CN115195216B - 负载氧化锌纳米线静电纺丝膜层间增强增韧连续纤维增强树脂基复合材料及其制备方法 - Google Patents
负载氧化锌纳米线静电纺丝膜层间增强增韧连续纤维增强树脂基复合材料及其制备方法 Download PDFInfo
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- CN115195216B CN115195216B CN202210828441.5A CN202210828441A CN115195216B CN 115195216 B CN115195216 B CN 115195216B CN 202210828441 A CN202210828441 A CN 202210828441A CN 115195216 B CN115195216 B CN 115195216B
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- zinc oxide
- electrostatic spinning
- composite material
- fiber reinforced
- reinforced resin
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 244
- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 135
- 239000002131 composite material Substances 0.000 title claims abstract description 104
- 229920005989 resin Polymers 0.000 title claims abstract description 100
- 239000011347 resin Substances 0.000 title claims abstract description 100
- 239000000835 fiber Substances 0.000 title claims abstract description 95
- 239000011159 matrix material Substances 0.000 title claims abstract description 56
- 239000011229 interlayer Substances 0.000 title claims abstract description 45
- 239000012528 membrane Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 239000011787 zinc oxide Substances 0.000 claims abstract description 94
- 238000000034 method Methods 0.000 claims abstract description 42
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 239000010410 layer Substances 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 98
- 238000000465 moulding Methods 0.000 claims description 35
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 24
- 239000002121 nanofiber Substances 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000004305 biphenyl Substances 0.000 claims description 12
- 235000010290 biphenyl Nutrition 0.000 claims description 12
- 239000004917 carbon fiber Substances 0.000 claims description 12
- 239000011258 core-shell material Substances 0.000 claims description 12
- 239000004697 Polyetherimide Substances 0.000 claims description 10
- 229920001601 polyetherimide Polymers 0.000 claims description 10
- -1 polyphenylene pyridoimidazole Polymers 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 9
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 9
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- 229960000314 zinc acetate Drugs 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- 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 7
- 239000004695 Polyether sulfone Substances 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920000090 poly(aryl ether) Polymers 0.000 claims description 7
- 229920006260 polyaryletherketone Polymers 0.000 claims description 7
- 229920006393 polyether sulfone Polymers 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical group [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004962 Polyamide-imide Substances 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229940057499 anhydrous zinc acetate Drugs 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012792 core layer Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004693 Polybenzimidazole Substances 0.000 claims description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920006376 polybenzimidazole fiber Polymers 0.000 claims description 2
- 229920002577 polybenzoxazole Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 150000004677 hydrates Chemical class 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 5
- 238000007731 hot pressing Methods 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 2
- 239000011157 advanced composite material Substances 0.000 abstract 1
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- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
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- 238000009987 spinning Methods 0.000 description 12
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
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- LSEBTZWHCPGKEF-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C=C1 LSEBTZWHCPGKEF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
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- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
- B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
- B29C70/342—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation using isostatic pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
- B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
- B29C70/345—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation using matched moulds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
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- B32—LAYERED PRODUCTS
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
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- 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
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Abstract
本发明属于先进复合材料科学技术领域,公开了一种负载氧化锌纳米线静电纺丝膜层间增强增韧连续纤维增强树脂基复合材料及其制备方法。将热塑性树脂和氧化锌种子剂溶解在极性有机溶剂中,配制成静电纺丝溶液,通过静电纺丝工艺,经过加热干燥,并在氧化锌生长液中生长,制备负载氧化锌纳米线的静电纺丝膜;将静电纺丝膜铺放于连续纤维增强树脂基复合材料层间,通过热压或真空热压成型工艺,制备负载氧化锌纳米线静电纺丝膜层间增强增韧连续纤维增强树脂基复合材料,使连续纤维增强树脂基复合材料层压板的层间剪切强度和层间韧性显著提高。本发明对于推动连续纤维增强树脂基复合材料的发展应用具有实用价值。
Description
技术领域
本发明属于高分子材料合成领域,具体地涉及一种负载氧化锌纳米线静电纺丝膜层间增强增韧连续纤维增强树脂基复合材料及其制备方法,其适用于连续纤维增强树脂基复合材料的层间增强增韧技术。
背景技术
连续纤维增强树脂基复合材料具有优异的力学性能、耐腐蚀性及轻质等优点,已经被广泛应用于航空航天、汽车、新能源、石油化工等诸多领域。连续纤维增强树脂基复合材料层压板在层内纤维方向性能优异,垂直面内方向主要依赖树脂承载,成为承载的薄弱点,在使用过程中易出现分层失效现象;此外,纤维增强热固性树脂基复合材料和纤维增强刚性耐高温热塑性树脂基复合材料的层间韧性也需要提高。因此,在连续纤维增强树脂基复合材料的层间增强增韧方面的研究对于材料满足应用需求具有十分重要的意义。常用的方法包括在预浸料铺层间引入颗粒、纤维、薄膜、静电纺丝膜等形式的增韧层,这种增韧材料一般为热塑性树脂、橡胶、碳纳米管(Carbon nanotubes,CNTs)、石墨烯(Graphene, GP)等纳米材料。然而,其对垂直面内方向的强度贡献很有限。此外,在复合材料厚度方向引入增强纤维对层间性能也有较好的改善效果,如通过三维编织、缝合和Z-pin等方法在复合材料厚度方向引入增强纤维,但采用这些方法容易造成面内性能的降低。在复合材料层间添加静电纺丝膜,是一种在复合材料富含树脂的夹层中引入韧性相的简单方法,由于其由纳米纤维组成,具有高比表面积和优异的力学性能,可以有效抑制层间裂纹扩展。Beylergil,B.等人(Composite Structures.2018,194:21-35)报道了尼龙-66静电纺丝膜层间增韧环氧树脂基复合材料,复合材料的层间I型和II型断裂韧性明显增加,层间剪切强度提高25%,但由于碳纤维的体积含量降低,使复合材料的拉伸、弯曲和压缩性能降低。
杂萘联苯结构聚芳醚系列高性能树脂是大连理工大学自主研发的一类高性能热塑性树脂基体,其玻璃化转变温度在250~370℃之间可调控,且可溶解于某些极性非质子有机溶剂,不仅可采用传统热塑性树脂的注塑挤出加工成型,还可采用溶液方式加工成型,综合性能优异,尤其是高温力学性能突出。本课题组王程浩等人以耐高温、可溶解的杂萘联苯聚芳醚腈酮树脂为前驱体,通过静电纺丝 -高温500℃热处理两步法成功制备了氮、氧杂原子掺杂的Fe3C@C纳米纤维吸波剂(Journal of Alloys and Compounds,2021,885:160968)和氧、氮原子掺杂的梳状Ni@C纳米纤维吸波剂(Composites Part B,2021,223:109114),但静电纺丝膜经过高温处理后均已碳化,其结构组成均与本发明不同。
尽管现有层间增韧方法有助于提高纤维增强树脂基复合材料的层间韧性,然而增韧效果有待于进一步提高,而且需要同步提高复合材料弯曲性能等力学性能。因此,随着诸多应用领域对连续纤维增强树脂基复合材料性能要求的不断提高,亟需开发能够同时提高复合材料层间韧性和力学性能的方法。而采用负载 ZnO纳米线静电纺丝膜层间增强增韧连续纤维增强树脂基复合材料的技术在国内外未见于报道。
发明内容
针对现有技术中存在的缺陷,本发明的目的在于提供了一种负载氧化锌纳米线静电纺丝膜层间增强增韧连续纤维增强树脂基复合材料及其制备法。本发明要解决的技术问题是通过原位生长的方法将氧化锌纳米线负载于热塑性树脂静电纤维膜上,负载氧化锌纳米线静电纺丝膜的多孔结构可促进层间基体树脂的相互浸润。与未负载氧化锌纳米线静电纺丝膜相比,负载有氧化锌纳米线静电纺丝膜具有类似毛毛虫结构,具有更大的比表面积(如附图1所示),有助于提高树脂基体与静电纺丝膜的相互作用。从层间增韧增强机理分析,存在以下几方面特点: (1)静电纺丝纳米纤维及其表面生长的氧化锌纳米线将有效阻止裂纹扩展;(2) 静电纺丝纳米纤维的塑性变形、拔出和断裂,以及负载氧化锌纳米线的纳米纤维可以吸收大量断裂能;(3)氧化锌纳米线所起的铆接作用及其在纳米纤维上的脱落会阻碍裂纹的扩展并改变扩展路径。因此,静电纺丝纤维膜和其表面生长的氧化锌纳米线协同作用,可提高连续纤维增强树脂基复合材料的层间韧性和力学性能,进而解决连续纤维增强树脂基复合材料层间强度和韧性不足的问题。
为了实现上述目的,本发明采用以下技术方案:
一种负载氧化锌纳米线静电纺丝膜层间增强增韧连续纤维增强树脂基复合材料,该复合材料是将多层连续纤维增强树脂基预浸片(或称为预浸料)与设置在相邻连续纤维增强树脂基预浸片间的负载氧化锌纳米线静电纺丝膜压制成型得到的,其中,
所述连续纤维增强树脂基预浸片包括树脂基体以及分散于所述树脂基体中的纤维;
所述负载氧化锌纳米线静电纺丝膜包括热塑性树脂形成的静电纺丝纳米纤维膜以及生长于所述静电纺丝纳米纤维膜上的氧化锌纳米线,氧化锌纳米线自所述静电纺丝纳米纤维膜中纤维丝表面向外生长。
连续纤维增强树脂基预浸片以及设置于相邻预浸片之间的负载氧化锌纳米线静电纺丝膜在压制成型过程中,静电纺丝膜上负载的氧化锌纳米线会插入连续纤维增强树脂基预浸片中,增加与连续纤维增强树脂基层的接触面积,从而进一步起到固定相邻连续纤维增强树脂基层的作用,增强层间韧性和强度,负载氧化锌纳米线的纳米纤维可以吸收大量断裂能、有效阻止裂纹扩展;而静电纺丝纳米纤维也因较大的比表面积和多孔结构而与相邻连续纤维增强树脂基体结合紧密,另外,静电纺丝纳米纤维的塑性变形、拔出和断裂也可以吸收大量断裂能,会阻碍裂纹的扩展并改变扩展路径。
在上述复合材料中,作为一种优选实施方式,所述氧化锌纳米线的长度为 0.5-5μm(比如0.6μm、1.0μm、1.5μm、2.0μm、2.5μm、3.0μm、3.5μm、4.0μm、 4.4μm、4.8μm)。氧化锌纳米线的长度也不宜太长,过长的氧化锌纳米线会导致静电纺丝膜中的孔隙率降低,不利于预浸料树脂基体的相互贯穿,进而影响层间剪切强度和韧性。
在上述复合材料中,作为一种优选实施方式,所述多层连续纤维增强树脂基预浸片为至少3层连续纤维增强树脂基预浸片。
在上述复合材料中,作为一种优选实施方式,所述连续纤维增强树脂基预浸片中,按照体积百分比,所述树脂基体的含量为30%~50%,所述纤维的含量为 50%~70%。
在上述复合材料中,作为一种优选实施方式,设置在相邻连续纤维增强树脂基预浸片间的所述负载氧化锌纳米线静电纺丝膜的面密度为1~40g/m2(比如 3g/m2、8g/m2、12g/m2、18g/m2、23g/m2、27g/m2、30g/m2、35g/m2、38g/m2)。
在上述复合材料中,作为一种优选实施方式,所述负载氧化锌纳米线静电纺丝膜是通过如下方法制备的:
步骤S1,含氧化锌种子剂的静电纺丝膜的制备:将含有热塑性树脂和氧化锌种子剂的静电纺丝液通过静电纺丝制成含氧化锌种子剂的静电纺丝膜;或者含氧化锌种子剂的核壳结构静电纺丝膜的制备:利用同轴针头,将含有氧化锌种子剂的壳层静电纺丝液和含热塑性树脂的核层静电纺丝液通过静电纺丝制成氧化锌种子剂作为壳、热塑性树脂纳米纤维作为核的含氧化锌种子剂的核壳结构静电纺丝膜;
步骤S2,将含氧化锌种子剂的静电纺丝膜或含氧化锌种子剂的核壳结构静电纺丝膜加热处理以使氧化锌种子剂分解为氧化锌,得到含有氧化锌的热塑性树脂静电纺丝膜;
步骤S3,将含有氧化锌的热塑性树脂静电纺丝膜浸入氧化锌生长液中进行氧化锌纳米线的生长,然后经干燥得到负载氧化锌纳米线静电纺丝膜。
在上述复合材料中,作为一种优选实施方式,氧化锌种子剂为无水醋酸锌或醋酸锌水合物。采用本发明优选的氧化锌种子剂来制备含有氧化锌的热塑性树脂静电纺丝膜,氧化锌可以在静电纺丝膜上更加均匀地分布,避免经过高温反应生成的氧化锌发生团聚。
在上述复合材料中,作为一种优选实施方式,含有热塑性树脂和氧化锌种子剂的静电纺丝液是将热塑性树脂和氧化锌种子剂溶解于有机溶剂中制备而成的,其中,热塑性树脂占有机溶剂的质量百分比为1%~30%(比如2%、8%、10%、 15%、20%、25%、28%),静电纺丝液中热塑性树脂的含量过高不利于静电纺丝膜的均匀性,且将使静电纺丝膜纤维直径增大,纤维强度降低,增韧增强效果降低,过低的浓度也不利于静电纺丝,纤维直径太小,容易断丝,增韧效果降低;氧化锌种子剂占有机溶剂的质量百分比为0.5~5%(比如0.6%、1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%、4.8%),过低的氧化锌种子剂浓度,将导致静电纺丝膜上生长的氧化锌纳米线数量降低,不利于复合材料增强增韧,过高的氧化锌种子剂浓度,将使静电纺丝膜含有过多的无机组分而导致韧性降低,对复合材料的层间韧性和强度不利。
在上述复合材料中,作为一种优选实施方式,含有氧化锌种子剂的壳层静电纺丝液是将氧化锌种子剂和热塑性树脂溶于有机溶剂中制备而成的,其中氧化锌种子剂占有机溶剂的质量百分比为0.5~5%(比如0.6%、1%、1.5%、2%、2.5%、 3%、3.5%、4%、4.5%、4.8%),热塑性树脂占有机溶剂的质量百分比为1%~30% (比如2%、8%、10%、15%、20%、25%、28%);含热塑性树脂的核层静电纺丝液是将热塑性树脂溶于有机溶剂中制备而成的,其中热塑性树脂占有机溶剂的质量百分比为1%~30%。优选地,含有氧化锌种子剂的壳层静电纺丝液中的热塑性树脂不同于含热塑性树脂的核层静电纺丝液中的热塑性树脂。
在上述复合材料中,作为一种优选实施方式,步骤S1中,静电纺丝的条件为:推进速度0.1~10.0mL/h(比如0.5mL/h、1mL/h、2mL/h、3mL/h、4mL/h、5mL/h、6mL/h、7mL/h、8mL/h、9mL/h、9.8mL/h),电压8~30KV(比如10KV、15KV、 20KV、25KV、28KV),接收距离8~30cm(比如10cm、15cm、20cm、25cm、 29cm)。
在上述复合材料中,作为一种优选实施方式,步骤S2中,所述加热处理的条件为:加热温度为150~250℃(比如160℃、180℃、200℃、220℃、240℃、 248℃),保温时间为0.5~15h(比如0.6h、1h、3h、5h、8h、10h、12h、14h)。
在上述复合材料中,作为一种优选实施方式,步骤S3中,所述氧化锌纳米线的生长条件为:在80~110℃(比如90℃、95℃、100℃、105℃)下生长10分钟~5小时(比如20min、40min、50min、55min、1h、1.2h、1.5h、2h、2.8h、3.5h、 4h、4.8h)。过低的生长温度或过短的生长时间,将使生长速度偏慢,氧化锌纳米线的长度太短,反之纳米线会生长太长,其都不利于增强复合材料的层间强度和韧性。
在上述复合材料中,作为一种优选实施方式,所述的氧化锌生长液包括以下组分:硝酸锌或其水合物、醋酸锌或其水合物的一种或两种混合,其主要作用是提供锌源,摩尔浓度为0.001~0.1mol/L(比如0.005mol/L、0.01mol/L、0.03mol/L、 0.05mol/L、0.08mol/L);乌洛托品或三乙醇胺的一种或两种混合,为催化剂,将锌源化合物催化转化成氧化锌,摩尔浓度为0.001~0.1mol/L(比如0.005mol/L、 0.01mol/L、0.03mol/L、0.05mol/L、0.08mol/L);氨水,质量浓度1%~20%(比如3%、8%、12%、15%、18%),作用是提供碱性环境;溶剂水。
在上述复合材料中,所述的有机溶剂包括但不限于以下几种:N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N,N-二甲基吡咯烷酮、二甲基亚砜、四氢呋喃、二氯甲烷、三氯甲烷、二氯乙烷、三氯乙烷、甲酸、乙酸中的一种或几种混合。
在上述复合材料中,所述树脂基体包括但不限于以下几种:环氧树脂、双马来酰亚胺树脂、乙烯基树脂、异氰酸酯树脂、聚醚醚酮、聚醚酮酮、聚砜、聚醚砜、聚亚苯基砜、聚芳醚砜、聚芳醚酮、杂萘联苯结构聚芳醚、聚醚酰亚胺、聚苯硫醚、聚碳酸酯、聚酰胺、聚酯中的一种或几种。
在上述复合材料中,所述纤维包括但不限于以下几种:碳纤维、玻璃纤维、玄武岩纤维、芳纶纤维、氮化硼纤维、石英纤维、聚苯并噁唑纤维、聚苯并咪唑纤维、陶瓷纤维、聚酰亚胺纤维、超高分子量聚乙烯纤维、聚苯硫醚纤维、聚酰胺酰亚胺纤维、聚苯撑吡啶并咪唑纤维中的一种或几种。
在上述复合材料中,所述热塑性树脂包括但不限于以下几种:杂萘联苯结构聚芳醚、聚砜、聚醚砜、聚亚苯基砜、酚酞型聚芳醚砜、酚酞型聚芳醚酮、聚醚酰亚胺、聚苯硫醚、聚偏氟乙烯、聚酰胺、聚芳酰胺、聚酰亚胺、聚酰胺酰亚胺的一种或几种混合。
优选地,所述杂萘联苯结构聚芳醚具有如下结构:
其中,R1、R2、R3、R4是氢、卤素取代基、苯基、苯氧基、烷基或烷氧基, R1、R2、R3和R4的结构相同或不同;烷基或烷氧基中含有至少1个碳原子,直链或带支链;m≥10,n≥10;
—Ar1—的结构是制备杂萘联苯结构聚芳醚时对应的芳香双卤单体反应产生,由所选用芳香双卤单体的结构决定,—Ar1—的结构为以下的一种或几种混合:
R是氢、甲基、甲氧基、苯基、烷基或烷氧基,其中烷基或烷氧基都含有1至20个碳原子,直链或带支链。
—Ar2—的结构是制备杂萘联苯结构聚芳醚时对应的双酚或类双酚单体反应产生,由所选用双酚或类双酚单体的结构决定,—Ar2—的结构为以下的一种或几种混合:
1,2位、1,3位或1,4位;
2,2′位或4,4′位;
1,4位、1,5位、1,6位、2,6位或2,7位;
3,3′位或4,4′位;
3,3′位或4,4′位;
3,3′位或4,4′位;
3,3′位或4,4′位;
3,3′位或4,4′位;
R1、R2、R3、R4是氢、卤素取代基、苯基、苯氧基、烷基或烷氧基,R1、R2、R3和R4的结构相同或不同;烷基或烷氧基中含有至少1个碳原子,直链或带支链;
Y为O、S或CH2;/>
一种上述负载氧化锌纳米线静电纺丝膜层间增强增韧连续纤维增强树脂基复合材料的制备方法,包括:
先将连续纤维增强树脂基预浸片和负载氧化锌纳米线静电纺丝膜裁剪成与模具匹配的大小,根据复合材料的厚度在模具内铺设相应层数的所述连续纤维增强树脂基预浸片,并在相邻连续纤维增强树脂基预浸片之间铺放负载氧化锌纳米线静电纺丝膜;然后进行热压成型;最后降温冷却制成负载氧化锌纳米线静电纺丝膜层间增强增韧连续纤维增强树脂基复合材料。
在上述制备方法中,所述热压成型可以是本领域常规成型方法,比如标准大气压下的热压成型、真空热压成型或热压罐成型。
在上述制备方法中,作为一种优选实施方式,所述热压成型的成型温度为 50~400℃(比如60℃、80℃、120℃、150℃、200℃、250℃、300℃、350℃、380℃),成型压力为0.1~10MPa(比如0.5MPa、1.5MPa、2MPa、3MPa、5MPa、7MPa、 9MPa),保压时间为10分钟~20小时(比如15min、30min、1h、4h、8h、12h、 15h、18h)。具体成型温度需要根据树脂基体的不同而确定,达到热固性树脂的固化温度或热塑性树脂的加工温度即可。
在上述制备方法中,作为一种优选实施方式,当所述热压成型为真空热压成型或热压罐成型时,还需要保持真空度为-0.05~-0.099MPa(比如-0.06MPa、 -0.07MPa、-0.08MPa、-0.09MPa、-0.095MPa)。
本发明所述预浸片的制备方法包括但不限于溶液预浸法(比如可参见专利CN104031376中公开的方法)、熔融预浸法、悬浮颗粒预浸法、静电粉末浸渍法等,由于这些方法均为常规方法,本说明书不再赘述。
本发明的效果和益处:
本发明提供了一种具有优异层间性能的连续纤维增强树脂基复合材料及其制备方法。通过复合材料层间负载氧化锌纳米线静电纺丝膜的协同作用,显著提高连续纤维增强树脂基复合材料的层间韧性和层间剪切强度,有助于抑制复合材料分层。本发明涉及的负载氧化锌纳米线静电纺丝膜层间增强增韧连续纤维增强树脂基复合材料可应用于航空航天、海洋工程、新能源、石油化工、汽车、轨道交通等领域,具有广泛应用前景。
附图说明
图1是负载氧化锌纳米线静电纺丝膜扫描电镜照片;
图2为负载氧化锌纳米线静电纺丝膜模拟示意图。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,以使本领域的技术人员能够实践和再现。基于本发明中的实施例,本领域普通技术人员所获得的所有其他实施例,都属于本发明保护的范围。
下述实施例中的试验方法中,如无特殊说明,均为常规方法,可按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。
实施例1
复合材料的制备方法如下:
(1)将0.1g无水醋酸锌和2.8g杂萘联苯结构聚芳醚腈酮(PPENK)溶于 10g N,N-二甲基吡咯烷酮,配制得到静电纺丝溶液。
(2)将静电纺丝溶液通过静电纺丝机纺丝成含有氧化锌种子的PPENK静电纺丝膜,其中,纺丝电压为15KV,推进速度0.5mL/h,接收距离10cm。
(3)将得到的静电纺丝膜在240℃下保持8h,形成含有ZnO的静电纺丝膜。
(4)将得到的含有ZnO的静电纺丝膜在氧化锌生长液(硝酸锌浓度为 0.003mol/L,乌洛托品浓度为0.03mol/L,氨水质量浓度5%)中95℃生长30min,烘干水分后形成负载ZnO纳米线静电纺丝膜,ZnO纳米线的长度为1.5±0.2μm,参见图1和图2。
(5)取16片碳纤维/杂萘联苯结构聚芳醚酮(PPEK)树脂基预浸片(缩写为CF/PPEK,以PPEK为树脂基体,参照CN104031376中记载的方法制备,树脂基体体积含量37%,纤维体积含量63%),将面密度为3g/m2的负载ZnO纳米线静电纺丝膜分别铺放在连续碳纤维/杂萘联苯结构聚芳醚酮(PPEK)树脂基预浸料的相邻层间,在热压机中热压成型,成型温度为330℃,5MPa下保压30min,制备得到连续碳纤维增强树脂基复合材料层压板。
PPENK的结构如下:
m:n=1:1,数均分子量为1.5×104,玻璃化转变温度为278℃。
PPEK的结构如下:
数均分子量为1.8×104,玻璃化转变温度为263℃。
与未添加负载ZnO纳米线静电纺丝膜的复合材料层压板(具体制备参见对比例1)相比,其按照相应标准测定的Ⅰ型(ASTM D5528-13标准)和Ⅱ型层间断裂韧性(ASTM D7905标准)分别由0.82KJ/m2和1.2KJ/m2提高至0.93KJ/m2和 2.1KJ/m2;按照ISO 14130标准测定的层间剪切强度由60MPa提升至66MPa,弯曲强度(ASTM D790标准)从1294MPa提高到1324MPa,弯曲模量(ASTM D790 标准)从101GPa提升至105GPa。
实施例2
复合材料的制备方法如下:
(1)将0.05g无水醋酸锌和0.8g聚偏氟乙烯溶于10g N,N-二甲基甲酰胺,配制得到静电纺丝溶液,聚偏氟乙烯为阿科玛公司产品,密度为1.78g·cm-3,熔融指数为2.28g·min-1,长期使用温度可达150℃。
(2)将静电纺丝溶液通过静电纺丝机纺丝成静电纺丝膜,纺丝电压为18KV,推进速度1.5mL/h,接收距离25cm。
(3)将得到的静电纺丝膜在200℃下放置5h,形成含有ZnO的静电纺丝膜。
(4)将得到的含有ZnO的静电纺丝膜在氧化锌生长液(六水合硝酸锌浓度为0.08mol/L,乌洛托品浓度为0.1mol/L,氨水质量浓度15%)中80℃生长1h,烘干后形成负载ZnO纳米线静电纺丝膜,ZnO纳米线的长度为2.1±0.2μm。
(5)取16片连续玻璃纤维增强环氧树脂基预浸片(树脂基体体积含量32%,玻璃纤维体积含量68%,环氧树脂为E51,环氧当量为185,25℃粘度为8Pa·s),在预浸料层间铺放面密度为5g/m2负载ZnO纳米线聚偏氟乙烯静电纺丝膜,在真空热压机中真空热压成型,成型温度为100℃,真空度为-0.055MPa,0.5MPa下保压18小时,制备复合材料层压板。
与未添加负载ZnO纳米线静电纺丝膜的复合材料层压板(具体制备参见对比例2)相比,该复合材料按照相应标准测定的Ⅰ型(ASTM D5528-13标准)和Ⅱ型层间断裂韧性(ASTM D7905标准)分别由0.72KJ/m2和0.98KJ/m2提高至 0.92KJ/m2和1.72KJ/m2;按照ISO14130标准测定的层间剪切强度由36MPa提升至46MPa,弯曲强度(ASTM D790标准)从780MPa提高到850,弯曲模量 (ASTM D790标准)从45GPa提升至48GPa。
实施例3
复合材料的制备方法如下:
(1)将0.8g醋酸锌和1g聚醚砜溶于10g N,N-二甲基乙酰胺,配制得到静电纺丝溶液。
聚醚砜的结构如下:
数均分子量为5.3×104,玻璃化转变温度为225℃。
(2)将静电纺丝溶液通过静电纺丝机纺丝成静电纺丝膜,纺丝电压为21KV,推进速度1mL/h,接收距离15cm。
(3)将得到的静电纺丝膜在160℃下放置15h,形成含有ZnO的静电纺丝膜。
(4)将得到的含有ZnO的静电纺丝膜在氧化锌生长液(六水合硝酸锌浓度为0.001mol/L,乌洛托品浓度为0.001mol/L,氨水质量浓度8%)中110℃生长 2h,干燥后形成负载ZnO纳米线静电纺丝膜,ZnO纳米线的长度为3.4±0.2μm。
(5)取16片连续碳纤维增强双马树脂预浸料(树脂基体体积含量36%,纤维体积含量64%),在预浸料层间铺放面密度为32g/m2负载ZnO纳米线聚醚砜静电纺丝膜,在热压罐中真空热压成型,成型温度为210℃,真空度为-0.099MPa,在1.2MPa下保压7h,制备复合材料层压板。
双马树脂为二苯甲烷型双马来酰亚胺和烯丙基双酚A混合物,二者摩尔比为 1:0.8。
与未添加负载ZnO纳米线静电纺丝膜的复合材料层压板(具体制备参见对比例3)相比,其按照相应标准测定的Ⅰ型(ASTM D5528-13标准)和Ⅱ型层间断裂韧性(ASTM D7905标准)分别由0.40KJ/m2和1.05KJ/m2提高至0.55KJ/m2和1.75KJ/m2;按照ISO 14130标准测定的层间剪切强度由85MPa提升至 108MPa,弯曲强度(ASTM D790标准)从1350MPa提高到1410,弯曲模量(ASTM D790标准)从128GPa提升至136GPa。
实施例4
复合材料的制备方法如下:
(1)将0.08g醋酸锌和0.9g尼龙-66溶于10g甲酸中,配制得到静电纺丝溶液。
(2)将静电纺丝溶液通过静电纺丝机纺丝成静电纺丝膜,纺丝电压为15KV,推进速度8mL/h,接收距离15cm。
(3)将得到的静电纺丝膜在160℃下保持15h,形成含有ZnO的静电纺丝膜。
(4)将得到的含有ZnO的静电纺丝膜在氧化锌生长液(六水合硝酸锌浓度为0.08mol/L,乌洛托品浓度为0.08mol/L),氨水质量浓度5%)中110℃生长4h,干燥后形成负载ZnO纳米线静电纺丝膜,ZnO纳米线的长度为4.0±0.2μm。
(5)取16片连续玻璃纤维增强环氧乙烯基树脂预浸料(树脂基体体积含量 47%,纤维体积含量53%),在预浸料层间铺放面密度为35g/m2负载ZnO纳米线尼龙-66静电纺丝膜,在热压罐中真空热压成型,成型温度为60℃,真空度为 -0.05MPa,在0.8MPa下保压15h,制备复合材料层压板。
环氧乙烯基树脂的结构如下:
25℃的粘度不低于为245mPa·s。
该复合材料按照相应标准测定的Ⅰ型(ASTM D5528-13标准)和Ⅱ型层间断裂韧性(ASTM D7905标准)分别为0.40KJ/m2和1.05KJ/m2,按照ISO 14130 标准测定的层间剪切强度为45MPa,弯曲强度(ASTM D790标准)为460MPa,弯曲模量(ASTM D790标准)为26GPa。
实施例5
复合材料的制备方法如下:
(1)将0.12g醋酸锌和1.0g聚醚酰亚胺(PEI)溶于10g的N,N-二甲基乙酰胺溶剂中,配制得到含醋酸锌的静电纺丝溶液;将2.0g杂萘联苯聚芳醚砜 (PPES)溶于9gN,N-二甲基乙酰胺溶剂中配置静电纺丝溶液。
(2)采用同轴静电纺丝针头,通过同轴静电纺丝机纺丝(参考Composites Scienceand Technology.2019,175:143-150报道的同轴静电纺丝方法),制成以 PPES为核、PEI为壳的核壳结构静电纺丝膜,纺丝电压为15KV,推进速度1mL/h,接收距离15cm。
(3)将得到的核壳结构静电纺丝膜放入180℃烘箱放置10h,形成壳层含有 ZnO的核壳结构静电纺丝膜。
(4)将得到的含有ZnO种子的静电纺丝膜在氧化锌生长液(醋酸锌浓度为0.001mol/L,三乙醇胺浓度为0.03mol/L,氨水质量浓度6%)中110℃生长2h,干燥后形成负载ZnO纳米线的核壳结构静电纺丝膜,ZnO纳米线长度为2.1± 0.2μm。
(5)取16片连续碳纤维增强聚苯硫醚(PPS)树脂预浸料(树脂基体体积含量37%,纤维体积含量63%),在预浸料层间铺放面密度为10g/m2负载ZnO纳米线的杂萘联苯聚芳醚砜-聚醚酰亚胺核壳结构静电纺丝膜,在真空热压机中真空热压成型,成型温度为230℃,真空度为-0.085MPa,在5MPa下保压40min,制备复合材料层压板。
本实施例以外柔内刚的核壳结构静电纺丝膜层间增强增韧,以相对柔性的 PEI为壳,受外力冲击或载荷是,外层的柔性壳层有助于吸收能量。该复合材料Ⅰ型(ASTM D5528-13标准)和Ⅱ型层间断裂韧性(ASTM D7905标准)分别为0.95KJ/m2和1.8KJ/m2;按照ISO14130标准测定的层间剪切强度为98MPa,弯曲强度(ASTM D790标准)为1480MPa,弯曲模量(ASTM D790标准)为 120GPa。
PEI的结构为:
数均分子量为3.6×104,玻璃化转变温度为217℃。
PPES的结构如下:
数均分子量为2.6×104,玻璃化转变温度为305℃。
PPS为四川德阳科吉高新材料有限责任公司1000-300G型号树脂。
实施例6
复合材料的制备方法如下:
除了将实施例1中步骤(4)静电纺丝膜在氧化锌生长液中生长时间调整为1 小时(ZnO纳米线的长度为2.1±0.2μm)以外,其他工艺同实施例1。
该复合材料按照相应标准测定的Ⅰ型(ASTM D5528-13标准)和Ⅱ型层间断裂韧性(ASTM D7905标准)分别为1.12KJ/m2和2.6KJ/m2;按照ISO 14130 标准测定的层间剪切强度为78MPa,弯曲强度(ASTM D790标准)和弯曲模量(ASTM D790标准)分别为1360MPa和113GPa。
实施例7
除了将实施例1中步骤(4)静电纺丝膜在氧化锌生长液中生长时间调整为3 小时(ZnO纳米线的长度为2.9±0.2μm)以外,其他工艺同实施例1。
该复合材料按照相应标准测定的Ⅰ型(ASTM D5528-13标准)和Ⅱ型层间断裂韧性(ASTM D7905标准)分别为1.29KJ/m2和1.6KJ/m2;按照ISO 14130 标准测定的层间剪切强度为68MPa,弯曲强度(ASTM D790标准)和弯曲模量(ASTM D790标准)分别为1363MPa和114GPa。
对比例1
将16片连续碳纤维/杂萘联苯结构聚芳醚酮(PPEK)树脂基预浸片(预浸片和制备方法与实施例1一致,树脂基体体积含量37%,纤维体积含量63%)铺放在模具中,在热压机中根据热压工艺成型,成型温度为330℃,5MPa下保压 30min,制备得到连续碳纤维增强杂萘联苯结构聚芳醚酮树脂基复合材料层压板。
该复合材料按照相应标准测定的Ⅰ型断裂韧性(ASTM D5528-13标准)和Ⅱ型层间断裂韧性(ASTM D7905标准)分别为0.82KJ/m2和1.2KJ/m2;按照ISO 14130标准测定的层间剪切强度为60MPa,弯曲强度(ASTM D790标准)为 1294MPa,弯曲模量(ASTM D790标准)为101GPa。
对比例2
取16片连续玻璃纤维增强环氧树脂基预浸片(预浸片和制备方法与实施例2 一致,树脂基体体积含量32%,玻璃纤维体积含量68%),在真空热压机中真空热压成型,成型温度为100℃,真空度为-0.055MPa,0.5MPa下保压18小时,制备复合材料层压板。
该复合材料按照相应标准测定的Ⅰ型断裂韧性(ASTM D5528-13标准)和Ⅱ型层间断裂韧性(ASTM D7905标准)分别为0.72KJ/m2和0.98KJ/m2;按照 ISO 14130标准测定的层间剪切强度为36MPa,弯曲强度(ASTM D790标准)为 780MPa,弯曲模量(ASTM D790标准)为45GPa。
对比例3
取16片连续碳纤维增强双马树脂预浸片(预浸片和制备方法与实施例3一致,树脂基体体积含量36%,纤维体积含量64%),在热压罐中真空热压成型,成型温度为210℃,真空度为-0.099MPa,在1.2MPa下保压8h,制备复合材料层压板。
该复合材料按照相应标准测定的Ⅰ型断裂韧性(ASTM D5528-13标准)和Ⅱ型层间断裂韧性(ASTM D7905标准)分别为0.40KJ/m2和1.05KJ/m2;按照 ISO 14130标准测定的层间剪切强度为85MPa,弯曲强度(ASTM D790标准)为 1350MPa,弯曲模量(ASTM D790标准)为128GPa。
对比例4
复合材料的制备方法如下:
(1)将2.8g杂萘联苯结构聚芳醚腈酮(PPENK,结构同实施例1)溶于10g N,N-二甲基吡咯烷酮,配制得到静电纺丝溶液。
(2)将静电纺丝溶液通过静电纺丝机纺丝成PPENK静电纺丝膜,其中,纺丝电压为15KV,推进速度0.5mL/h,接收距离10cm。
(3)将得到的静电纺丝膜在240℃下保持8h。
(4)取16片碳纤维/杂萘联苯结构聚芳醚酮(PPEK,结构同实施例1)树脂基预浸片(缩写为CF/PPEK,以PPEK为树脂基体,参照CN104031376中记载的方法制备,树脂基体体积含量37%,纤维体积含量63%),将面密度为3g/m2的步骤(3)的静电纺丝膜分别铺放在连续碳纤维/杂萘联苯结构聚芳醚酮(PPEK) 树脂基预浸料的相邻层间,在热压机中热压成型,成型温度为330℃,5MPa下保压30min,制备得到连续碳纤维增强树脂基复合材料层压板。
该复合材料按照相应标准测定的Ⅰ型断裂韧性(ASTM D5528-13标准)和Ⅱ型层间断裂韧性(ASTM D7905标准)分别为0.86KJ/m2和1.7KJ/m2;按照ISO 14130标准测定的层间剪切强度为62MPa,弯曲强度(ASTM D790标准)为 1310MPa,弯曲模量(ASTM D790标准)为104GPa。
对比例5
除了将实施例1中的醋酸锌换为氧化锌以外,其他工艺同实施例1。
该复合材料按照相应标准测定的Ⅰ型断裂韧性(ASTM D5528-13标准)和Ⅱ型层间断裂韧性(ASTM D7905标准)分别为0.89KJ/m2和1.95KJ/m2;按照 ISO 14130标准测定的层间剪切强度为64MPa,弯曲强度(ASTM D790标准)为 1315MPa,弯曲模量(ASTM D790标准)为105GPa。
Claims (15)
1.一种负载氧化锌纳米线静电纺丝膜层间增强增韧连续纤维增强树脂基复合材料,其特征在于,所述复合材料是将多层连续纤维增强树脂基预浸片与设置在相邻连续纤维增强树脂基预浸片间的负载氧化锌纳米线静电纺丝膜压制成型得到的,其中,
所述连续纤维增强树脂基预浸片包括树脂基体以及分散于所述树脂基体中的纤维;
所述负载氧化锌纳米线静电纺丝膜包括热塑性树脂形成的静电纺丝纳米纤维膜以及生长于所述静电纺丝纳米纤维膜上的氧化锌纳米线,氧化锌纳米线自所述静电纺丝纳米纤维膜中纤维丝表面向外生长;
所述负载氧化锌纳米线静电纺丝膜是通过如下方法制备的:
步骤S1,含氧化锌种子剂的静电纺丝膜的制备:将含有热塑性树脂和氧化锌种子剂的静电纺丝液通过静电纺丝制成含氧化锌种子剂的静电纺丝膜;或者含氧化锌种子剂的核壳结构静电纺丝膜的制备:利用同轴针头,将含有氧化锌种子剂的壳层静电纺丝液和含热塑性树脂的核层静电纺丝液通过静电纺丝制成氧化锌种子剂作为壳、热塑性树脂纳米纤维作为核的含氧化锌种子剂的核壳结构静电纺丝膜;
步骤S2,将含氧化锌种子剂的静电纺丝膜或含氧化锌种子剂的核壳结构静电纺丝膜加热处理以使氧化锌种子剂分解为氧化锌,得到含有氧化锌的热塑性树脂静电纺丝膜;
步骤S3,将含有氧化锌的热塑性树脂静电纺丝膜浸入氧化锌生长液中进行氧化锌纳米线的生长,然后经干燥得到负载氧化锌纳米线静电纺丝膜。
2.根据权利要求1所述的复合材料,其特征在于,所述氧化锌纳米线的长度为0.5-5μm。
3.根据权利要求2所述的复合材料,其特征在于,设置在相邻连续纤维增强树脂基预浸片间的所述负载氧化锌纳米线静电纺丝膜的面密度为1~40g/m2。
4.根据权利要求1-3任一项所述的复合材料,其特征在于,所述多层连续纤维增强树脂基预浸片为至少3层连续纤维增强树脂基预浸片。
5.根据权利要求4所述的复合材料,其特征在于,所述连续纤维增强树脂基预浸片中,按照体积百分比,所述树脂基体的含量为30%~50%,所述纤维的含量为50%~70%。
6.根据权利要求1所述的复合材料,其特征在于,所述氧化锌种子剂为无水醋酸锌或醋酸锌水合物。
7.根据权利要求1所述的复合材料,其特征在于,
所述含有热塑性树脂和氧化锌种子剂的静电纺丝液是将热塑性树脂和氧化锌种子剂溶解于有机溶剂中制备而成的,其中,热塑性树脂占有机溶剂的质量百分比为1%~30%,氧化锌种子剂占有机溶剂的质量百分比为0.5~5%;
所述含有氧化锌种子剂的壳层静电纺丝液是将氧化锌种子剂和热塑性树脂溶于有机溶剂中制备而成的,其中氧化锌种子剂占有机溶剂的质量百分比为0.5~5%,热塑性树脂占有机溶剂的质量百分比为1%~30%;含热塑性树脂的核层静电纺丝液是将热塑性树脂溶于有机溶剂中制备而成的,其中热塑性树脂占有机溶剂的质量百分比为1%~30%。
8.根据权利要求7所述的复合材料,其特征在于,
所述有机溶剂包括:N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N,N-二甲基吡咯烷酮、二甲基亚砜、四氢呋喃、二氯甲烷、三氯甲烷、二氯乙烷、三氯乙烷、甲酸、乙酸中的一种或几种混合;
所述树脂基体包括:环氧树脂、双马来酰亚胺树脂、乙烯基树脂、异氰酸酯树脂、聚醚醚酮、聚醚酮酮、聚砜、聚醚砜、聚亚苯基砜、聚芳醚砜、聚芳醚酮、杂萘联苯结构聚芳醚、聚醚酰亚胺、聚苯硫醚、聚碳酸酯、聚酰胺、聚酯中的一种或几种;
所述纤维包括:碳纤维、玻璃纤维、玄武岩纤维、芳纶纤维、氮化硼纤维、石英纤维、聚苯并噁唑纤维、聚苯并咪唑纤维、陶瓷纤维、聚酰亚胺纤维、超高分子量聚乙烯纤维、聚苯硫醚纤维、聚酰胺酰亚胺纤维、聚苯撑吡啶并咪唑纤维中的一种或几种;
所述热塑性树脂包括:杂萘联苯结构聚芳醚、聚砜、聚醚砜、聚亚苯基砜、酚酞型聚芳醚砜、酚酞型聚芳醚酮、聚醚酰亚胺、聚苯硫醚、聚偏氟乙烯、聚酰胺、聚芳酰胺、聚酰亚胺、聚酰胺酰亚胺的一种或几种混合。
9.根据权利要求8所述的复合材料,其特征在于,
所述杂萘联苯结构聚芳醚具有如下结构:
其中,R1、R2、R3、R4是氢、卤素取代基、苯基、苯氧基、烷基或烷氧基,R1、R2、R3和R4的结构相同或不同;烷基或烷氧基中含有至少1个碳原子,直链或带支链;m≥10,n≥10;
—Ar1—的结构为以下的一种或几种混合:
R是氢、甲基、甲氧基、苯基、烷基或烷氧基,其中烷基或烷氧基都含有1至20个碳原子,直链或带支链;
—Ar2—的结构为以下的一种或几种混合:
1,2位、1,3位或1,4位;
2,2′位或4,4′位;
1,4位、1,5位、1,6位、2,6位或2,7位;
3,3′位或4,4′位;
3,3′位或4,4′位;
3,3′位或4,4′位;
3,3′位或4,4′位;
3,3′位或4,4′位;
R1、R2、R3、R4是氢、卤素取代基、苯基、苯氧基、烷基或烷氧基,R1、R2、R3和R4的结构相同或不同;烷基或烷氧基中含有至少1个碳原子,直链或带支链;
Y为O、S或CH2;
10.根据权利要求1所述的复合材料,其特征在于,步骤S1中,静电纺丝的条件为:推进速度0.1~10.0mL/h,电压8~30KV,接收距离8~30cm。
11.根据权利要求1所述的复合材料,其特征在于,步骤S2中,所述加热处理的条件为:加热温度为150~250℃,保温时间为0.5~15h。
12.根据权利要求1所述的复合材料,其特征在于,步骤S3中,所述氧化锌纳米线的生长条件为:在80~110℃下生长10分钟~5小时。
13.根据权利要求1所述的复合材料,其特征在于,所述的氧化锌生长液包括以下组分:硝酸锌或其水合物、醋酸锌或其水合物的一种或两种混合,摩尔浓度为0.001~0.1mol/L;乌洛托品或三乙醇胺的一种或两种混合,摩尔浓度为0.001~0.1mol/L;氨水,质量浓度1%~20%;溶剂水。
14.一种如权利要求1-13任一项所述负载氧化锌纳米线静电纺丝膜层间增强增韧连续纤维增强树脂基复合材料的制备方法,其特征在于,包括:
先将连续纤维增强树脂基预浸片和负载氧化锌纳米线静电纺丝膜裁剪成与模具匹配的大小,根据复合材料的厚度在模具内铺设相应层数的所述连续纤维增强树脂基预浸片,并在相邻连续纤维增强树脂基预浸片之间铺放负载氧化锌纳米线静电纺丝膜;然后进行热压成型;最后降温冷却制成负载氧化锌纳米线静电纺丝膜层间增强增韧连续纤维增强树脂基复合材料。
15.根据权利要求14所述的制备方法,其特征在于,所述热压成型的成型温度为50~400℃,成型压力为0.1~10MPa,保压时间为10分钟~20小时;
当所述热压成型为真空热压成型或热压罐成型时,保持真空度为-0.05~-0.099MPa。
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