CN101629024A - Self-repairing fiber reinforced polymer matrix composite and preparation method thereof - Google Patents
Self-repairing fiber reinforced polymer matrix composite and preparation method thereof Download PDFInfo
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- CN101629024A CN101629024A CN200910041625A CN200910041625A CN101629024A CN 101629024 A CN101629024 A CN 101629024A CN 200910041625 A CN200910041625 A CN 200910041625A CN 200910041625 A CN200910041625 A CN 200910041625A CN 101629024 A CN101629024 A CN 101629024A
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- Prior art keywords
- capsule
- repairing
- self
- fiber reinforced
- polymer matrix
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- 239000011159 matrix material Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 41
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- 239000011151 fibre-reinforced plastic Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
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- 229920005989 resin Polymers 0.000 claims abstract description 36
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- 239000000203 mixture Substances 0.000 claims abstract description 21
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- 239000003054 catalyst Substances 0.000 claims abstract description 4
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- 239000002841 Lewis acid Substances 0.000 claims description 11
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- 150000001875 compounds Chemical class 0.000 claims description 10
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 8
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- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- ACTRVOBWPAIOHC-UHFFFAOYSA-N succimer Chemical compound OC(=O)C(S)C(S)C(O)=O ACTRVOBWPAIOHC-UHFFFAOYSA-N 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- PXJUBOLFJDSAQQ-UHFFFAOYSA-M tetrapropylazanium;acetate Chemical compound CC([O-])=O.CCC[N+](CCC)(CCC)CCC PXJUBOLFJDSAQQ-UHFFFAOYSA-M 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ADBMSVFHVFJBFR-UHFFFAOYSA-N triethyl(hexadecyl)azanium Chemical compound CCCCCCCCCCCCCCCC[N+](CC)(CC)CC ADBMSVFHVFJBFR-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a self-repairing fiber reinforced polymer matrix composite and a preparation method thereof. In the method, a double-capsule repairing system respectively containing epoxy resin prepolymer and curing agent is evenly mixed into a resin matrix, then, the matrix curing agent and catalyst are added to be evenly mixed, the obtained mixture is used for dipping fiber reinforcing material, and at last, the self-repairing fiber reinforced polymer matrix composite is obtained by solidifying and shaping. When the self-repairing composite of the invention generates cracks or fiber unsticking damage owing to heat, force, environment corrosion and the like during processing, storing and using process, cracks pass through a restorative capsule which cracks along with the matrix to release reacting substance and quickly polymerize, thus preventing crack from expanding, repairing crack damage, keeping the mechanical property of the composites and prolonging the service life thereof. The self-repairing composite prepared by the invention can automatically finish repairing cracks at the temperature of negative 50-250 DEG C, and the repairing process totally needs no artificial intervention.
Description
Technical field
The present invention relates to fiber reinforced polymer matrix composite, be specifically related to a kind of self-repairing fiber reinforced polymer matrix composite and preparation method thereof.
Background technology
Fiber reinforced polymer matrix composite has plurality of advantages such as lightweight, high-strength, good electrical properties and erosion resistance, has obtained widespread use in industries such as aerospace, communications and transportation, chemical industry, building, machinery, microelectronics, sports goodss.But, in processing and use,, can produce local damage and tiny crack in composite inner inevitably owing to effects such as manufacturing deficiency, mechanical fatigue, thermal fatigue, impact, radiation, chemical degradations.On the composite part surface that is hit, though damage is not obvious even cannot see fully, the inside of parts has produced delamination damage, and this damage can reduce the rigidity and the intensity of material structure, and the reduction of its compressive strength is also more obvious.The matrix material damage process is followed successively by: matrix damage, fortifying fibre and matrix unsticking, fortifying fibre fracture.Studies show that, the tiny crack damage has a strong impact on mechanics, electricity, corrosion-resistant and other performance of matrix material, especially outside power is particularly under the fatigability periodic loading, and the stress level that these microdefects are born is much larger than mean stress, the local stress concentration that produces height of material.Therefore, bear before mean stress do not reach critical breaking tenacity at matrix material, be distributed in that material part in the region of stress concentration at first reaches critical breaking tenacity thresholding and the expansion and the merging that cause tiny crack, thereby even more serious destruction is taken place, make composite property descend until inefficacy.Therefore, early discovery and the reparation to the polymer matrix composite internal tiny crack is a very actual problem.Because the crackle of polymkeric substance is portion depths appearance within it often, be difficult to adopt conventional means to survey and repair.If these damages can not in time be repaired, can have a strong impact on normally using and shortening the life-span of material, cause the accident.Therefore, the early discovery of interior microscopic damage and repair stability in use to matrix material, to prolong its work-ing life very important.
The repairing of fiber reinforced polymer matrix composite structure is a technical skill, and main the employing gluedd joint repairing, comprises the method for subsidizing, mends method and injection by replacing a damaged part.Above method is primarily aimed at macrocrack and destroys.Though Dynamic Non-Destruction Measurements such as x-ray inspection at present, ultrasonic scanning and acoustic emission can detect the damage of material internal, but because the limitation of these detection techniques itself, on the comfort level to the degree of depth, size and the detection of internal injury relative merits are arranged respectively, and in fact be difficult to a large amount of structured materials are in time detected.Add the limitation of service technique, cause the microscopic damage of composite inner in time not found, early stage reparation is not known where to begin especially.
For reaching the early stage purpose of repair composite material internal fissure damage automatically, three kinds of intelligent materials with self-repair function have appearred at present.
(1) use the microcapsule and the metal Ru title complex Grubbs catalyzer that are enclosed with dicyclopentadiene (DCPD) to be embedded in the resin matrix of fibre enhancement epoxy composite material as the reparation system.When tiny crack passed microcapsule, effusive DCPD contacted with the Grubbs catalyzer and rapid polymerization reaction take place, thereby the bonding crackle reaches the reparation purpose.But because the Grubbs catalyst activity is very easily decayed, the environment ability to bear is poor, and its self-healing properties will descend greatly behind the material life-time service; DCPD is unstable properties at high temperature, volatile and generation self-polymeric reaction; DCPD fusing point higher (32.5 ℃) can not flow at a lower temperature, does not possess repair ability; DCPD is as a kind of unsaturated polyester, and its cross-linking products and most resin matrixes interface bonding are relatively poor.Therefore, DCPD and Grubbs catalyzer reparation system are not suitable for the renovation agent as the hot setting fibre reinforced composites, and simultaneously, this system does not possess the low temperature self-reparing capability yet.
(2) adopt renovation agents such as hollow pipes filling cyanoacrylate, Resins, epoxy-solidifying agent such as tubular fibre or Glass tubing, further with common fortifying fibre heeling-in in resin matrix.This kind method seems simple possible, and in fact, the diameter of hollow fiber is the mechanical property of conference reduction matrix material too, and too for a short time its processing and preparing that causes of diameter is very difficult; The selection filling and the port sealing technology of renovation agent have also limited its large-scale production and application.
(3) adopt and to contain the epoxy prepolymer microcapsule and imidazoles metal-salt Latence catalyst prepares the hot setting fibre enhancement epoxy composite material as the reparation system.Use Resins, epoxy as renovation agent, not only solved the stability and the endurance issues of renovation agent, also improved adhesive property and repairing effect simultaneously greatly.But, this reparation system must be under comparatively high temps the automatic repairing effect of (＞100 ℃) competence exertion, when being lower than this temperature, then do not possess self-reparing capability.
Summary of the invention
The objective of the invention is to the deficiency that exists at prior art, provide a kind of can self-regeneration under the wide temperature range condition, and the high fiber reinforced polymer matrix composite of remediation efficiency.
Another object of the present invention provides the preparation method of above-mentioned self-repairing fiber reinforced polymer matrix composite.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
Self-repairing fiber reinforced polymer matrix composite of the present invention, form by the following component of meter by weight:
(1) polymeric matrix, 30～90 parts;
(2) fiber reinforced material, 5～70 parts;
(3) contain the capsule of liquid-state epoxy resin prepolymer, 1～30 part;
(4) contain the capsule of LCM, 1～30 part;
(5) coupling agent, 0.1～5 part.
In above-mentioned self-repairing fiber reinforced polymer matrix composite, described polymeric matrix is preferably Resins, epoxy, unsaturated polyester, resol, urethane, polymeric amide or polyacrylic resin.
In above-mentioned self-repairing fiber reinforced polymer matrix composite, described fiber reinforced material is preferably glass fibre, carbon fiber, aramid fiber, silicon carbide fiber, sapphire whisker, boron fibre, whisker fibre, glass fibre, the short fabric of cutting felt, continuous felt, winding yarn or carbon fiber and aramid fiber braiding.
In above-mentioned self-repairing fiber reinforced polymer matrix composite, the described capsular core that contains the liquid-state epoxy resin prepolymer is preferably Resins, epoxy, and the capsule wall material is urethane, polyester, polymeric amide, polyacrylic ester, polyureas, poly(urea formaldehyde), melamine formaldehyde resin or their modifier; Capsule-core accounts for 40～98% of capsule total mass, and the capsule median size is 0.5 μ m～1mm, wall thickness 50nm～10 μ m.The mixture of two or more of the preferred part bisphenol A type epoxy resin of described capsule core Resins, epoxy, part bisphenol f type epoxy resin, part dihydroxyphenyl propane D type Resins, epoxy, Resorcinol type Resins, epoxy, methylol bisphenol A type epoxy resin, part glycidyl ester type epoxy resin or above-mentioned Resins, epoxy.
In above-mentioned self-repairing fiber reinforced polymer matrix composite, the described capsule that contains LCM is preferably Lewis acid capsule or polythiol capsule.
In the above-mentioned capsule that contains LCM, the capsular core of described Lewis acid is preferably: boron trifluoride, boron trichloride, aluminum chloride, iron trichloride, ferric bromide, tin tetrachloride, titanium tetrachloride, zirconium tetrachloride, antimony pentachloride, the dichloride beryllium, the mixture of one or more in the zinc dichloride, and aforesaid compound and ether, glycerine, tetrahydrofuran (THF), in the polyoxyethylene glycol any one or multiple formed complex compound, and hexafluoro arsenate, hexafluoro antimonate, hexa chloro-antimonate, the tetrachloro aluminate, the pentachloro-stannate, the mixture of one or more in the pentachloro-titanate; The capsule wall material is melamine formaldehyde resin, poly(urea formaldehyde), polyureas, urethane, polyester, polymeric amide, polyacrylic ester or their modifier, and the sorptive material that contains vesicular structure through the inside of embedding encapsulation; Capsule-core accounts for 10～96% of capsule total mass, and the capsule median size is 0.5 μ m～1mm, wall thickness 50nm～6 μ m.
In the above-mentioned capsule that contains LCM, the capsular core of described polythiol is preferably liquid polythiol and mixture of catalysts; The capsule wall material is melamine formaldehyde resin, poly(urea formaldehyde), polyureas, urethane, polyester, polymeric amide, polyacrylic ester or their modifier, what capsule-core accounted for the capsule total mass is 30～96%, the capsule median size is 0.5 μ m～1mm, wall thickness 50nm～6 μ m.
In the capsular core of above-mentioned polythiol, described polythiol is preferably methane two mercaptan, propane two mercaptan, hexanaphthene two mercaptan, 2,3-dimercaptosuccinic acid(DMSA)-2-mercaptoethyl ester, 2,3-dimercapto-1-propyl alcohol (2-mercaptoacetate), 1,2-dimercapto propyl group methyl ether, glycol ether two (2-mercaptoacetate), two (2-mercaptoethyl) ether, ethylene glycol dimercapto acetate, trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (mercaptopropionic acid ester), three thiol derivatives of the three-glycidyl ether of propoxylation alkane, tetramethylolmethane four (mercaptoacetate), tetramethylolmethane four (mercaptopropionic acid ester), dipentaerythritol many (thiopropionates), two, three, four sulfydryl benzene, two, three, four mercaptoalkyl benzene, dimercapto biphenyl, toluene two mercaptan and naphthyl disulfide alcohol, amino-4,6-two mercaptan-s-triazine, alkoxyl group-4,6-two mercaptan-s-triazine, aryloxy-4,6-two mercaptan-s-triazine, 1,3,5-three (tri-thiol propyl group) chlorinated isocyanurates, two, three, four (sulfydryl alkylthio) benzene, two, three, four (sulfydryl alkylthio) alkane, two (mercaptoalkyl) disulphide, hydroxyalkyl sulphur two (mercaptoacetate), hydroxyalkyl sulphur two (mercaptopropionic acid ester), mercaptoethyl ether two (mercaptopropionic acid ester), 1,4-dithian-2,5-glycol two (2-mercaptoalkyl ester), 4,4-Thiobutyric acid two (2-mercaptoalkyl ester), 3,4-two thiophene two mercaptan, bismuth mercaptan, 2,5-dimercapto-1,3, the 4-thiadiazoles, and trade mark is LP-33, ThioplastG-44 (Thioplast Chemicals GmbH ﹠amp; Co.KG), the alkane ether polythiol series derivates of CAPCURAE 3-800 (Germany Cognis GmbH Inc.).
In the capsular core of above-mentioned polythiol, described catalyzer is preferably tertiary amine, tertiary phosphine, contains the anionic quaternary amine of nucleophilic, contains phosphonium salt of anionic season of nucleophilic, imidazoles, contain arsenic salt or contain sulfonium salt of anionic season of nucleophilic of anionic season of nucleophilic.
In the catalyzer in the capsular core of above-mentioned polythiol, described tertiary amine is preferably methyldiethanolamine, trolamine, diethyl amino propylamine, between-xylylene two (dimethylamine), N, N '-lupetazin, N-crassitude, N-methyl hydroxy piperidine, N, N, N ', N '-tetramethyl-diaminoethanes, N, N, N ', N ', N '-five methyl diethylentriamine, Tributylamine, Trimethylamine, triethylenediamine, N-methylmorpholine, N-methyl piperidine or pyridine.
In the catalyzer in the capsular core of above-mentioned polythiol, described tertiary amine most preferably is 1,8-diazo bicyclic [5,4,0] 11 carbon-7-alkene, 1,8-diazabicyclo [2,2,2] octane, 4-dimethylaminopyridine, 4-(N-pyrrolidino) pyridine, triethylamine, benzyl dimethyl amine, the benzyl diethylamide, dimethylaminomethyl phenol, 2,6-two (dimethylaminomethyl) phenol or 2,4,6-three (dimethylaminomethyl) phenol.
In the catalyzer in the capsular core of above-mentioned polythiol, the described anionic quaternary ammonium salt of nucleophilic that contains is preferably TEA chloride, tetrapropyl ammonium acetate, hexyl trimethylammonium bromide, benzyl trimethyl ammonium cyanide, hexadecyl triethyl ammonium trinitride or N-picoline phenates.
In above-mentioned self-repairing fiber reinforced polymer matrix composite, described coupling agent is preferably silane coupling agent, chromium complex coupling agent, titanate coupling agent or zirconium class coupling agent.
The preparation method's of above-mentioned self-repairing fiber reinforced polymer matrix composite step is as follows: the capsule that will contain epoxy prepolymer joins in the resin matrix with the capsule that contains LCM, again matrix solidifying agent and catalyzer adding are wherein mixed, with gained impregnation mixture fiber reinforced material, under-50～250 ℃, be cured and after fixing.
In the preparation process of above-mentioned self-repair type matrix material, also can be by containing the Resins, epoxy and the unidirectional or braided fiber strongthener of the capsular resin compound infiltration of LCM of particle diameter less than 10 μ m, preparation prepreg or directly curing molding separately, then capsule can enter in the fibrous bundle, repairs fiber unsticking or rupture failure.
The damage rehabilitation method of above-mentioned self-repairing fiber reinforced polymer matrix composite is: material is positioned in-50～250 ℃ the environment, can repairs in the 24h.
The injury repairing principle of self-repairing fiber reinforced polymer matrix composite of the present invention is: when matrix material in processing, storage and use, be subjected to external force act on its inner produce tiny crack, fiber unsticking or fracture after, crackle passes capsule, make it to split simultaneously with matrix, under-50～250 ℃, discharge two kinds of reactive material of liquid-state epoxy resin and LCM, polymerization rapidly, thus stop crack growth, reparation crackle, fiber unsticking or fracture equivalent damage to destroy.
Compared with prior art, the present invention has following beneficial effect:
1. the present invention adopts the reparation system that epoxy resin micro-capsule and the Lewis acid that matches or polythiol solidifying agent microcapsule are formed, and the renovation agent component can be protected by the microcapsule parcel respectively; And physicals of renovation agent component own and stable chemical performance, have lower zero pour, viscosity is low, easily mobile, and vapour pressure is lower, be difficult in the capsule to exosmosis and volatilization standing storage or under severe condition such as higher temperatures, self-polymeric reaction can not take place.
2. the present invention is prepared into the microcapsule system with Resins, epoxy and Lewis acid or polythiol solidifying agent, can the control volume median size, physicals such as density is close, cyst material also can be similar, help their homodisperse in matrix, the renovation agent microcapsule can bear with body material, strongthener recombination process in the external force effect; Have good intermiscibility between the renovation agent component, help the phase mutual diffusion.
3. show high reaction activity and high after two kinds of microcapsule cores of the present invention are in contact with one another, can be under low temperature, normal temperature and high temperature fast setting; There are chemical action or stronger physical action after the renovation agent polyreaction and between matrix or fiber, can reach good bonding repairing effect.
4. the present invention wraps up and has bonding preferably between the microcapsule of renovation agent and body material, guarantees that capsule ftractures simultaneously with matrix in the crackle forming process.
5. adopt particle diameter to repair the system impregnation of fibers less than the capsule of 10 μ m, then capsule can enter between the fibrous bundle internal fiber space, repairs fibrous bundle internal fiber unsticking or fracture;
6. technical matters of the present invention is simple, and cost is low, and prepared fiber reinforced material possesses good self-healing properties keeping original mechanical property, improving on the basis of fracture toughness property.
Embodiment
Below further explain the present invention with regard to specific embodiment, but embodiment does not do any qualification to the present invention.
Embodiment 1
(capsule-core is the tetrahydrophthalic acid glycidyl ester to take by weighing 10g Resins, epoxy capsule, capsule-core content is 81%, median size 7.2 μ m) and 10g polythiol capsule (tetramethylolmethane four (mercaptopropionic acid ester), content 78%, benzyldimethylamine content 6%, (median size 6.9 μ m) evenly spread under 40～50 ℃ of conditions in 100g EPON 828 Resins, epoxy, add 2gKH-560,12.5g diethylenetriamine short mix, the degassing.Soak into 80g fiber reinforced material (C-glass fibre woven roving) with said mixture, the shop layer solidifies and the after fixing moulding.Curing and after fixing process are: room temperature 24h, 40 ℃ of 24h.
Adopt ultrasonic scanning (T-scan) test compound material to stand the remediation efficiency that the changing conditions of damaged area behind the drop impact is come evaluating material: (1.5J, matrix cracking are main collapse mode to adopt two kinds of representative different impact energys; 3.5J, fortifying fibre and matrix unsticking, part fibre breakage are main collapse mode), by ASTM D 3763-08 and D 7136/D7136M-07 standard matrix material is carried out impact fracture, except that immediately destroyed area being carried out the ultrasonic scanning test behind the de-chucking, calculate repairing preceding damaged area.To destroy sample then and after repairing different time under the differing temps, carry out the ultrasonic scanning test once more, and calculate and repair the back damaged area.Adopt formula: remediation efficiency=(damaged area before repairing-reparation back damaged area)/damaged area before repairing, calculate remediation efficiency.
Embodiment 2
(capsule-core is a bisphenol A diglycidyl ether to take by weighing 15g Resins, epoxy capsule, capsule-core content is 93%, median size 52 μ m) and 15g polythiol capsule (tetramethylolmethane four (mercaptopropionic acid ester), content 86%, 2,4,6-three (dimethylaminomethyl) phenol, content 8%, median size 49 μ m)), under 40～50 ℃ of conditions, evenly spread in 100g EPON 828 Resins, epoxy, add 1g KH-570,7g matrix solidifying agent (2-ethyl-4-methyl-imidazoles) short mix, the degassing.Soak into 65g fiber reinforced material (aramid fiber woven roving) with said mixture, the shop layer solidifies and the after fixing moulding.Curing and after fixing process are: 50 ℃ of 1h, 80 ℃ of 1h, 100 ℃ of 2h.
Evaluation method is with embodiment 1.
Embodiment 3
(capsule-core is a bisphenol A diglycidyl ether to take by weighing 10g Resins, epoxy capsule, capsule-core content is 93%, median size 52 μ m) and 5g Lewis acid capsule (boron trifluoride glycerine complex compound, capsule-core content 58%, median size 12 μ m), under 40～50 ℃ of conditions, evenly spread in 100g EPON 828 Resins, epoxy, add 1g KH-570,20g matrix solidifying agent (affixture of tetraethylene pentamine and vinyl cyanide) short mix, the degassing.Soak into 40g fiber reinforced material (E-glass fibre woven roving) with said mixture, the shop layer solidifies and the after fixing moulding.Curing and after fixing process are: 120 ℃ of 1h, 160 ℃ of 1h, 180 ℃ of 1h.
Evaluation method is with embodiment 1.
Embodiment 4
(capsule-core is that methylol dihydroxyphenyl propane and Resorcinol glycidyl ether mass ratio are 1: 1 mixture to take by weighing 10g Resins, epoxy capsule, capsule-core content is 81%, median size 6.7 μ m) and 5g Lewis acid capsule (boron trifluoride ethyl ether complex, capsule-core content 53%, median size 7.5 μ m), under 40～50 ℃ of conditions, evenly spread in 100g EPON 828 Resins, epoxy, add 1g KH-570,20g matrix solidifying agent (affixture of tetraethylene pentamine and vinyl cyanide) short mix, the degassing.Soak into 70g E-glass fibre unidirectional cloth, preparation prepreg with said mixture.Further adopt the matrix resin mixture that contains two kinds of capsule reparation systems among the embodiment 2 to fill above-mentioned prepreg gap, the shop layer solidifies and the after fixing moulding.Curing and after fixing process are: 60 ℃ of 2h, 80 ℃ of 2h, 120 ℃ of 2h.
Evaluation method is with embodiment 1.
Embodiment 5
Adopt unsaturated polyester as matrix resin, with 60g unsaturated polyester, 24g vinylbenzene, 1.2g methylethyl ketone peroxide, mix with the renovation agent capsule among the embodiment 1, add the 0.5g cobalt naphthenate at last, other component, preparation process and evaluation method are with embodiment 1.
Embodiment 6
Lewis acid capsule among the embodiment 1 changed into contain 2 of 72% trimethylolpropane tris (mercaptoacetate) and 4%, 4, the solidifying agent capsule of 6-three (dimethylaminomethyl) phenol, median size 5.3 μ m, other component, preparation process and evaluation method are with embodiment 1.
Embodiment 7
Lewis acid capsule among the embodiment 3 changed into contain 68% boron trifluoride polyoxyethylene glycol complex compound, the solidifying agent capsule of median size 26 μ m, other component, preparation process and evaluation method are with embodiment 3.
Embodiment 8
Change the strongthener among the embodiment 1 into E-glass fibre unidirectional cloth, other component, preparation process and evaluation method are with embodiment 1.
Embodiment 9
Change the strongthener among the embodiment 3 into T300 carbon fiber woven roving, other component, preparation process and evaluation method are with embodiment 2.
Embodiment 10
Change the strongthener among the embodiment 3 into T300 carbon fiber one-way cloth, other component, preparation process and evaluation method are with embodiment 2.
Comparative Examples 1
Adopt the pure matrix resin that does not contain renovation agent to soak into fiber reinforced material, other component, preparation process and evaluation method are with embodiment 1.
Comparative Examples 2
Take by weighing 20g Resins, epoxy capsule (capsule-core is the tetrahydrophthalic acid glycidyl ester, and capsule-core content is 81%, median size 7.2 μ m) and, do not add the curing agent capsules as renovation agent.Other component, preparation process and evaluation method are with embodiment 1
Comparative Examples 3
Take by weighing 20g polythiol capsule (tetramethylolmethane four (mercaptopropionic acid ester), capsule-core content 78%, benzyldimethylamine content 6%, median size 6.9 μ m) and, do not add the Resins, epoxy capsule as renovation agent.Other component, preparation process and evaluation method are with embodiment 1.
Comparative Examples 4
Take by weighing 15g Resins, epoxy capsule (capsule-core is a bisphenol A diglycidyl ether, and capsule-core content is 93%, median size 52 μ m) and, do not add the curing agent capsules as renovation agent.Other component, preparation process and evaluation method are with embodiment 2.
Comparative Examples 5
Take by weighing 15g Lewis acid capsule (boron trifluoride glycerine complex compound, capsule-core content 58%, median size 12 μ m) and, do not add the Resins, epoxy capsule as renovation agent.Other component, preparation process and evaluation method are with embodiment 2.
The remediation efficiency of embodiment and Comparative Examples sees Table 1.
Table 1 self-repairing fiber reinforced polymer matrix composite remediation efficiency
Indicate: test and repairing condition comprise impact energy 1.5 or 3.5J, reparation temperature-50～250 ℃, time 1min～24h.
Claims (10)
1. self-repairing fiber reinforced polymer matrix composite, form by the following component of meter by weight:
(1) polymeric matrix, 30～90 parts;
(2) fiber reinforced material, 5～70 parts;
(3) contain the capsule of liquid-state epoxy resin prepolymer, 1～30 part;
(4) contain the capsule of LCM, 1～30 part;
(5) coupling agent, 0.1～5 part.
2. self-repairing fiber reinforced polymer matrix composite as claimed in claim 1 is characterized in that described polymeric matrix is Resins, epoxy, unsaturated polyester, resol, urethane, polymeric amide or polyacrylic resin.
3. self-repairing fiber reinforced polymer matrix composite as claimed in claim 1 is characterized in that described fiber reinforced material is glass fibre, carbon fiber, aramid fiber, silicon carbide fiber, sapphire whisker, boron fibre, whisker fibre, glass fibre, the short fabric of cutting felt, continuous felt, winding yarn or carbon fiber and aramid fiber braiding.
4. self-repairing fiber reinforced polymer matrix composite as claimed in claim 1, it is characterized in that the described capsular core that contains the liquid-state epoxy resin prepolymer is a Resins, epoxy, the capsule wall material is urethane, polyester, polymeric amide, polyacrylic ester, polyureas, poly(urea formaldehyde), melamine formaldehyde resin or their modifier; Capsule-core accounts for 40～98% of capsule total mass, and the capsule median size is 0.5 μ m～1mm, wall thickness 50nm～10 μ m.
5. self-repairing fiber reinforced polymer matrix composite as claimed in claim 1 is characterized in that the described capsule that contains LCM is Lewis acid capsule or polythiol capsule.
6. self-repairing fiber reinforced polymer matrix composite as claimed in claim 5, it is characterized in that the capsular core of described Lewis acid is: boron trifluoride, boron trichloride, aluminum chloride, iron trichloride, ferric bromide, tin tetrachloride, titanium tetrachloride, zirconium tetrachloride, antimony pentachloride, the dichloride beryllium, the mixture of one or more in the zinc dichloride, and aforesaid compound and ether, glycerine, tetrahydrofuran (THF), in the polyoxyethylene glycol any one or multiple formed complex compound, and hexafluoro arsenate, hexafluoro antimonate, hexa chloro-antimonate, the tetrachloro aluminate, the pentachloro-stannate, the mixture of one or more in the pentachloro-titanate; The capsule wall material is melamine formaldehyde resin, poly(urea formaldehyde), polyureas, urethane, polyester, polymeric amide, polyacrylic ester or their modifier, and the sorptive material that contains vesicular structure through the inside of embedding encapsulation; Capsule-core accounts for 10～96% of capsule total mass, and the capsule median size is 0.5 μ m～1mm, wall thickness 50nm～6 μ m.
7. self-repairing fiber reinforced polymer matrix composite as claimed in claim 5 is characterized in that the capsular core of described polythiol is liquid polythiol and mixture of catalysts; The capsule wall material is melamine formaldehyde resin, poly(urea formaldehyde), polyureas, urethane, polyester, polymeric amide, polyacrylic ester or their modifier, what capsule-core accounted for the capsule total mass is 30～96%, the capsule median size is 0.5 μ m～1mm, wall thickness 50nm～6 μ m.
8. self-repairing fiber reinforced polymer matrix composite as claimed in claim 1 is characterized in that described coupling agent is silane coupling agent, chromium complex coupling agent, titanate coupling agent or zirconium class coupling agent.
9. the preparation method of the described self-repairing fiber reinforced polymer matrix composite of claim 1, it is characterized in that comprising the steps: that the capsule with containing epoxy prepolymer joins in the resin matrix with the capsule that contains LCM, again matrix solidifying agent and catalyzer adding are wherein mixed, with gained impregnation mixture fiber reinforced material, under-50～250 ℃, be cured and after fixing; Perhaps adopt and contain Resins, epoxy and LCM capsular resin compound the dipping unidirectional or braided fiber strongthener of particle diameter, prepare prepreg or direct curing molding separately less than 10 μ m.
10. the damage rehabilitation method of self-repairing fiber reinforced polymer matrix composite as claimed in claim 1 is characterized in that comprising the steps: material is positioned in-50～250 ℃ the environment, can repair in the 24h.
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Cited By (37)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102010523A (en) * | 2010-10-22 | 2011-04-13 | 广东新粤建材有限公司 | Latent curing agent and preparation method thereof |
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