnation cloth fracture toughness, mechanical property and hot property and during the contrast of toughened system and solvent method film toughened system is not listed in the table below.
Description of drawings:
Fig. 1 is the electromicroscopic photograph of polysulfones nanofiber mats.
Fig. 2 is the fracture toughness G of the nanofiber toughened carbon fiber/epoxy resin system of polysulfones
ICThe section electromicroscopic photograph of batten.
Fig. 3 is preparation method's process flow diagram of the present invention.
The number in the figure explanation
The preform of the carbon fibre resin matrix after 1-cutting
2-electrostatic spinning apparatus schematic diagram
3-contain the carbon fiber preform of 1 layer of nanofiber mats or film
4-contain the carbon fiber preform of nanofiber sandwich structure
5-composite board
The specific embodiment:
According to technology shown in Figure 3, at first the preform with carbon fiber is cut into suitable dimension, as the negative pole receiver of electrostatic spinning apparatus; Directly with the nanofiber spinning of thermoplastic engineering plastic on preform, form 1 layer of nanofiber mats or film; Repeat above-mentioned steps, obtain shop layer behind the preform of carbon fiber that multilayer contains nanofiber mats or film, preparation contains the carbon fiber preform of nanofiber sandwich structure; Moulding process according to composite solidifies, and is prepared into toughness reinforcing carbon fiber resin matrix composite.Wherein committed step is spinning, at first with thermoplastic vacuum drying oven drying under high temperature, is dissolved in suitable solvent then and makes solution before the spinning.At last the electrospinning wire connection is closed on the carbon fiber preform of receiving belt top of transversely movable sheet metal or continuous motion, the content of nanofiber is that the weight by preform before and after the spinning calculates.
Embodiment 1:
Choose the carbon fiber/epoxy resin preimpregnation cloth of hot setting, wherein resin system is that (ratio of weight and number is 100:30 to glycidyl amine epoxy resin (TGDDM)/DADPS (DDS)/boron trifluoride mono aminoethane: 1), carbon fiber is toray T700SC, by 180 * 150mm
2Size preimpregnation cloth is cut into 24, by 80 * 80mm
2Size preimpregnation cloth is cut into 16.Polysulfones (PSF) is chosen the P-1700 of AMOCO. company, after vacuum drying, is dissolved in the mixed solvent of dimethylacetylamide and acetone, is made into concentration and is 25% polysulfones solution.At voltage is 24KV, and flow velocity is 1.5ml/h, is under the condition of 16cm to the distance of preimpregnation cloth receiver, with polysulfones solution direct fabrics on preimpregnation cloth.The diameter of prepared nanofiber is 100～400nm, and as shown in Figure 1, through the calculating of weighing, the weight content of nanofiber is 1.0%.Then with 24 layers of tiling, wherein the shop is gone into the long poly tetrafluoroethylene (thickness 50 μ m) of 50mm (this pre-crackle is not the layer that the toughness reinforcing composite of preparation needs as pre-crackle between 12 layers and 13 layers, just in order to test fracture critical energy rate of release, this layer not in the actual product.Following embodiment is identical).At last according to curing process cure under pressure on vulcanizing press of 130 ℃/2h+180 ℃/2h+200 ℃/1h, pressure is 20MPa.The thickness of pressed sheet is 3mm, and sheet material cuts into 180 * 25mm, is made into the double cantilever beam sample again, can test fracture critical energy rate of release (G
Ic), be specially 0.493KJ/m
2With 16 layers of tiling, become sheet material according to above-mentioned process stempressing, the thickness of pressed sheet is 2mm, sheet material cuts into the sample of 80 * 6mm, can test bending strength, bending modulus and dynamic thermomechanical property, and bending strength is 1633MPa, bending modulus is 112GPa, and glass transition temperature is 265 ℃.
Embodiment 2:
Choose the carbon fiber/epoxy resin preimpregnation cloth of hot setting, wherein resin system is that (ratio of weight and number is 100:30 to glycidyl amine epoxy resin (TGDDM)/DADPS (DDS)/boron trifluoride mono aminoethane: 1), carbon fiber is toray T700SC, by 180 * 150mm
2Size preimpregnation cloth is cut into 24, by 80 * 80mm
2Size preimpregnation cloth is cut into 16.Polysulfones (PSF) is chosen the P-1700 of AMOCO. company, after vacuum drying, is dissolved in the mixed solvent of dimethylacetylamide and acetone, is made into concentration and is 25% polysulfones solution.At voltage is 24KV, and flow velocity is 1.5ml/h, is under the condition of 16cm to the distance of preimpregnation cloth receiver, with polysulfones solution direct fabrics on preimpregnation cloth.The diameter of prepared nanofiber is 100～400nm, and through the calculating of weighing, the weight content of nanofiber is 3.O%.With 24 layers of tiling, wherein the long poly tetrafluoroethylene (thickness 50 μ m) of 50mm is gone into as pre-crackle in the shop between 12 layers and 13 layers then.At last according to curing process cure under pressure on vulcanizing press of 130 ℃/2h+180 ℃/2h+200 ℃/1h, pressure is 20MPa.The thickness of pressed sheet is 3mm, and sheet material cuts into 180 * 25mm, is made into the double cantilever beam sample again, can test fracture critical energy rate of release (G
IC), be specially 0.808KJ/m
2With 16 layers of tiling, become sheet material according to above-mentioned process stempressing, the thickness of pressed sheet is 2mm, sheet material cuts into the sample of 80 * 6mm, can test bending strength, bending modulus and dynamic thermomechanical property, and bending strength is 1668MPa, bending modulus is 114GPa, and glass transition temperature is 263 ℃.
Embodiment 3:
Choose the carbon fiber/epoxy resin preimpregnation cloth of hot setting, wherein resin system is that (ratio of weight and number is 100:30 to glycidyl amine epoxy resin (TGDDM)/DADPS (DDS)/boron trifluoride mono aminoethane: 1), carbon fiber is toray T700SC, by 180 * 150mm
2Size preimpregnation cloth is cut into 24, by 80 * 80mm
2Size preimpregnation cloth is cut into 16.Polysulfones (PSF) is chosen the P-1700 of AMOCO. company, after vacuum drying, is dissolved in the mixed solvent of dimethylacetylamide and acetone, is made into concentration and is 25% polysulfones solution.At voltage is 24KV, and flow velocity is 1.5ml/h, is under the condition of 16cm to the distance of preimpregnation cloth receiver, with polysulfones solution direct fabrics on preimpregnation cloth.The diameter of prepared nanofiber is 100～400nm, and through the calculating of weighing, the weight content of nanofiber is 5.0%.With 24 layers of tiling, wherein the long poly tetrafluoroethylene (thickness 50 μ m) of 50mm is gone into as pre-crackle in the shop between 12 layers and 13 layers then.At last according to curing process cure under pressure on vulcanizing press of 130 ℃/2h+180 ℃/2h+200 ℃/1h, pressure is 20MPa.The thickness of pressed sheet is 3mm, and sheet material cuts into 180 * 25mm, is made into the double cantilever beam sample again, can test fracture critical energy rate of release (G
IC), be specially 0.868KJ/m
2From accompanying drawing 2, can obviously find out the thermoplastic phase microballoon that nanofiber is separated and forms, so fracture toughness improves significantly.With 16 layers of tiling, become sheet material according to above-mentioned process stempressing, the thickness of pressed sheet is 2mm, sheet material cuts into the sample of 80 * 6mm, can test bending strength, bending modulus and dynamic thermomechanical property, and bending strength is 1695MPa, bending modulus is 115GPa, and glass transition temperature is 260 ℃.
Comparative example 1:
Choose the carbon fiber/epoxy resin preimpregnation cloth of hot setting, wherein resin system is that (ratio of weight and number is 100:30 to glycidyl amine epoxy resin (TGDDM)/DADPS (DDS)/boron trifluoride mono aminoethane: 1), carbon fiber is toray T700SC, by 180 * 150mm
2Size 24 that preimpregnation cloth is cut into, by 80 * 80mm
2Size preimpregnation cloth is cut into 16.Polysulfones (PSF) is chosen the P-1700 of AMOCO. company, after vacuum drying, is dissolved in that to be made into concentration in the carrene be 10% polysulfones solution, solution is poured on the glass plate and with glass bar wipes off repeatedly.After at room temperature placing 6 hours, scrape the PS membrane that obtains the solvent method preparation, put into vacuum drying oven again and be warmed up to 150 ℃ of removal residual solvents.Be cut into 180 * 150mm then
2Size spread in 24 layers of preimpregnation cloth, wherein the long poly tetrafluoroethylene (thickness 50 μ m) of 50mm is gone into as pre-crackle in the shop between 12 layers and 13 layers.Through the calculating of weighing, the weight content of solvent method film is 1.0%.Curing process according to embodiment 1 is molded into sheet material at last, and the thickness of pressed sheet is 3mm, and sheet material cuts into 180 * 25mm, is made into the double cantilever beam sample again, can test fracture critical energy rate of release (G
IC), be specially 0.370KJ/m
2Be cut into 80 * 80mm
2Size spread in 16 layers of preimpregnation cloth, become sheet material according to above-mentioned process stempressing, the thickness of pressed sheet is 2mm, sheet material cuts into the sample of 80 * 6mm, can test bending strength, bending modulus and dynamic thermomechanical property, bending strength is 1564MPa, and bending modulus is 107GPa, and glass transition temperature is 263 ℃.
Comparative example 2:
Choose the carbon fiber/epoxy resin preimpregnation cloth of hot setting, wherein resin system is that (ratio of weight and number is 100:30 to glycidyl amine epoxy resin (TGDDM)/DADPS (DDS)/boron trifluoride mono aminoethane: 1), carbon fiber is toray T700SC, by 180 * 150mm
2Size 24 that preimpregnation cloth is cut into, by 80 * 80mm
2Size preimpregnation cloth is cut into 16.Polysulfones (PSF) is chosen the P-1700 of AMOCO. company, after vacuum drying, is dissolved in that to be made into concentration in the carrene be 10% polysulfones solution, solution is poured on the glass plate and with glass bar wipes off repeatedly.After at room temperature placing 6 hours, scrape the PS membrane that obtains the solvent method preparation, put into vacuum drying oven again and be warmed up to 150 ℃ of removal residual solvents.Be cut into the size that conforms to preimpregnation cloth then and spread in 24 layers of preimpregnation cloth, wherein the long poly tetrafluoroethylene (thickness 50 μ m) of 50mm is gone into as pre-crackle in the shop between 12 layers and 13 layers.Through the calculating of weighing, the weight content of solvent method film is 3.0%.Curing process according to embodiment 1 is molded into sheet material at last, and the thickness of pressed sheet is 3mm, and sheet material cuts into 180 * 25mm, is made into the double cantilever beam sample again, can test fracture critical energy rate of release (G
IC), be specially 0.536KJ/m
2Be cut into 80 * 80mm
2Size spread in 16 layers of preimpregnation cloth, become sheet material according to above-mentioned process stempressing, the thickness of pressed sheet is 2mm, sheet material cuts into the sample of 80 * 6mm, can test bending strength, bending modulus and dynamic thermomechanical property, bending strength is 1460MPa, and bending modulus is 105GPa, and glass transition temperature is 258 ℃.
Comparative example 3:
Choose the carbon fiber/epoxy resin preimpregnation cloth of hot setting, wherein resin system is that (ratio of weight and number is 100:30 to glycidyl amine epoxy resin (TGDDM)/DADPS (DDS)/boron trifluoride mono aminoethane: 1), carbon fiber is toray T700SC, by 180 * 150mm
2Size 24 that preimpregnation cloth is cut into, by 80 * 80mm
2Size preimpregnation cloth is cut into 16.Polysulfones (PSF) is chosen the P-1700 of AMOCO. company, after vacuum drying, is dissolved in that to be made into concentration in the carrene be 10% polysulfones solution, solution is poured on the glass plate and with glass bar wipes off repeatedly.After at room temperature placing 6 hours, scrape the PS membrane that obtains the solvent method preparation, put into vacuum drying oven again and be warmed up to 150 ℃ of removal residual solvents.Be cut into the size that conforms to preimpregnation cloth then and spread in 24 layers of preimpregnation cloth, wherein the long poly tetrafluoroethylene (thickness 50 μ m) of 50mm is gone into as pre-crackle in the shop between 12 layers and 13 layers.Through the calculating of weighing, the weight content of solvent method film is 5.0%.Curing process according to embodiment 1 is molded into sheet material at last, and the thickness of pressed sheet is 3mm, and sheet material cuts into 180 * 25mm, is made into the double cantilever beam sample again, can test fracture critical energy rate of release (G
IC), be specially 0.618KJ/m
2Be cut into 80 * 80mm
2Size spread in 16 layers of preimpregnation cloth, become sheet material according to above-mentioned process stempressing, the thickness of pressed sheet is 2mm, sheet material cuts into the sample of 80 * 6mm, can test bending strength, bending modulus and dynamic thermomechanical property, bending strength is 1367MPa, and bending modulus is 102GPa, and glass transition temperature is 253 ℃.
Embodiment 4:
Choose the carbon fiber/epoxy resin preimpregnation cloth of hot setting, wherein resin system is that (ratio of weight and number is 100:30 to glycidyl amine epoxy resin (TGDDM)/DADPS (DDS)/boron trifluoride mono aminoethane: 1), carbon fiber is toray T300B, by 180 * 150mm
2Size preimpregnation cloth is cut into 24, by 80 * 80mm
2Size preimpregnation cloth is cut into 16.Polysulfones (PSF) is chosen the P-1700 of AMOCO. company, after vacuum drying, is dissolved in the mixed solvent of dimethylacetylamide and acetone, is made into concentration and is 23% polysulfones solution.At voltage is 24KV, and flow velocity is 2.4ml/h, is under the condition of 15cm to the distance of preimpregnation cloth receiver, with polysulfones solution direct fabrics on preimpregnation cloth.The diameter of prepared nanofiber is 550～1000nm, and through the calculating of weighing, the weight content of nanofiber is 3.3%.With 24 layers of tiling, wherein the long poly tetrafluoroethylene (thickness 50 μ m) of 50mm is gone into as pre-crackle in the shop between 12 layers and 13 layers then.At last according to curing process cure under pressure on vulcanizing press of 130 ℃/2h+180 ℃/2h+200 ℃/1h, pressure is 20MPa.The thickness of pressed sheet is 3mm, and sheet material cuts into 180 * 25mm, is made into the double cantilever beam sample again, can test fracture critical energy rate of release (G
IC), be specially 0.789KJ/m
2With 16 layers of tiling, be molded into sheet material according to above-mentioned curing process, the thickness of pressed sheet is 2mm, sheet material cuts into the sample of 80 * 6mm, can test bending strength, bending modulus and dynamic thermomechanical property, bending strength is 1420MPa, and bending modulus is 125GPa, and glass transition temperature is 251 ℃.
Comparative example 4:
Choose the carbon fiber/epoxy resin preimpregnation cloth of hot setting, wherein resin system is that (ratio of weight and number is 100:30 to glycidyl amine epoxy resin (TGDDM)/DADPS (DDS)/boron trifluoride mono aminoethane: 1), carbon fiber is toray T300B, by 180 * 150mm
2Size 24 that preimpregnation cloth is cut into, by 80 * 80mm
2Size preimpregnation cloth is cut into 16.Polysulfones (PSF) is chosen the P-1700 of AMOCO. company, after vacuum drying, is dissolved in that to be made into concentration in the carrene be 10% polysulfones solution, solution is poured on the glass plate and with glass bar wipes off repeatedly.After at room temperature placing 6 hours, scrape the PS membrane that obtains the solvent method preparation, put into vacuum drying oven again and be warmed up to 150 ℃ of removal residual solvents.Be cut into the size that conforms to preimpregnation cloth then and spread in 24 layers of preimpregnation cloth, wherein the long poly tetrafluoroethylene (thickness 50 μ m) of 50mm is gone into as pre-crackle in the shop between 12 layers and 13 layers.Through the calculating of weighing, the weight content of solvent method film is 3.3%.Curing process according to embodiment 1 is molded into sheet material at last, and the thickness of pressed sheet is 3mm, and sheet material cuts into 180 * 25mm, is made into the double cantilever beam sample again, can test fracture critical energy rate of release (G
IC), be specially 0.517KJ/m
2Be cut into 80 * 80mm
2Size spread in 16 layers of preimpregnation cloth, become sheet material according to above-mentioned process stempressing, the thickness of pressed sheet is 2mm, sheet material cuts into the sample of 80 * 6mm, can test bending strength, bending modulus and dynamic thermomechanical property, bending strength is 1273MPa, and bending modulus is 115GPa, and glass transition temperature is 246 ℃.
Embodiment 5:
Choose the preimpregnation cloth of the two dimension two of hot setting to carbon cloth/epoxy resin, wherein resin system is bisphenol-A glycidol ether (DGEBA)/DADPS (DDS)/boron trifluoride mono aminoethane (ratio of weight and number is 100: 33: 1), carbon cloth is the G803 of toray, by 180 * 150mm
2Size preimpregnation cloth is cut into 24, by 80 * 80mm
2Size preimpregnation cloth is cut into 16.The polyether sulfone (PES) that thermoplastic selects for use Jilin University to provide after vacuum drying, is dissolved in the dimethyl formamide, is made into concentration and is 20% solution.At voltage is 18KV, and flow velocity is 1.7ml/h, is under the condition of 14cm to the distance of preimpregnation cloth receiver, with polyether sulfone solution direct fabrics on preimpregnation cloth.The diameter of prepared nanofiber is 150～550nm, and through the calculating of weighing, the weight content of nanofiber is 1.78%.With 24 layers of tiling, wherein the long poly tetrafluoroethylene (thickness 50 μ m) of 50mm is gone into as pre-crackle in the shop between 12 layers and 13 layers then.At last according to curing process cure under pressure on vulcanizing press of 120 ℃/0.5h+190 ℃/2h, pressure is 20MPa.The thickness of pressed sheet is 3mm, and sheet material cuts into 180 * 25mm, is made into the double cantilever beam sample again, can test fracture critical energy rate of release (G
IC), 0.469KJ/m
2(the G of toughened system not
ICBe 0.324KJ/m
2).With 16 layers of tiling, be molded into sheet material according to above-mentioned curing process, the thickness of pressed sheet is 2mm, sheet material cuts into the sample of 80 * 6mm, can test bending strength, bending modulus and dynamic thermomechanical property, bending strength is 1606MPa, and bending modulus is 100.6GPa, and glass transition temperature is 218 ℃.
Embodiment 6:
Choose the preimpregnation cloth of the carbon fiber/bismaleimide resin of hot setting, carbon fiber is the T300 of Japanese eastern nation, by 180 * 150mm
2Size preform is cut into 24, by 80 * 80mm
2Size preimpregnation cloth is cut into 16.Thermoplastic engineering plastic is selected the PEI (PEI) of GE company for use, after vacuum drying, is dissolved in the trichloroethanes, is made into concentration and is 14% solution.At voltage is 15KY, and flow velocity is 1.4ml/h, is under the condition of 15cm to the distance of preimpregnation cloth receiver, with polyetherimide amine aqueous solution direct fabrics on preimpregnation cloth.The diameter of prepared nanofiber is 400～700nm, and through the calculating of weighing, the weight content of nanofiber is 4.32%.Then according to a graded with 24 layers of tiling, wherein the long poly tetrafluoroethylene (thickness 50 μ m) of 50mm is gone into as pre-crackle in the shop between 12 layers and 13 layers.At last according to curing process cure under pressure on vulcanizing press of 180 ℃/2h+200 ℃/4h, pressure is 20MPa.The thickness of pressed sheet is 3mm, and sheet material cuts into 180 * 25mm, is made into the double cantilever beam sample again, test fracture critical energy rate of release (G
IC) be 0.709KJ/m
2(the G of toughened system not
ICBe 0.294KJ/m
2).With 16 layers of tiling, become sheet material according to above-mentioned process stempressing, the thickness of pressed sheet is 2mm, sheet material cuts into the sample of 80 * 6mm, can test bending strength, bending modulus and dynamic thermomechanical property, and bending strength is 1491MPa, bending modulus is 109GPa, and glass transition temperature is 259 ℃.
Claims (3)
1. the preparation method of a nanofiber toughening carbon fiber reinforced composite is characterized by, and may further comprise the steps:
1) adopt electrospinning process to prepare the nanofiber of thermoplastic engineering plastic, with the preform of carbon fiber/resin matrix receiver as electrostatic spinning, directly with the nanofiber spinning on preform, form one deck nanofiber mats or film; The nanofiber mats of thermoplastic engineering plastic or film are 1.0%～5.0% with respect to the mass ratio of resin matrix in the carbon fiber preform; The diameter of nanofiber is between the 100-1000nm; And the volume content of carbon fiber is 50%-70% in the preform;
2) repeat above step 1), after obtaining a plurality of carbon fiber preforms that contain nanofiber mats or film, by shop layer nanofiber is layed in the interlayer of the carbon fiber preform that contains resin matrix, preparation contains the carbon fiber preform of nanofiber sandwich structure;
3) moulding process according to composite solidifies, and is prepared into toughness reinforcing carbon fiber resin matrix composite.
2. the preparation method of nanofiber toughening carbon fiber reinforced composite according to claim 1, it is characterized in that: described step 1) adopts electrospinning process to prepare the nanofiber of thermoplastic engineering plastic, and wherein thermoplastic engineering plastic is one or several of polyether sulfone, polysulfones, PEI, polyether-ketone, polyester, Polyamide Engineering Plastic; Thermoplastic engineering plastic is dissolved in dimethyl formamide, dimethylacetylamide, acetone, carrene, trichloroethanes, dimethyl sulfoxide (DMSO), one or more solvents of oxolane, makes electrostatic spinning behind the solution.
3. the preparation method of nanofiber toughening carbon fiber reinforced composite according to claim 1, it is characterized in that: contain resin matrix in the described carbon fiber preform, resin matrix is one of epoxy resin, bimaleimide resin, polyimide resin, phenolic resins, cyanate ester resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710063099XA CN101007443B (en) | 2007-01-26 | 2007-01-26 | Preparation method of nanofiber toughening carbon fiber reinforced composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710063099XA CN101007443B (en) | 2007-01-26 | 2007-01-26 | Preparation method of nanofiber toughening carbon fiber reinforced composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101007443A CN101007443A (en) | 2007-08-01 |
| CN101007443B true CN101007443B (en) | 2010-09-01 |
Family
ID=38696212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710063099XA Expired - Fee Related CN101007443B (en) | 2007-01-26 | 2007-01-26 | Preparation method of nanofiber toughening carbon fiber reinforced composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101007443B (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107535A (en) * | 2010-12-22 | 2011-06-29 | 成都飞机工业（集团）有限责任公司 | Method for manufacturing carbon fiber reinforced resin matrix composite structure |
| JP5715884B2 (en) * | 2011-05-31 | 2015-05-13 | 住友ベークライト株式会社 | Scroll molding |
| CN102382318B (en) * | 2011-10-08 | 2013-08-14 | 中国科学院山西煤炭化学研究所 | Preparation method of continuous carbon fiber reinforced composite with improved water erosion resistance |
| CN102382317B (en) * | 2011-10-08 | 2013-08-14 | 中国科学院山西煤炭化学研究所 | Method for raising interlayer shearing strength of continuous carbon fiber reinforced composite |
| CN102862355B (en) * | 2012-10-09 | 2014-12-03 | 扬州大学 | Biodegradable polymer composite material |
| CN103000851B (en) * | 2012-12-20 | 2015-08-26 | 中国东方电气集团有限公司 | A kind of lithium battery polysulfones nano fiber diaphragm and preparation method thereof |
| CN107254740B (en) * | 2013-02-14 | 2019-06-28 | 纳米帕雷尔股份有限公司 | Nanofiber mixing felt |
| CN103230622A (en) * | 2013-04-19 | 2013-08-07 | 南通纺织职业技术学院 | Conduit for tissue-engineered nerve transplanting and preparation method thereof |
| CN103552357B (en) * | 2013-10-25 | 2016-06-29 | 中航复合材料有限责任公司 | A kind of preparation method of composite enhanced fabrics |
| CN104031590B (en) * | 2014-07-01 | 2015-09-02 | 黑龙江省科学院石油化学研究院 | The preparation method of epoxyn |
| CN104407060B (en) * | 2014-11-12 | 2017-10-13 | 上海飞机制造有限公司 | A kind of manufacture method of composite porosity reference block |
| CN105150612A (en) * | 2015-06-26 | 2015-12-16 | 中国航空工业集团公司北京航空材料研究院 | Graphene polymer composite fiber film reinforced and toughened composite material |
| CN105153640A (en) * | 2015-06-26 | 2015-12-16 | 中国航空工业集团公司北京航空材料研究院 | Preparation method for graphene polymer composite fiber film reinforced and toughened composite material |
| CN105401335A (en) * | 2015-09-06 | 2016-03-16 | 天津工业大学 | Manufacturing method for polyaryletherketone group micro/nano fiber |
| CN105401339A (en) * | 2015-09-06 | 2016-03-16 | 天津工业大学 | Manufacturing method for polyether sulfonyl micro/nano fibers |
| CN106521722B (en) * | 2015-09-15 | 2019-02-05 | 国网智能电网研究院 | A kind of mixed fibre device |
| CN106811847A (en) * | 2015-12-02 | 2017-06-09 | 国网智能电网研究院 | A kind of fiber reinforced thermolplastic composite material mixed fiber yarn and preparation method thereof |
| CN105733175A (en) * | 2016-02-19 | 2016-07-06 | 苏州振瑞昌材料科技有限公司 | Bakelite purline manufactured by pre-fabricated member with flow guide layer and manufacturing method thereof |
| CN105694354A (en) * | 2016-02-19 | 2016-06-22 | 苏州振瑞昌材料科技有限公司 | Bakelite corrugated board made of preliminarily woven components with flow guide layers and method for manufacturing bakelite corrugated board |
| 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 |
| CN110280229B (en) * | 2019-06-28 | 2022-03-11 | 东南大学 | Preparation and application method of pterin compound selective separation enrichment material |
| CN110818306B (en) * | 2019-11-21 | 2020-08-18 | 四川大学 | Reinforcing and toughening agent for concrete and preparation method and application thereof |
| CN114561082B (en) * | 2022-01-27 | 2023-11-28 | 武汉理工大学 | Polyamide nanofiber toughened self-healing carbon fiber/epoxy resin matrix composite material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6265333B1 (en) * | 1998-06-02 | 2001-07-24 | Board Of Regents, University Of Nebraska-Lincoln | Delamination resistant composites prepared by small diameter fiber reinforcement at ply interfaces |
| CN1460534A (en) * | 2003-05-28 | 2003-12-10 | 东南大学 | Nano fibre protective filtering material and its preparation method |
| CN1511200A (en) * | 2002-03-26 | 2004-07-07 | Manufacturing device and method of preparing for nanofibers via electro-blown spinning process |
-
2007
- 2007-01-26 CN CN200710063099XA patent/CN101007443B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6265333B1 (en) * | 1998-06-02 | 2001-07-24 | Board Of Regents, University Of Nebraska-Lincoln | Delamination resistant composites prepared by small diameter fiber reinforcement at ply interfaces |
| CN1511200A (en) * | 2002-03-26 | 2004-07-07 | Manufacturing device and method of preparing for nanofibers via electro-blown spinning process | |
| CN1460534A (en) * | 2003-05-28 | 2003-12-10 | 东南大学 | Nano fibre protective filtering material and its preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101007443A (en) | 2007-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101007443B (en) | Preparation method of nanofiber toughening carbon fiber reinforced composite | |
| CN102794952B (en) | Preparation method of CFRP (Carbon Fiber Reinforced Plastics) composite material with height orientation MWNTs and synchronously reinforced and toughened by hybrid nanofiber | |
| CN102785437B (en) | A kind of composite conducting thin layer and its preparation method and application | |
| CN102166862B (en) | Preparation method of high-performance prefabricated reinforced fabric for facilitating resin flow | |
| JP6161108B2 (en) | Fiber-reinforced composite material and method for producing the same | |
| EP2013003B1 (en) | A thermoplastic toughening material and related method | |
| TWI505928B (en) | Compatible carrier for secondary toughening | |
| JP5158778B2 (en) | Epoxy resin impregnated yarn and its use for producing preforms | |
| AU2016354491B2 (en) | Hybrid veil as interlayer in composite materials | |
| WO2016080238A1 (en) | Laminate, integrated molding, and method for producing same | |
| CN102516569A (en) | Preparation method for carbon nanotube non-woven fabric interlayer modified fiber reinforced composite materials | |
| TW202006025A (en) | Fiber-reinforced resin composite body, production method therefor, and non-woven fabric for use in fiber-reinforced resin composite body | |
| CN103552357B (en) | A kind of preparation method of composite enhanced fabrics | |
| JP6956300B1 (en) | Reinforced fiber stitch base material, preform material, and fiber reinforced composite material, and methods for manufacturing them. | |
| CN108943767B (en) | Toughening modification method of composite material | |
| CN113544322B9 (en) | Continuous filament nonwoven fabric, laminate, composite material, and method for producing same | |
| CN110202905B (en) | In-situ three-dimensional resin composite material and application thereof | |
| CN108943888B (en) | Method for toughening interlamination of composite material | |
| CN104401070B (en) | One has composite sizing-toughness reinforcing bifunctional non-weaving cloth concurrently | |
| JP6961131B1 (en) | Reinforced fiber stitch base material, preform material, and fiber reinforced composite material, and methods for manufacturing them. | |
| CN111699211A (en) | Prepreg sheets and prepreg stacks useful for making low void content fiber reinforced composites | |
| KR20180094851A (en) | Binder resin composition for preform, binder particle, reinforcing fiber base, preform and fiber reinforced composite material | |
| CN116288930A (en) | Polyamide imide nanofiber membrane and preparation method and application thereof | |
| CN114933778A (en) | Automatic fiber-laying prepreg with crosslinked reticular toughening structure and preparation method thereof | |
| JP2020029011A (en) | Reinforced fiber tape material, and fiber reinforced resin molded body by immersing and curing matrix resin in the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100901 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |