CN115505260A - Composite material part, lightning protection structural part thereof, preparation method and application - Google Patents
Composite material part, lightning protection structural part thereof, preparation method and application Download PDFInfo
- Publication number
- CN115505260A CN115505260A CN202211164751.8A CN202211164751A CN115505260A CN 115505260 A CN115505260 A CN 115505260A CN 202211164751 A CN202211164751 A CN 202211164751A CN 115505260 A CN115505260 A CN 115505260A
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- CN
- China
- Prior art keywords
- composite material
- inorganic fiber
- fiber membrane
- micro
- resin
- 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.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 184
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000012784 inorganic fiber Substances 0.000 claims abstract description 189
- 239000012528 membrane Substances 0.000 claims abstract description 159
- 239000002245 particle Substances 0.000 claims abstract description 145
- 238000002679 ablation Methods 0.000 claims abstract description 104
- 239000000835 fiber Substances 0.000 claims abstract description 91
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 37
- 239000004917 carbon fiber Substances 0.000 claims abstract description 37
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims description 139
- 239000011347 resin Substances 0.000 claims description 139
- 239000010410 layer Substances 0.000 claims description 74
- 239000003795 chemical substances by application Substances 0.000 claims description 66
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 63
- 239000004643 cyanate ester Substances 0.000 claims description 55
- 239000004005 microsphere Substances 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 44
- 239000010453 quartz Substances 0.000 claims description 39
- 239000002238 carbon nanotube film Substances 0.000 claims description 34
- 239000011259 mixed solution Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 238000002955 isolation Methods 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 239000004964 aerogel Substances 0.000 claims description 16
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 15
- 239000012745 toughening agent Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 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 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 12
- 239000004695 Polyether sulfone Substances 0.000 claims description 12
- 229920006393 polyether sulfone Polymers 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000001913 cyanates Chemical class 0.000 claims description 10
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 239000003822 epoxy resin Substances 0.000 claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 9
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 9
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 8
- 229920002748 Basalt fiber Polymers 0.000 claims description 8
- 239000004642 Polyimide Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229920001721 polyimide Polymers 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 claims description 6
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229920000459 Nitrile rubber Polymers 0.000 claims description 6
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 6
- VNZQQAVATKSIBR-UHFFFAOYSA-L copper;octanoate Chemical compound [Cu+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O VNZQQAVATKSIBR-UHFFFAOYSA-L 0.000 claims description 6
- UKRVECBFDMVBPU-UHFFFAOYSA-N ethyl 3-oxoheptanoate Chemical compound CCCCC(=O)CC(=O)OCC UKRVECBFDMVBPU-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229920002050 silicone resin Polymers 0.000 claims description 6
- 150000003512 tertiary amines Chemical class 0.000 claims description 6
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 claims description 6
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- RXKXNTWILAIQBI-UHFFFAOYSA-L C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].C(CCC)[Co+2]CCCC Chemical compound C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].C(CCC)[Co+2]CCCC RXKXNTWILAIQBI-UHFFFAOYSA-L 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 239000010881 fly ash Substances 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- YHDKKRANKSHQQT-UHFFFAOYSA-N C(CCCCCCCCCCC)(=O)O.C(CCCCCCCCCCC)(=O)O.C(CCC)[Cu]CCCC Chemical compound C(CCCCCCCCCCC)(=O)O.C(CCCCCCCCCCC)(=O)O.C(CCC)[Cu]CCCC YHDKKRANKSHQQT-UHFFFAOYSA-N 0.000 claims description 3
- DZBANPFAPFSAJJ-UHFFFAOYSA-N CCCC[Zn]CCCC.CCCCCCCCCCCC(O)=O.CCCCCCCCCCCC(O)=O Chemical compound CCCC[Zn]CCCC.CCCCCCCCCCCC(O)=O.CCCCCCCCCCCC(O)=O DZBANPFAPFSAJJ-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004944 Liquid Silicone Rubber Substances 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001940 conductive polymer Polymers 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000007766 curtain coating Methods 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 229920001225 polyester resin Polymers 0.000 claims description 3
- 239000004645 polyester resin Substances 0.000 claims description 3
- 229920001955 polyphenylene ether Polymers 0.000 claims description 3
- 229920001021 polysulfide Polymers 0.000 claims description 3
- 239000005077 polysulfide Substances 0.000 claims description 3
- 150000008117 polysulfides Polymers 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
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- 239000002356 single layer Substances 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 2
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 claims description 2
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
- B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
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- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/047—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material made of fibres or filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
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Abstract
The invention provides an inorganic fiber membrane/micro-nano hollow particle composite material part, a lightning protection structural member thereof, a preparation method and application thereof. The insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material workpiece provided by the invention has good compatibility with composite materials, and has the characteristics of excellent insulation, heat insulation, ablation resistance, toughness and the like after curing and forming. The insulating heat-insulating ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part is arranged between the composite material and the conductive film, the effect of current injection to the composite material is isolated, meanwhile, the ablation-resistant effect based on the insulating heat-insulating ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part is realized, the ablation is resisted within a short time when the part is subjected to lightning impact, meanwhile, the excellent heat-insulating property of the part can also avoid the heat from being transferred downwards to a carbon fiber composite material region to cause the damage of the carbon fiber composite material region, in addition, the whole mechanical property of the lightning protection part can be enhanced by the fiber membrane part with regular orientation, so that the lightning protection effect of the conductive film is integrally and greatly improved, and the effects of weight reduction, cost reduction and the like are realized.
Description
Technical Field
The invention belongs to the field of composite material lightning protection, and particularly relates to an inorganic fiber membrane/micro-nano hollow particle composite material part, a lightning protection structural member thereof, a preparation method and application thereof.
Background
The fiber reinforced resin matrix composite material has the characteristics of light weight, high specific strength and specific modulus, corrosion resistance, fatigue resistance, strong designability and the like, and is widely used in aerospace aircrafts, wind power generation blades and the like. Compared with metal materials, the fiber composite material has weak conductivity and anisotropy, and when the composite material member is struck by lightning, the composite material member is difficult to conduct away gathered current in a short time, so that a large amount of joule heat is generated locally and instantly, the composite material is seriously ablated or generates a layering phenomenon, even generates fracture, normal use is influenced, and safety is threatened.
At present, the main solution of lightning protection of composite materials is to add a conductive functional layer on the surface of the composite material, including adhering or embedding a metal mesh or a metal foil on the surface, spraying an aluminum coating on the surface, and the like. The introduction of the conductive functional layer can lead away static charges generated by the friction of the surface of the composite material or strong current injected by lightning in time, thereby reducing the damage to the aircraft. However, the introduction of metals also brings about problems of (1) high metal density and heavy weight; (2) Metal is easy to generate electrochemical corrosion, and an insulating layer needs to be additionally introduced; (3) The compatibility of metal and resin is poor, the metal is easy to delaminate, the roughness of the metal surface is large, and the resin is needed to be added and supplemented; (4) The process for adding the conductive function layer is complex, and higher cost is caused.
At present, most researchers are researching new light conductive materials to replace the existing metal materials to achieve the lightning protection effect. In recent years, the light conductive nano carbon material is reported to be adopted to enhance the conductivity of the composite material, and the method is mainly realized by the following modes: (1) High-conductivity carbon nano-materials such as carbon nano-tubes, graphene and the like are doped in the resin matrix, so that the conductivity of the resin is improved; (2) Depositing the high-conductivity nano carbon material on the surface of the carbon fiber to reduce the contact resistance between the fibers; (3) The high-conductivity nano carbon material is prepared into a light conductive film to be adhered to the surface of the composite material. Due to the size effect, the nano carbon material is easy to agglomerate, so that the prepared composite material has anisotropy, poor conductivity and mechanical property, and is difficult to repair after being damaged by lightning impact, and compared with the two methods, the light conductive film is more suitable for practical application by being adhered to the surface of the composite material.
There are few cases where weight reduction of lightning protection structures is achieved by the design of insulating barriers. This is because the recognition of the role of the insulating barrier layer remains that it only acts as an insulating against electrochemical corrosion, and it is believed that the lightning protection effect is contributed only by the conductive layer, so that only thicker and heavier conductive layers can be used. The prior art provides an insulating heat-conducting ablation-resistant adhesive and an application thereof in lightning protection, and the insulating heat-conducting ablation-resistant adhesive with a certain thickness is used for preventing current from being conducted to a continuous carbon fiber laminated composite material part when a conductive film is adhered to the surface of the continuous carbon fiber laminated composite material part, and the heat is conducted away by utilizing the heat conductivity of the conductive film, so that the lightning protection effect of the conductive film is improved. However, the filler is easy to agglomerate, and the performance of the composite material of the isolation layer is reduced due to disordered orientation, so that the lightning protection effect is influenced; in addition, the required conductive layer is heavy and costly. More importantly, in the prior art, understanding and research on the action mechanism of the insulating layer for lightning protection are not sufficient, and the important significance of good thermal insulation performance (rather than good thermal conductivity) and mechanical enhancement property of the insulating layer on improving the lightning protection effect is not recognized.
Disclosure of Invention
Therefore, the invention aims to overcome the defects in the prior art and provide an inorganic fiber membrane/micro-nano hollow particle composite material part, a lightning protection structural member thereof, a preparation method and application thereof, which can be used for improving the lightning protection effect of the surface of the composite material.
In order to achieve the above object, a first aspect of the present invention provides an inorganic fiber membrane/micro-nano hollow particle composite material part, which includes a mixture of a high temperature resistant resin, a curing agent and micro-nano hollow particles, and an inorganic fiber membrane skeleton, wherein:
the inorganic fiber membrane/micro-nano hollow particle composite material part is preferably layered, and the thickness of the inorganic fiber membrane/micro-nano hollow particle composite material part is more than 10 micrometers, preferably 30-400 micrometers, and more preferably 50-400 micrometers.
According to the first aspect of the invention, the inorganic fiber membrane/micro-nano hollow particle composite material part is provided, wherein,
the high-temperature resistant resin is selected from one or more of the following: cyanate ester resin, phenolic resin, bismaleimide resin, organic silicon resin, modified epoxy resin, modified cyanate ester resin, modified phenolic resin and modified bismaleimide resin, preferably selected from one or more of the following: cyanate ester resin, phenolic resin, silicone resin, modified epoxy resin, modified cyanate ester resin, modified phenolic resin, modified polyester resin, modified silicone resin, bismaleimide resin, more preferably selected from one or more of the following: cyanate ester resin, modified epoxy resin, modified cyanate ester resin, bismaleimide resin;
the curing agent is selected from: imidazole curing agents and/or amine curing agents; preferably selected from one or more of the following: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, ethylenediamine, diethylenetriamine, triethylenetetramine, diaminodiphenylalum (DDS), diaminodiphenylmethane (DDM), 4,4 diaminodiphenylmethane (DDM), 4,4 diaminodiphenylether (DDE), 4,4 diaminodiphenylalum (DDS), m-phenylenediamine (m-PDA), polyetheramine D-230, more preferably selected from one or more of: 2-methylimidazole, 2-ethyl-4-methylimidazole, polyetheramine D-230;
the micro-nano hollow particles are selected from one or more of the following: aerogel, hollow alumina microspheres, hollow glass microspheres, hollow silica microspheres, hollow ceramic microspheres, hollow titanium dioxide microspheres, hollow fly ash microspheres, hollow zirconium dioxide microspheres, and/or hollow carbon microspheres, preferably selected from one or more of the following: aerogel, hollow alumina microspheres, hollow silica microspheres, hollow ceramic microspheres, hollow titanium dioxide microspheres, hollow fly ash microspheres, hollow zirconium dioxide microspheres and/or hollow carbon microspheres; more preferably one or more selected from the group consisting of: aerogels, hollow alumina microspheres, and/or hollow silica microspheres; and/or
The inorganic fiber membrane skeleton is selected from one or more of the following: unidirectional films, laminated films and woven films with regular orientation, and most preferably continuous fiber woven films with regular orientation;
preferably, the inorganic fiber membrane/micro-nano hollow particle composite material part further comprises a processing aid;
more preferably, the processing aids include accelerators, catalysts and/or tougheners; the accelerator is further preferably selected from one or more of the following: tertiary amine, methyldiethanolamine and/or aminophenol, more preferably tertiary amine or aminophenol; the catalyst is further preferably selected from one or more of the following: dibutyl cobalt dilaurate, dibutyl zinc dilaurate, dibutyl copper dilaurate, zinc octoate, manganese octoate, copper octoate, cobalt acetylacetonate, zinc acetylacetonate, manganese acetylacetonate, more preferably selected from one or more of the following: zinc octoate, manganese octoate, copper octoate, cobalt acetylacetonate, zinc acetylacetonate, manganese acetylacetonate; and/or the toughening agent is further preferably selected from one or more of the following: polyether sulfone, polyimide, carboxylated nitrile rubber, liquid nitrile rubber, polyvinyl butyral, polyether sulfone, polyphenylene ether ketone, polysulfide rubber, liquid silicone rubber, polyether sulfone, and more preferably polyether sulfone or polyimide.
According to the first aspect of the invention, the inorganic fiber membrane/micro-nano hollow particle composite material part is formed by a first step,
the mass parts of the high-temperature resistant resin, the curing agent, the micro-nano hollow particles and the inorganic fiber membrane skeleton are 3-90;
preferably, when the inorganic fiber membrane/micro-nano hollow particle composite material product comprises a processing aid, the mass parts of the high-temperature resistant resin, the curing agent, the processing aid, the micro-nano hollow particles and the inorganic fiber membrane skeleton are 3-90;
more preferably, in the processing aid, the mass parts ratio of the accelerator, the catalyst and the flexibilizer is (0-1:0-0.2).
According to the first aspect of the invention, the inorganic fiber membrane/micro-nano hollow particle composite material part is characterized in that the fiber units contained in the inorganic fiber membrane skeleton are insulating, heat-insulating and ablation-resistant continuous fibers, and the length of the continuous fibers is continuous in the inorganic fiber membrane/micro-nano hollow particle composite material part; wherein, the first and the second end of the pipe are connected with each other,
the length of the continuous fibers is greater than 1mm, preferably greater than 1cm, more preferably greater than 30cm;
preferably, the mass fraction of the inorganic fiber membrane in the inorganic fiber membrane/micro-nano hollow particle composite material part is 40-70%, preferably 50-70%, and most preferably 60%; and/or
Preferably, the inorganic fiber membrane in the inorganic fiber membrane/micro-nano hollow particle composite material part is selected from one or more of the following: quartz fibers, glass fibers, ceramic fibers, basalt fibers, alumina fibers, zinc oxide fibers, silicon nitride fibers, aluminum silicate fibers, boron fibers, more preferably selected from one or more of the following: quartz fibers, glass fibers, alumina fibers, zinc oxide fibers, basalt fibers, aluminum silicate fibers, boron fibers; further preferred is one or more selected from the group consisting of: quartz fibers, glass fibers, alumina fibers, zinc oxide fibers, basalt fibers.
A second aspect of the present invention provides a method for preparing the inorganic fiber membrane/micro-nano hollow particle composite material part according to the first aspect, wherein the method comprises: mixing high-temperature resin, a curing agent and micro-nano hollow particles and uniformly dispersing the mixture to obtain a mixed solution, then impregnating the mixed solution with an inorganic fiber membrane framework, or coating the mixed solution on the inorganic fiber membrane framework, and curing and drying at room temperature or under a heating condition to obtain an inorganic fiber membrane/micro-nano hollow particle composite material workpiece;
preferably, the method for coating the mixed solution on the inorganic fiber membrane skeleton is selected from one or more of the following methods: spraying, blade coating and curtain coating;
preferably, the mass ratio of the high-temperature resin, the curing agent and the micro-nano hollow particle mixture is 5-95: 1 to 25:1 to 10, more preferably 20 to 60:1 to 20:1 to 9, more preferably 35 to 45:1 to 15:1 to 8; and/or
Preferably, the mass ratio of the mixed solution to the inorganic fiber membrane skeleton is 5-95: 5 to 95, more preferably 20 to 60, and still more preferably 35 to 45:55 to 65.
The third aspect of the present invention provides a method for preparing the inorganic fiber membrane/micro-nano hollow particle composite material part of the first aspect, wherein the method comprises: melting high-temperature resin, adding a curing agent and micro-nano hollow particles into the high-temperature resin, mixing to obtain a mixed solution containing the molten resin, directly soaking an inorganic fiber membrane framework in a mixed solution glue tank containing the molten resin, drying and rolling to obtain an inorganic fiber membrane/micro-nano hollow particle composite material workpiece;
preferably, the mass ratio of the mixed solution containing the molten resin to the inorganic fiber membrane skeleton is 5 to 95:5 to 95, more preferably 20 to 60, and still more preferably 35 to 45:55 to 65.
The fourth aspect of the present invention provides a method for preparing the inorganic fiber membrane/micro-nano hollow particle composite material part of the first aspect, wherein the method comprises: melting high-temperature resin, adding a curing agent and micro-nano hollow particles into the high-temperature resin for mixing to obtain a mixed solution containing the molten resin, uniformly coating the mixed solution containing the molten resin on a molding machine to prepare a film, overlapping the film with an inorganic fiber film framework for high-temperature treatment, and rolling to obtain an inorganic fiber film/micro-nano hollow particle composite material part;
preferably, the mass ratio of the mixed solution containing the molten resin to the inorganic fiber membrane skeleton is 5 to 95:5 to 95, more preferably 20 to 60, and still more preferably 35 to 45:55 to 65.
A fifth aspect of the present invention provides a lightning protection structural member, which includes, sequentially from top to bottom:
a conductive layer;
an isolation layer; and
a continuous carbon fiber composite layer;
wherein the isolation layer is the inorganic fiber membrane/micro-nano hollow particle composite material product of the first aspect or the inorganic fiber membrane/micro-nano hollow particle composite material product prepared by the method of the second aspect, the third aspect or the fourth aspect;
preferably, the conductive layer is a conductive film, and the material of the conductive film is selected from one or more of the following materials: copper, nickel, aluminum, conductive metal oxides, conductive polymers, metal-modified nanocarbon materials, light conductive nanocarbon materials, and more preferably light conductive nanocarbon materials;
further preferably, the light conductive nanocarbon material is selected from one or more of the following: the film comprises a super-ordered carbon nanotube film, bucky paper, a graphene film and a graphene oxide film, and the most preferable is the super-ordered carbon nanotube film;
still further preferably, the super-aligned carbon nanotube film changes the conductivity of the entire film by adjusting the orientation of the carbon nanotubes in the carbon nanotube film, wherein the orientation of the super-aligned carbon nanotube film is arranged between the single-layer carbon nanotube layers along 0 to 90 °, and most preferably along 90 °.
The lightning protection structure according to the fifth aspect of the invention, wherein,
the thickness of the conductive layer is not less than 30nm, preferably not less than 1 μm, and more preferably not less than 15 μm;
the conductive layer has an areal density of not more than 30g/m 2 Preferably not more than 25g/m 2 More preferably not more than 20g/m 2 ；
The conductivity of the conductive layer is 10 4 ～10 8 S/m；
The surface density of the isolation layer is 10-200g/m 2 Preferably 20 to 180g/m 2 More preferably 30 to 150g/m 2 (ii) a And/or
The thickness of the isolation layer is greater than 10 μm, preferably 30 to 400 μm, more preferably 50 to 400 μm, and most preferably 200 μm.
A sixth aspect of the invention provides an application of the inorganic fiber membrane/micro-nano hollow particle composite material part according to the first aspect or the lightning protection structure part according to the fifth aspect in preparing a lightning protection product;
preferably, the lightning protection product is an aircraft fuselage surface product, a wind turbine blade structure surface product, an urban railway traffic surface product.
According to a specific embodiment of the present invention, aiming at the problems in the prior art, the object of the present invention is to provide an application of an article containing insulating, heat-insulating, ablation-resistant inorganic fiber membranes/micro-nano hollow particles in lightning protection, wherein the insulating, heat-insulating, ablation-resistant inorganic fiber membranes/micro-nano hollow particles are oriented unidirectional membranes, laminated membranes or woven membranes, and the fiber units of the article are insulating, heat-insulating, ablation-resistant continuous fibers (length >1 mm). The composite material is placed between a carbon fiber composite material and a conductive film, the effect of current injection to the composite material is isolated, meanwhile, the ablation resistance effect based on an insulation and heat insulation ablation-resistant inorganic fiber film/micro-nano hollow particle composite material part is resistant to ablation in a short time when the composite material part is subjected to lightning impact, meanwhile, the excellent heat insulation performance of the composite material part can also prevent heat from being transmitted downwards to a carbon fiber composite material region to damage the composite material region, in addition, the whole mechanical property of a lightning protection part can be enhanced by the inorganic fiber film part with regular orientation, the micro-nano hollow particles and the inorganic fiber film are used simultaneously, the lightning protection effect of the conductive film is integrally and greatly improved, and the effects of reducing weight, reducing cost and the like are achieved.
The invention is realized by the following technical scheme:
in a first aspect, the invention provides an insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part, which has the advantages of high insulation, high ablation temperature resistance, high heat insulation, uniform part, large-scale preparation and the like, and can be used in the field of lightning protection.
In the invention, the insulating heat-insulating ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material workpiece is prepared from the following components in percentage by mass: the mass ratio of the high-temperature-resistant resin, the curing agent, the insulating heat-insulating ablation-resistant micro-nano hollow particle mixture to the insulating heat-insulating ablation-resistant inorganic fiber membrane skeleton is as follows: 5 to 95:5 to 95.
Preferably, the mass fraction of the insulating and ablation-resistant inorganic fibers is 40% to 70%, for example, 40%, 45%, 50%, 60%, 65%, 70%, preferably 60%.
Preferably, the insulating, heat-insulating and ablation-resistant inorganic fibers are any one or more of quartz fibers, glass fibers, ceramic fibers, basalt fibers, alumina fibers, zinc oxide fibers, silicon nitride fibers, aluminum silicate fibers and boron fibers.
Preferably, the insulating, heat-insulating and ablation-resistant inorganic fibers are any one or more of glass fibers, quartz fibers, alumina fibers, zinc oxide fibers and basalt fibers.
Preferably, the inorganic fiber membrane skeleton structure is a unidirectional membrane with regular orientation, a laminated membrane or a woven membrane, and preferably, the inorganic fiber membrane skeleton structure is a continuous fiber woven membrane with regular orientation.
Preferably, the length of the insulating, heat insulating, ablation resistant inorganic fibers is continuous throughout the fibrous membrane article.
Preferably, the high-temperature resistant resin is cyanate ester resin, phenolic resin, bismaleimide resin, organic silicon resin, modified epoxy resin, modified cyanate ester resin, modified phenolic resin, modified bismaleimide resin, preferably selected from one or more of the following: cyanate ester resin, phenolic resin, silicone resin, modified epoxy resin, modified cyanate ester resin, modified phenolic resin, modified polyester resin, modified silicone resin, bismaleimide resin; more preferably selected from one or more of the following: any one or more of cyanate resin, modified epoxy resin, modified cyanate resin and bismaleimide resin.
Preferably, the curing agent accounts for 1-25% of the total mass of the insulating and ablation-resistant inorganic fiber part, and can be 1%, 5%, 10%, 15%, 20% and 25% for example.
Preferably, the raw material of the inorganic fiber membrane/micro-nano hollow particle composite material workpiece also comprises 0-5% of processing aid;
preferably, the processing aid comprises an accelerator, a catalyst and/or a toughening agent.
Preferably, the accelerator is further selected from one or more of the following: tertiary amines, methyldiethanolamine and/or aminophenols, even more preferably selected from one or more of: tertiary amines, aminophenols;
preferably, the catalyst is further selected from one or more of the following: transition metal organic compounds such as dibutyl cobalt dilaurate, dibutyl zinc dilaurate, dibutyl copper dilaurate, zinc octoate, manganese octoate, copper octoate, cobalt acetylacetonate, zinc acetylacetonate, manganese acetylacetonate, and the like, more preferably selected from one or more of the following: zinc octoate, manganese octoate, copper octoate, cobalt acetylacetonate, zinc acetylacetonate, manganese acetylacetonate, and/or;
preferably, the toughening agent is selected from one or more of: polyether sulfone, polyimide, carboxylated nitrile rubber, liquid nitrile rubber, polyvinyl butyral, polyether sulfone, polyphenylene ether ketone, polysulfide rubber, liquid silicone rubber, polyether sulfone, and more preferably polyether sulfone, or polyimide.
Preferably, the curing agent accounts for 0-3% of the total mass of the insulating and ablation-resistant inorganic fiber product, and can be 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, and preferably 2%.
Preferably, the insulating and heat-insulating micro-nano mixture accounts for 1-10% of the total mass of the insulating and heat-insulating ablation-resistant inorganic fiber product, and may be, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%.
Preferably, the insulating and heat-insulating micro-nano mixture comprises one or more of aerogel, hollow glass microsphere, hollow silica microsphere, hollow ceramic microsphere, hollow titanium dioxide microsphere, hollow zirconium dioxide microsphere, hollow carbon microsphere and hollow fly ash microsphere, wherein the aerogel accounts for 0.5-3% of the total mass of the prepreg, and may be, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, and preferably 2%. Preferably, the high-temperature-resistant resin, the curing agent, the micro-nano hollow particles and the insulating, heat-insulating and ablation-resistant inorganic fiber membrane can be mixed in any mode, and the resin, the curing agent and the micro-nano hollow particles are uniformly dispersed in the insulating, heat-insulating and ablation-resistant inorganic fiber membrane. The insulating, heat-insulating and ablation-resistant inorganic fiber membrane, the high-temperature-resistant resin, the curing agent and the micro-nano hollow particles can be pre-cured into a prepreg or prepared into the prepreg on a large scale for later use.
Preferably, the method for preparing the prepreg by using the insulating, heat-insulating and ablation-resistant inorganic fibers, the high-temperature-resistant resin and the curing agent comprises the following steps:
(1) The preparation method comprises the steps of mixing the components according to the formula, dissolving a resin matrix in a diluent solvent to form a solution, adding micro-nano hollow particles, a curing agent and a processing aid to mix, then impregnating the resin solution with insulating, heat-insulating and ablation-resistant inorganic fibers at a certain impregnation speed (1-10 m/min), controlling the content of resin by using a metering roller, then drying the prepreg by using an oven, volatilizing the solvent with a low boiling point, and finally winding the prepreg.
(2) Melting resin at high temperature, adding micro-nano hollow particles, a curing agent and a processing aid, uniformly mixing, directly dipping the insulating, heat-insulating and ablation-resistant inorganic fibers in a glue tank containing the molten resin, and then drying and rolling.
(3) Melting resin at high temperature, adding micro-nano hollow particles, uniformly mixing a curing agent and a processing aid, uniformly coating the melted resin on release paper on a film making machine to prepare a film, then laminating the film with insulating heat-insulating ablation-resistant inorganic fibers, performing high-temperature treatment, and finally rolling.
Preferably, the method for pre-curing the insulating, heat-insulating and ablation-resistant inorganic fiber film, the high-temperature-resistant resin, the curing agent and the micro-nano hollow particles into the prepreg comprises the following steps: mixing high-temperature-resistant resin, a curing agent and micro-nano hollow particles, uniformly dispersing the mixture, spraying, blade coating, curtain coating or brushing the mixed solution on an inorganic fiber membrane framework, and curing and drying at room temperature or under a heating condition to obtain a prepreg, namely the inorganic fiber membrane/micro-nano hollow particle composite material product.
Preferably, the prepreg prefabricated by the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particles, the high-temperature-resistant resin and the curing agent has certain mechanical strength and viscosity, and can be stably stored at room temperature and low temperature. According to the difference of resin and curing agent, the resin can be cured and formed into a finished piece, the pressure of the common resin system is 1 MPa-10 MPa, and the temperature is 80-150 ℃.
Preferably, the size of the prepreg prepared by the insulating, heat-insulating and ablation-resistant inorganic fiber film/micro-nano hollow particles, the high-temperature-resistant resin and the curing agent is as follows: the width is (100-1000) mm, and the length can reach 100m.
In a second aspect, the invention provides an application method of the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part in the lightning protection field.
In the invention, the method for applying the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part to the lightning protection part comprises the following steps: the parts are respectively as follows from top to bottom: a conductive film serving as a conductive layer; an insulating heat-insulating ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material workpiece serving as an isolation layer; a continuous carbon fiber laminated composite material.
Preferably, the conductive film is made of any one or more of copper, nickel, aluminum, conductive metal oxide, conductive polymer, metal-modified nano-carbon material and light conductive nano-carbon material.
Preferably, the light conductive nano carbon material is any one or more of a super-aligned carbon nanotube film, bucky paper, a graphene film and a graphene oxide film, preferably the super-aligned carbon nanotube film is a carbon nanotube film which is obtained by synthesizing a super-aligned carbon nanotube array by a chemical vapor deposition method and drawing the super-aligned carbon nanotube array by using dry spinning.
Preferably, the carbon nanotube film consists of more than one layer of carbon nanotube film, the thickness of the film is adjustable, the thickness is not less than 30nm, and the surface density is not more than 1g/m 2 Electrical conductivity of 10 4 ～10 6 And S/m, the conductivity of the whole film can be changed by adjusting the orientation of the carbon nanotubes in the carbon nanotube film, wherein the orientation of the super-ordered carbon nanotube film is preferably arranged between the single-layer carbon nanotube layers along 0-90 degrees. For example, it may be 10 °, 20 °, 30 °, 40 °, 50 °,60 °, 70 °, 80 °, 90 °, preferably 90 °. Most preferably along 90.
Preferably, the thickness of the insulating and ablation-resistant inorganic fiber product as the adhesive layer is adjustable, and the minimum thickness is not less than 10 μm, preferably, the thickness of the insulating and ablation-resistant inorganic fiber product is 50-400 μm, such as 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, and for the lightning protection product needing to protect 100kA, 200 μm is preferred.
Preferably, the surface density of the insulating heat-insulating ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material product is 10-200g/m 2 。
Preferably, the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material workpiece is placed between the carbon fiber composite material and the conductive film to serve as an isolation layer, and the workpiece is prepared through curing and molding through a mold pressing process or an autoclave process, so that the application of the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material workpiece in lightning protection is realized.
Preferably, when the composite material and the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part are prepregs, the lightning protection part containing the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle can be prepared in one step by a hot-pressing method, and the preparation method comprises the following steps: and sequentially laying carbon fiber prepreg, an insulating heat-insulating ablation-resistant inorganic fiber film/micro-nano hollow particle prepreg and a conductive film layer in a preheated die, carrying out hot pressing on the whole die, and demoulding to obtain the lightning protection part containing the insulating heat-insulating ablation-resistant inorganic fiber film/micro-nano hollow particles.
Preferably, the preparation method of the lightning protection part containing the insulating, heat-insulating and ablation-resistant inorganic fibers comprises the following steps: selecting a tool for a hot press molding process, cleaning the tool, coating a release agent, preheating the die for 5-20min at 40-60 ℃, and sequentially laying a carbon fiber reinforced cyanate ester prepreg, an insulating heat-insulating ablation-resistant quartz fiber reinforced cyanate ester prepreg and a conductive film layer in the preheated die; and placing the whole die on a die press preheated to 70-90 ℃ for 20-40min, installing the die, heating to 140-160 ℃, pressurizing to 2-3MPa, curing for 0.5-3h, and demolding to obtain the lightning protection part containing the insulating, heat-insulating and ablation-resistant inorganic fibers.
The invention relates to a product containing insulating, heat-insulating and ablation-resistant inorganic fiber membranes/micro-nano hollow particles and application thereof in lightning protection, wherein the lightning protection product comprises: a conductive film as a conductive layer; an insulating heat-insulating ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material workpiece serving as an isolation layer; a carbon fiber composite material includes carbon fibers and a resin filled in the carbon fibers. The insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material workpiece provided by the invention has the characteristics of easiness in large-scale preparation, uniformity, good compatibility with a composite material, excellent insulation, heat insulation, ablation resistance, toughness and the like after curing and forming. The insulating heat-insulating ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part is arranged between the composite material and the conductive film, the effect of current injection to the composite material is isolated, meanwhile, the ablation-resistant effect based on the insulating heat-insulating ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part is realized, the ablation is resisted within a short time when the part is subjected to lightning impact, meanwhile, the excellent heat-insulating property of the part can also avoid the heat from being transferred downwards to a carbon fiber composite material region to cause the damage of the carbon fiber composite material region, in addition, the whole mechanical property of the lightning protection part can be enhanced by the fiber membrane part with regular orientation, so that the lightning protection effect of the conductive film is integrally and greatly improved, and the effects of weight reduction, cost reduction and the like are realized.
The inorganic fiber membrane/micro-nano hollow particle composite material part and the lightning protection structure thereof have the following beneficial effects that:
1. according to the inorganic fiber membrane/micro-nano hollow particle composite material part and the lightning protection structure thereof, inorganic fibers (with the length being more than 1 mm) are consistent in orientation and continuous in length in the part, compared with the isolation layer part prepared by taking chopped fibers (with the length being 100-1000 mu m) and the like as fillers, the inorganic fiber membrane/micro-nano hollow particle composite material part has more remarkable excellent insulation and heat insulation ablation resistance after being cured and molded, can enhance the overall mechanical strength, has a better lightning protection effect, can greatly reduce the using amount of a conductive film layer, and realizes the effects of reducing the weight of the whole body and reducing the cost.
2. The carbon nanotube film can be used as an isolation layer (adhesive layer) between the carbon nanotube film and the fiber composite material part, so that current can be isolated from being injected into the fiber composite material part, and the carbon fiber composite material part can be prevented from being damaged. Meanwhile, based on the ablation resistance of the insulating, heat-insulating and ablation-resistant inorganic fibers, the composite material can resist ablation in a short time when subjected to lightning impact. Meanwhile, the heat insulation performance of the aerogel and the hollow alumina microspheres can prevent heat from being transferred to the carbon fiber composite material area downwards to cause damage of the carbon fiber composite material area, so that the lightning protection effect of the conductive film is greatly improved.
3. The inorganic fiber membrane and the micro-nano hollow particles are mixed for use to have a synergistic effect, and the lightning protection effect of the lightning protection structure obtained by using the inorganic fiber membrane as the isolation layer has a better protection effect than that of the inorganic fiber membrane and the micro-nano hollow particles which are used independently.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1 shows a schematic structural diagram of a lightning protection structure 5 containing an insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part in the embodiment of the invention.
FIG. 2 shows a microstructure of a carbon nanotube film in example 6 of the present invention.
Fig. 3 shows a morphology diagram of the micro-nano hollow microspheres, the high temperature resistant resin and the curing agent after blending and curing in comparative example 7.
FIG. 4 shows the morphology of the inorganic fiber film with high temperature resistance, curing agent, insulation, heat insulation and ablation resistance in comparative example 6 after curing.
Fig. 5 shows an appearance and appearance diagram of a lightning protection structure in example 6, which includes an insulating, heat-insulating, ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material product.
Fig. 6 shows an appearance and appearance diagram of a lightning protection structure member containing an insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material member in example 6 after lightning impact.
FIG. 7 is a diagram showing the appearance and appearance of the composite material part without the isolation layer in comparative example 1 after lightning strike.
FIG. 8 is a graphical representation of the appearance of a composite article comprising a chopped quartz fiber reinforced membrane after lightning strike.
FIG. 9 is a topographic map of an insulation, heat insulation and ablation resistance inorganic fiber membrane/micro-nano hollow particle composite material part in example 5 of the present invention
Description of reference numerals:
1. a conductive layer (conductive film); 2. an isolation layer (inorganic fiber membrane/micro-nano hollow particle composite material product); 3. a continuous carbon fiber composite layer.
Detailed Description
The invention is further illustrated by the following specific examples, which, however, are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
This section generally describes the materials used in the testing of the present invention, as well as the testing methods. Although many materials and methods of operation are known in the art for the purpose of carrying out the invention, the invention is nevertheless described herein in as detail as possible. It will be apparent to those skilled in the art that the materials and methods of operation used in the present invention are well within the skill of the art, provided that they are not specifically illustrated.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions in the embodiments of the present invention will be described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention, and based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without creative efforts belong to the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the following examples, the lightning protection part containing the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material and the lightning protection part containing the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material are prepared in one step by using a hot-pressing method, wherein the carbon fiber composite material is a prepreg and/or a prepreg. However, it should be noted that the following is not all examples, and the insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material product may be any product as long as the mixture of the insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle and the curing agent.
The reagents and apparatus used in the following examples are as follows
Materials:
silica hollow microspheres, available from forsmann technologies ltd.
Carbon fiber prepregs are available from wehel glaucor limited.
A woven cloth of quartz fiber, available from handsome glass fiber products ltd.
Release agents were purchased from DAIKIN.
Aerogel powders were purchased from forsman technologies ltd.
The instrument comprises the following steps:
a laboratory programmed temperature Hydraulic tablet press, model LP-S-50/S.ASTM, available from AZZOTA (Oibota) Inc. of USA.
A planetary debubbling blender, model ARV-310, was purchased from THINKY hashin-Kagaku.
Example 1
The embodiment is used for explaining the preparation method of the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part.
(1) In the embodiment, the high-temperature-resistant resin is cyanate ester resin, the curing agent is 2-methylimidazole, the cyanate ester resin and the 2-methylimidazole are weighed according to the mass ratio of 9:1 and placed in a container, the resin and the curing agent account for 40% of the mass of the inorganic fiber membrane/micro-nano hollow particle composite material workpiece, then the silicon dioxide hollow microspheres accounting for 7% of the total mass of the workpiece are weighed and added into the container, and the container is placed in a planetary defoaming stirrer to be mixed and defoamed to obtain the mixed solution containing the high-temperature-resistant resin, the curing agent and the micro-nano hollow microspheres.
(2) Adopting a blade coating process, blade-coating the mixed solution obtained in the step (1) on quartz fiber woven cloth (the quartz fiber woven cloth accounts for 53 percent of the mass of the inorganic fiber membrane/micro-nano hollow particle composite material product), controlling the blade coating thickness to be 200 mu m, placing the inorganic fiber membrane/micro-nano hollow particle composite material product in a polytetrafluoroethylene mold,heating the mixture in a 60 ℃ oven for 6 hours to be semi-cured to form a semi-cured sheet, thus obtaining the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part, wherein the thickness of the obtained composite material part is 180 +/-8 mu m, and the surface density is 179 +/-5.5 g/m 2 。
Example 2
This example is used to illustrate a method for preparing an insulating, heat-insulating, ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part according to the present invention.
(1) The high temperature resistant resin of the embodiment is cyanate ester resin, which is formed by combining bisphenol a cyanate ester and phenolic aldehyde cyanate ester, and has a mass ratio of 1:1, 2-methylimidazole is used as a curing agent, dibutyl cobalt dilaurate is used as a catalyst, polyimide is used as a toughening agent, a mixture of aerogel and hollow silica microspheres is used as micro-nano hollow microspheres, the mass ratio of the aerogel to hollow silica microspheres is 1:1, and quartz fiber woven cloth is used as an inorganic fiber membrane framework. The high-temperature-resistant resin, the curing agent, the catalyst, the toughening agent, the micro-nano hollow microspheres and the quartz fiber woven cloth respectively comprise the following components in percentage by mass: 30%,7%,0.1%,2.9%,7%,53%.
(2) Weighing a certain mass of cyanate ester resin according to the mass fraction in the step (1), placing the cyanate ester resin into a container, stirring the cyanate ester resin until the cyanate ester resin is completely molten under the conditions that the temperature is 80 ℃ and the stirring speed is 1500 rpm, cooling the cyanate ester resin to below 50 ℃ at room temperature, adding acetone and dissolving the cyanate ester to prepare a cyanate ester resin solution. Adding a mixture of a curing agent, a catalyst, a toughening agent and insulating heat-insulating hollow micro-nano particles into a cyanate resin solution according to the mass ratio of the step (1), and fully stirring until the mixture is uniformly mixed to obtain a mixture of cyanate resin, the curing agent and the insulating heat-insulating hollow micro-nano particles.
(3) Uniformly coating a mixture solution of cyanate ester resin, a curing agent and insulating and heat-insulating hollow micro-nano particles on the surface of quartz fiber woven cloth to prepare the insulating and heat-insulating type quartz fiber cyanate ester resin prepreg.
The surface density of the prepared insulating and heat-insulating quartz fiber cyanate resin prepreg is 103 +/-3 g/m 2 The thickness is 100 +/-2.5 mu m. This exampleA cyanate ester quartz fiber prepreg can be obtained, and it should be noted that when the types of the resin, the insulating and heat-insulating inorganic particles and the inorganic fibers are changed, different prepregs can be prepared in the same manner.
Example 3
The embodiment is used for explaining the preparation method of the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part.
(1) The mass fractions of the high-temperature-resistant resin, the curing agent, the catalyst, the toughening agent, the micro-nano hollow microspheres and the quartz fiber woven cloth selected in the embodiment are the same as those in the embodiment 2.
(2) Weighing a certain mass of cyanate ester resin according to mass fraction, placing the cyanate ester resin into a container, stirring the cyanate ester resin and the container at the temperature of 80 ℃ and 1500 rpm until the cyanate ester resin and the container are completely melted, and adding a curing agent, a toughening agent, a catalyst and a mixture of insulating heat-insulating hollow micro-nano particles to obtain the mixture of the cyanate ester resin, the curing agent and the insulating heat-insulating hollow micro-nano particles.
(3) And (3) mixing the mixture of the cyanate ester resin, the curing agent and the insulating heat-insulating hollow micro-nano particles with quartz fiber woven cloth by using a hot-melt pre-dipping machine to obtain the quartz fiber cyanate ester prepreg.
The surface density of the prepared insulating and heat-insulating quartz fiber cyanate resin prepreg is 101 +/-2 g/m 2 The thickness is 102 +/-4.2 mu m. This example can obtain a cyanate ester quartz fiber prepreg, and it should be noted that, when the types of the resin, the insulating and heat-insulating inorganic particles and the inorganic fibers are changed, different prepregs can be prepared in the same manner.
Example 4
The embodiment is used for explaining the preparation method of the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part.
(1) The high temperature resistant resin of this embodiment is bisphenol a cyanate ester resin, and the maleic anhydride end-capped thioether imide with a polymerization degree of 1, the mass ratio of which is 9:1, the two occupy 40 +/-1% of the mass of the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material workpiece, the two are weighed and put into a reaction bottle, and the volume ratio of the two is 1:1, adding a mixture of 7% of aerogel and hollow silica microspheres into a dioxane and ethylene glycol dimethyl ether mixed solvent, wherein the mass ratio of the aerogel to the hollow silica microspheres is 1:1. And refluxing for 1-2 h to obtain a mixed solution of the resin, the curing agent and the micro-nano hollow microspheres.
(2) The obtained solution is soaked on quartz fiber woven cloth to obtain quartz fiber modified cyanate prepreg, and in the inorganic fiber membrane/micro-nano hollow particle composite material part prepared in the embodiment, the mass fraction of a quartz fiber woven cloth skeleton is 53 +/-1%, and the areal density is 98 +/-5.5 g/m 2 The thickness is 101 +/-5.2 mu m. This example can obtain a cyanate ester quartz fiber prepreg, and it should be noted that, when the types of the resin, the insulating and heat-insulating inorganic particles and the inorganic fibers are changed, different prepregs can be prepared in the same manner.
Example 5
This example is used to illustrate a method for preparing a lightning protection structure member containing an insulating, heat-insulating, ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part according to the present invention.
The forming method in the preparation method adopts a low-cost compression molding process, and the composite material lightning protection structure can be obtained by a one-step method. The preparation method comprises the following steps:
(1) S1, selecting a tool for a compression molding process, cleaning the tool, coating a release agent (purchased from DAIKIN, the trade name: GA 9700), and preheating the mold coated with the release agent in a 50 ℃ oven for 5 minutes;
(2) S2, the tool is used for manually laying 20 layers of cyanate ester carbon fiber prepregs and 2 layers of cyanate ester quartz fiber prepregs or prepregs from bottom to top in sequence, wherein the prepregs prepared in the embodiment 3 and 1200 layers of 30-degree crossed super-straight carbon nanotube films are selected in the embodiment;
(3) S3, installing a tool, preheating for 30min at 80 ℃, heating to 150 ℃, and pressurizing to 3Mpa for curing for 3h;
(4) And S4, after cooling, removing the tool to obtain the lightning protection structural member of the insulating heat-insulating ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material workpiece.
Example 6
The embodiment is used for illustrating the lightning protection effect of the lightning protection structural member containing the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part prepared by the invention.
A 100kA lightning impact test is performed on the lightning protection part containing the insulating, heat-insulating and ablation-resistant inorganic fibers prepared in example 6, and fig. 1 shows a schematic structural diagram of the lightning protection structure containing the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part in example 6 of the present invention. FIG. 2 shows a microstructure of a carbon nanotube film in example 7 of the present invention. Fig. 4 shows a topography of the insulating and ablation-resistant inorganic fiber membrane fabricated part after curing. Fig. 9 shows a topography of an insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part in example 1 of the present invention. Fig. 5 shows an appearance and appearance diagram of a lightning protection structural member containing an insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part. Fig. 6 shows an appearance and appearance diagram of a lightning protection structural member containing an insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part after lightning impact.
As can be seen from fig. 1 to 6 and 9, in a lightning impact test, only the carbon nanotube film on the surface of the lightning protection structure containing the insulating, heat-insulating, ablation-resistant inorganic fiber film/micro-nano hollow particle composite material part prepared in this embodiment is slightly damaged, and the surface and the interior of the carbon fiber composite material part are not damaged, which indicates that the lightning protection structure containing the insulating, heat-insulating, ablation-resistant inorganic fiber film/micro-nano hollow particle composite material part prepared in the present invention can be used for lightning protection.
Example 7
The embodiment is used for illustrating the lightning protection effect of the lightning protection structural member containing the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part prepared by the invention.
Conditions were the same as those in example 2 except that the 1200-layer 30 ° crossed super-aligned carbon nanotube film was changed to 1000-layer super-aligned carbon nanotube film. After the prepared composite material part is subjected to a lightning impact test, a test result shows that only the carbon nano tube film on the surface is slightly ablated, the isolation layer is not damaged, and the surface and the interior of the carbon fiber composite material part are not damaged, which indicates that the lightning protection structural member containing the insulating, heat-insulating and ablation-resistant inorganic fiber film/micro-nano hollow particle composite material part prepared by the invention can be used for lightning protection.
Comparative example 1
This comparative example serves to illustrate the insulating and insulating ablation-resistant inorganic fiber membrane according to the invention the existence of the micro-nano hollow particle composite material part has influence on lightning protection.
In the current research, an insulating heat-insulating ablation-resistant inorganic fiber part is not generally adopted as an isolation layer, and a composite material part is obtained by directly curing and molding a conductive carbon nano film, an adhesive film and a carbon fiber prepreg. The molding method comprises the following steps:
(1) S1, selecting a tool for a compression molding process, cleaning the tool, coating a release agent (purchased from DAIKIN, the brand: GA 9700), and preheating a mold coated with the release agent in a 50 ℃ oven for 5 minutes;
(2) S2, manually laying 20 layers of cyanate ester carbon fiber prepregs, two layers of adhesive films (comprising cyanate ester resin and a curing agent, wherein the proportion of each part is the same as that in the embodiment 1) and 1200 layers of 30-degree crossed super-parallel carbon nanotube films by a tool from bottom to top;
(3) S3, installing a tool, preheating for 30min at 80 ℃, heating to 150 ℃, and pressurizing to 3Mpa for curing for 3h;
(4) And S4, after cooling, removing the tool to obtain the composite material workpiece.
The composite material part prepared by the comparative example is subjected to a 100kA lightning impact test, FIG. 6 is an appearance diagram of the composite material part without an isolation layer after lightning impact, and the result of the lightning protection test shows that the composite material part without the insulating heat-insulating ablation-resistant layer is very seriously ablated and damaged on the conductive carbon nano film on the surface of the part, the inside of the carbon fiber composite material part is also seriously damaged, even cracks are generated in the longitudinal direction, the splitting phenomenon is generated, and the lightning protection effect cannot be achieved.
Comparative example 2
The comparative example is used for illustrating the influence of the types of the inorganic fibers in the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part on lightning protection.
(1) The high temperature resistant resin of the comparative example is cyanate ester resin, which is formed by combining bisphenol A cyanate ester and phenolic cyanate ester, the mass ratio of the cyanate ester resin is 1:1, the curing agent is 2-methylimidazole, the catalyst is dibutyl cobalt dilaurate, the toughening agent is polyimide and short-cut quartz fiber (the diameter is 7 μm, and the length is 200 +/-50 μm). The high-temperature-resistant resin, the curing agent, the catalyst and the toughening agent respectively comprise the following components in percentage by mass: 30%,7%,0.1%,2.9%,60%.
(2) Weighing a certain mass of cyanate ester resin according to the mass fraction in the step (1), placing the cyanate ester resin into a container, stirring the cyanate ester resin at the temperature of 80 ℃ and 1500 rpm until the cyanate ester resin is completely molten, and adding a curing agent, a toughening agent and a catalyst to obtain a cyanate ester resin mixture.
(3) Weighing the chopped quartz fibers in the mass fraction in the step (1), uniformly mixing the mixture with cyanate ester resin and a curing agent, clamping the mixture between an upper release film and a lower release paper, and pressing the mixture into the reinforcing film containing the chopped quartz fibers through a press roll.
The molding method comprises the following steps:
(1) S1, selecting a tool for a compression molding process, cleaning the tool, coating a release agent which is purchased from DAIKIN and is of a brand number: GA9700, placing the mold coated with the release agent in a 50 ℃ oven to preheat for 5 minutes;
(2) S2, manually laying 20 layers of cyanate ester carbon fiber prepregs, namely the chopped quartz fiber reinforced film and 1200 layers of 30-degree crossed super-parallel carbon nanotube films by a tool from bottom to top in sequence;
(3) S3, installing a tool, preheating for 30min at 80 ℃, heating to 150 ℃, and pressurizing to 3Mpa for curing for 3h;
(4) And S4, after cooling, removing the tool to obtain the lightning protection part containing the short-cut quartz fiber reinforced composite material isolation layer.
The barrier layer comprising the chopped quartz fiber reinforced composite material prepared as described above had a thickness of 200. + -. 5 μm and an areal density of 320g/m 2 . After the lightning impact test, the test result shows that only the carbon nanotube film on the surface is slightly damaged, and the surface and the interior of the carbon fiber composite material part are not damaged, which indicates that the prepared composite material part can be used for lightning protection.
Comparative example 3
The comparative example is used for illustrating the influence of the types of the inorganic fibers in the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part on lightning protection.
Except that the silica microspheres (particle size: 15 μm) were used instead of the short quartz fibers, the conditions were the same as in comparative example 2. Wherein, the silicon dioxide microspheres with the mass fraction of 60 percent are highly adhered in the resin, are difficult to be uniformly dispersed, have complex preparation operation and the cured surface density of 356g/m 2 . After the lightning impact test, the test result shows that only the carbon nanotube film on the surface is slightly ablated, and the surface and the interior of the carbon fiber composite material part are not damaged, which indicates that the prepared composite material part can be used for lightning protection.
Comparative example 4
The comparative example is used for illustrating the influence of the content of the inorganic fibers in the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part on lightning protection.
Except that the mass fraction of the chopped Dan Yingqian d and was changed to 20%, the other conditions were in accordance with comparative example 2. The thickness of the composite material isolation layer is controlled to be 200 +/-5 mu m, and the surface density is 240g/m 2 FIG. 7 is a diagram showing the appearance of a composite material part containing a chopped quartz fiber reinforced film after lightning strike, which shows that the carbon nanotube film on the surfaceModerate ablation occurs, the middle insulating layer is slightly damaged, and the surface and the interior of the carbon fiber composite material part are not damaged, which indicates that the lightning protection effect of the prepared composite material part is general.
Comparative example 5
The comparative example is used for illustrating the influence of the content of the inorganic fibers in the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part on lightning protection.
Except that the mass fraction of the silica microspheres was changed to 20%, the other conditions were in accordance with comparative example 3. The thickness of the composite material isolation layer is controlled to be 200 +/-5 mu m, and the surface density is 256g/m 2 The lightning impact test shows that the carbon nanotube film on the surface is moderately ablated, the insulating layer in the middle is slightly damaged, and the surface and the interior of the carbon fiber composite material part are not damaged, so that the lightning protection effect of the prepared composite material part is general.
Comparative example 6
The comparative example is used for illustrating the influence of the inorganic fiber membrane and the micro-nano hollow particles in the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part on lightning protection.
The conditions are the same as those in example 5 except that the micro-nano hollow microspheres and the aerogel are not added. Namely high-temperature resistant resin, a curing agent, a catalyst and a toughening agent, wherein the mass fractions of the quartz fiber woven cloth are respectively as follows: 30%,7%,0.1%,2.9%,60%. The thickness of the composite material isolation layer is controlled to be 200 +/-5 microns, and a lightning impact test shows that the carbon nanotube film on the surface is slightly ablated, the insulating layer in the middle is slightly damaged, and the surface and the interior of the carbon fiber composite material part are not damaged, so that the prepared composite material part can be applied to lightning protection.
Comparative example 7
The comparative example is used for illustrating the influence of the inorganic fiber membrane and the micro-nano hollow particles in the insulating, heat-insulating and ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part on lightning protection.
Conditions were the same as those in example 5 except that the woven cloth of quartz fibers was not used as a skeleton. Namely high-temperature-resistant resin, a curing agent, a catalyst and a toughening agent, wherein the micro-nano hollow microspheres (including silicon dioxide microspheres and aerogel) respectively comprise the following components in percentage by mass: 30%,7%,0.1%,2.9%,60%. The viscosity found in the mixing process is too high, so that the lightning protection structure is difficult to prepare, and the mass fraction of the micro-nano hollow microspheres needs to be adjusted downwards.
The part is prepared after the mass fraction of the micro-nano hollow microspheres is changed to 40%, and a lightning impact test shows that the carbon nano tube film on the surface is moderately ablated, the insulating layer in the middle is slightly damaged, and the surface and the interior of the carbon fiber composite part are not damaged, so that the lightning protection effect of the prepared composite part is general.
According to the experimental data, the existence of the insulating heat-insulating ablation-resistant inorganic fiber membrane/micro-nano hollow particle composite material part is compared with a composite material isolation layer reinforced by powder/short fibers, the lightning protection performance of the conductive film can be greatly improved, the quantity of the conductive layer is reduced, the cost is reduced, and the overall weight reduction effect is achieved, the inorganic fiber membrane and the micro-nano hollow particles are mixed to be used to achieve a synergistic effect, and the lightning protection effect of the lightning protection structural part obtained by the inorganic fiber membrane as the isolation layer has a better protection effect than that of the inorganic fiber membrane and the micro-nano hollow particles which are used alone.
Although the present invention has been described to a certain extent, it is apparent that appropriate changes in the respective conditions may be made without departing from the spirit and scope of the present invention. It is to be understood that the invention is not limited to the described embodiments, but is to be accorded the scope consistent with the claims, including equivalents of each element described.
Claims (10)
1. The utility model provides an inorganic fiber membrane/little nano hollow particle composite material finished piece which characterized in that, inorganic fiber membrane/little nano hollow particle composite material finished piece includes mixture and inorganic fiber membrane skeleton that comprises high temperature resistant resin, curing agent and little nano hollow particle, wherein:
the inorganic fiber membrane/micro-nano hollow particle composite material part is preferably layered, and the thickness of the inorganic fiber membrane/micro-nano hollow particle composite material part is more than 10 micrometers, preferably 30-400 micrometers, and more preferably 50-400 micrometers.
2. The inorganic fiber membrane/micro-nano hollow particle composite material part as claimed in claim 1, wherein:
the high-temperature resistant resin is selected from one or more of the following: cyanate ester resin, phenolic resin, bismaleimide resin, organic silicon resin, modified epoxy resin, modified cyanate ester resin, modified phenolic resin and modified bismaleimide resin, preferably selected from one or more of the following: cyanate ester resin, phenolic resin, silicone resin, modified epoxy resin, modified cyanate ester resin, modified phenolic resin, modified polyester resin, modified silicone resin, bismaleimide resin, more preferably selected from one or more of the following: cyanate ester resin, modified epoxy resin, modified cyanate ester resin, bismaleimide resin;
the curing agent is selected from: imidazole curing agents and/or amine curing agents; preferably selected from one or more of the following: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, ethylenediamine, diethylenetriamine, triethylenetetramine, diaminodiphenylalum (DDS), diaminodiphenylmethane (DDM), 4,4 diaminodiphenylmethane (DDM), 4,4 diaminodiphenylether (DDE), 4,4 diaminodiphenylalum (DDS), m-phenylenediamine (m-PDA), polyetheramine D-230, more preferably selected from one or more of: 2-methylimidazole, 2-ethyl-4-methylimidazole, polyetheramine D-230;
the micro-nano hollow particles are selected from one or more of the following: the hollow silica-based composite material comprises aerogels, hollow alumina microspheres, hollow glass microspheres, hollow silica microspheres, hollow ceramic microspheres, hollow titanium dioxide microspheres, hollow fly ash microspheres, hollow zirconium dioxide microspheres and/or hollow carbon microspheres, and is preferably selected from one or more of the following components: aerogel, hollow alumina microspheres, hollow silica microspheres, hollow ceramic microspheres, hollow titanium dioxide microspheres, hollow fly ash microspheres, hollow zirconium dioxide microspheres and/or hollow carbon microspheres; more preferably selected from one or more of the following: aerogels, hollow alumina microspheres, and/or hollow silica microspheres; and/or
The inorganic fiber membrane skeleton is selected from one or more of the following: unidirectional films, laminated films and woven films with regular orientation, and most preferably continuous fiber woven films with regular orientation;
preferably, the inorganic fiber membrane/micro-nano hollow particle composite material part further comprises a processing aid;
more preferably, the processing aid comprises an accelerator, a catalyst and/or a toughening agent; the accelerator is further preferably selected from one or more of the following: tertiary amine, methyldiethanolamine and/or aminophenol, more preferably tertiary amine or aminophenol; the catalyst is further preferably selected from one or more of the following: dibutyl cobalt dilaurate, dibutyl zinc dilaurate, dibutyl copper dilaurate, zinc octoate, manganese octoate, copper octoate, cobalt acetylacetonate, zinc acetylacetonate, manganese acetylacetonate, and more preferably one or more selected from the group consisting of: zinc octoate, manganese octoate, copper octoate, cobalt acetylacetonate, zinc acetylacetonate, manganese acetylacetonate; and/or the toughening agent is further preferably selected from one or more of the following: polyether sulfone, polyimide, carboxylated nitrile rubber, liquid nitrile rubber, polyvinyl butyral, polyether sulfone, polyphenylene ether ketone, polysulfide rubber, liquid silicone rubber, polyether sulfone, and more preferably polyether sulfone or polyimide.
3. The inorganic fiber membrane/micro-nano hollow particle composite material part as claimed in claim 1 or 2, wherein:
the mass parts of the high-temperature resistant resin, the curing agent, the micro-nano hollow particles and the inorganic fiber membrane skeleton are 3-90;
preferably, when the inorganic fiber membrane/micro-nano hollow particle composite material product comprises a processing aid, the mass parts of the high-temperature resistant resin, the curing agent, the processing aid, the micro-nano hollow particles and the inorganic fiber membrane skeleton are 3-90;
more preferably, in the processing aid, the mass parts ratio of the accelerator, the catalyst and the flexibilizer is 0-1:0-0.2, preferably 0.1-0.7, 0.01-0.1, more preferably 0-0.6.
4. The inorganic fiber membrane/micro-nano hollow particle composite material part as claimed in any one of claims 1 to 3, wherein: the fiber units contained in the inorganic fiber membrane skeleton are insulating, heat-insulating and ablation-resistant continuous fibers, and the length of the continuous fibers is continuous in the inorganic fiber membrane/micro-nano hollow particle composite material workpiece in a penetrating manner; wherein the content of the first and second substances,
the length of the continuous fibers is greater than 1mm, preferably greater than 1cm, more preferably greater than 30cm;
preferably, the mass fraction of the inorganic fiber membrane in the inorganic fiber membrane/micro-nano hollow particle composite material part is 40-70%, preferably 50-70%, and most preferably 60%; and/or
Preferably, the inorganic fiber membrane in the inorganic fiber membrane/micro-nano hollow particle composite material part is selected from one or more of the following: quartz fibers, glass fibers, ceramic fibers, basalt fibers, alumina fibers, zinc oxide fibers, silicon nitride fibers, aluminum silicate fibers, boron fibers, more preferably selected from one or more of the following: quartz fibers, glass fibers, alumina fibers, zinc oxide fibers, basalt fibers, aluminum silicate fibers, boron fibers; further preferred is one or more selected from the group consisting of: quartz fibers, glass fibers, alumina fibers, zinc oxide fibers, basalt fibers.
5. A method for preparing the inorganic fiber membrane/micro-nano hollow particle composite material part as claimed in any one of claims 1 to 4, wherein the method comprises the following steps: mixing high-temperature resin, a curing agent and micro-nano hollow particles and uniformly dispersing the mixture to obtain a mixed solution, then impregnating an inorganic fiber membrane framework into the mixed solution, or coating the mixed solution on the inorganic fiber membrane framework, and curing and drying at room temperature or under a heating condition to obtain an inorganic fiber membrane/micro-nano hollow particle composite material workpiece;
preferably, the method for coating the mixed solution on the inorganic fiber membrane skeleton is selected from one or more of the following methods: spraying, blade coating and curtain coating;
preferably, the mass ratio of the high-temperature resin, the curing agent and the micro-nano hollow particle mixture is 5-95: 1 to 25:1 to 10, more preferably 20 to 60:1 to 20:1 to 9, more preferably 35 to 45:1 to 15:1 to 8; and/or
Preferably, the mass ratio of the mixed solution to the inorganic fiber membrane skeleton is 5-95: 5 to 95, more preferably 20 to 60, and still more preferably 35 to 45:55 to 65.
6. A method for preparing the inorganic fiber membrane/micro-nano hollow particle composite material part as claimed in any one of claims 1 to 4, wherein the method comprises the following steps: melting high-temperature resin, adding a curing agent and micro-nano hollow particles into the high-temperature resin, mixing to obtain a mixed solution containing the molten resin, directly soaking an inorganic fiber membrane framework in a mixed solution glue tank containing the molten resin, drying and rolling to obtain an inorganic fiber membrane/micro-nano hollow particle composite material workpiece;
preferably, the mass ratio of the mixed solution containing the molten resin to the inorganic fiber membrane skeleton is 5 to 95:5 to 95, more preferably 20 to 60, and still more preferably 35 to 45:55 to 65.
7. A method for preparing the inorganic fiber membrane/micro-nano hollow particle composite material part as claimed in any one of claims 1 to 4, wherein the method comprises the following steps: melting high-temperature resin, adding a curing agent and micro-nano hollow particles into the high-temperature resin for mixing to obtain a mixed solution containing the molten resin, uniformly coating the mixed solution containing the molten resin on a molding machine to prepare a film, superposing the film with an inorganic fiber film framework for high-temperature treatment, and rolling to obtain an inorganic fiber film/micro-nano hollow particle composite material workpiece;
preferably, the mass ratio of the mixed solution containing the molten resin to the inorganic fiber membrane skeleton is 5 to 95:5 to 95, more preferably 20 to 60, and still more preferably 35 to 45:55 to 65.
8. A lightning protection structure, characterized in that lightning protection structure includes that top-down sets gradually:
a conductive layer;
an isolation layer; and
a continuous carbon fiber composite layer;
wherein the isolation layer is the inorganic fiber membrane/micro-nano hollow particle composite material product of any one of claims 1 to 4 or the inorganic fiber membrane/micro-nano hollow particle composite material product prepared by the method of any one of claims 5 to 7;
preferably, the conductive layer is a conductive film, and the material of the conductive film is selected from one or more of the following materials: copper, nickel, aluminum, conductive metal oxides, conductive polymers, metal-modified nanocarbon materials, light conductive nanocarbon materials, and more preferably light conductive nanocarbon materials;
further preferably, the light conductive nanocarbon material is selected from one or more of the following: the film comprises a super-ordered carbon nanotube film, bucky paper, a graphene film and a graphene oxide film, and the most preferable is the super-ordered carbon nanotube film;
still further preferably, the super-aligned carbon nanotube film changes the conductivity of the entire film by adjusting the orientation of the carbon nanotubes in the carbon nanotube film, wherein the orientation of the super-aligned carbon nanotube film is arranged between the single-layer carbon nanotube layers along 0 to 90 °, and most preferably along 90 °.
9. A lightning protection structure according to claim 8, characterised in that:
the thickness of the conductive layer is not less than 30nm, preferably not less than 1 μm, and more preferably not less than 15 μm;
the surface density of the conductive layer is not more than 30g/m 2 Preferably not more than 25g/m 2 More preferably not more than 20g/m 2 ；
The conductivity of the conductive layer is 10 4 ～10 8 S/m；
The surface density of the isolating layer is 10-200g/m 2 Preferably 20 to 180g/m 2 More preferably 30 to 150g/m 2 (ii) a And/or
The thickness of the spacer layer is greater than 10 μm, preferably 30 to 400 μm, more preferably 50 to 400 μm, and most preferably 200 μm.
10. Use of the inorganic fiber membrane/micro-nano hollow particle composite article according to any one of claims 1 to 4 or the lightning protection structure according to claim 8 or 9 in the preparation of a lightning protection product;
preferably, the lightning protection product is an aircraft fuselage surface product, a wind turbine blade structure surface product, an urban railway traffic surface product.
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