CN112208161B - Layered fibrous body toughened resin-based composite material and preparation method thereof - Google Patents
Layered fibrous body toughened resin-based composite material and preparation method thereof Download PDFInfo
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- CN112208161B CN112208161B CN202010926132.2A CN202010926132A CN112208161B CN 112208161 B CN112208161 B CN 112208161B CN 202010926132 A CN202010926132 A CN 202010926132A CN 112208161 B CN112208161 B CN 112208161B
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- fiber
- mixing
- mixed solution
- fiber cloth
- fiber preform
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- 239000000463 material Substances 0.000 title claims abstract description 40
- 239000000805 composite resin Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000835 fiber Substances 0.000 claims abstract description 334
- 239000004744 fabric Substances 0.000 claims abstract description 118
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 55
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 55
- 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 abstract description 53
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002131 composite material Substances 0.000 claims abstract description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000005530 etching Methods 0.000 claims abstract description 20
- 230000004048 modification Effects 0.000 claims abstract description 17
- 238000012986 modification Methods 0.000 claims abstract description 17
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- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000003825 pressing Methods 0.000 claims abstract description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 239000008367 deionised water Substances 0.000 claims description 45
- 229910021641 deionized water Inorganic materials 0.000 claims description 45
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 39
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 36
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 33
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- 238000002791 soaking Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 23
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 21
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- 238000005406 washing Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 230000005415 magnetization Effects 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 229940071870 hydroiodic acid Drugs 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011347 resin Substances 0.000 abstract description 15
- 229920005989 resin Polymers 0.000 abstract description 15
- 239000011159 matrix material Substances 0.000 abstract description 11
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- 230000009471 action Effects 0.000 abstract description 2
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- 238000000465 moulding Methods 0.000 description 40
- 229960001922 sodium perborate Drugs 0.000 description 30
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 19
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 17
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- 125000000524 functional group Chemical group 0.000 description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
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- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 9
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 9
- 238000007731 hot pressing Methods 0.000 description 9
- 239000000395 magnesium oxide Substances 0.000 description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 9
- 229910001928 zirconium oxide Inorganic materials 0.000 description 9
- 230000001680 brushing effect Effects 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 8
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
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- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 1
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- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- ZLMJMSJWJFRBEC-OUBTZVSYSA-N potassium-40 Chemical compound [40K] ZLMJMSJWJFRBEC-OUBTZVSYSA-N 0.000 description 1
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Images
Classifications
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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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- 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
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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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- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- 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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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/30—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with oxides of halogens, oxyacids of halogens or their salts, e.g. with perchlorates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/165—Ethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/59—Polyamides; Polyimides
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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
- B32B2250/00—Layers arrangement
- B32B2250/20—All layers being fibrous or filamentary
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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
- B32B2255/00—Coating on the layer surface
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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
- B32B2260/021—Fibrous or filamentary layer
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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
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Mechanical Engineering (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a laminated fibrous body toughened resin-based composite material and a preparation method thereof. The preparation method comprises the following steps: carrying out surface etching and hydroxylation treatment on aluminum silicate fiber cloth to obtain a fiber preform A; sequentially carrying out hot filling treatment on the alumina fiber cloth by using a silica sol solution and surface modification on the carbon nano tube to obtain a fiber preform C; and coating polyamide resin solution on the surfaces of the fiber preform A and the fiber preform C, laying in a lamination way, and pressing and forming to obtain the layered fiber toughening resin matrix composite material. According to the preparation method, the modification group is introduced into the interface of the fiber layer, so that the microstructure of the fiber interface and the mechanical combination action between fibers in different component directions are effectively improved, and the excellent mechanical property is presented macroscopically.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a layered fibrous toughened resin-based composite material and a preparation method thereof.
Background
The mechanical strength of the oxide fiber is easily reduced greatly at high temperature, the sintering temperature of the traditional ceramic material is too high, the liquid phase is generated and the solid phase driving force is improved by adding a sintering aid and the like to the oxide resin matrix, but the effect of improving the mechanical property by the method is limited. At present, the high-performance fiber in China seriously depends on foreign import and is limited by certain technical blockade, and the realization of the mass production of the high-performance oxide fiber in China is one of the key breakthroughs in the preparation technology of the high-temperature oxide/oxide resin matrix composite material. The current commercial fibers mainly develop polycrystalline fibers, and how to realize the uniform dispersion of multiphase components and the reasonable design of structural components of the fibers is the key point for making technical breakthrough, which is also the development trend of oxide fibers in the future.
Disclosure of Invention
The invention aims to provide a layered fibrous toughening resin matrix composite and a preparation method thereof, and the method effectively improves the microstructure of a fiber interface and the mechanical bonding effect between fibers in different groups by introducing a modifying group into the interface of a fiber layer, and shows excellent mechanical properties macroscopically.
In order to achieve the purpose, the invention adopts the technical scheme that:
in a first aspect, the invention provides a preparation method of a layered fibrous toughened resin-based composite material, which comprises the following steps:
the method comprises the following steps: aluminum silicate fiber cloth is prepared by mixing 3-6 parts by mass of liquid to solid: 1, placing the fiber preform A in a solution containing ethylene glycol monomethyl ether, then using a solution containing hydroiodic acid to adjust the pH value to 3-4, soaking for 2-3 h, taking out the aluminum silicate fiber cloth, washing and drying to obtain a fiber preform A subjected to surface etching and hydroxylation treatment;
step two: mixing alumina fiber cloth in a liquid-solid mass ratio of 4-8: 1, soaking in a solution containing silica sol at the temperature of 60-80 ℃ for hot filling treatment for 1-2 h, and then adjusting the pH value to 8-9 by using a solution containing isobutanolamine to obtain a mixed precursor solution B;
step three: taking 80-120 g of the mixed precursor liquid B, transferring the mixed precursor liquid B into a magnetic induction reaction kettle, adding 5-15 g of carbon nano tubes, then adding aluminum sheets into the magnetic induction reaction kettle to serve as magnetic induction bodies, treating for 8-10 hours at the magnetic induction frequency of 600-1220 KHz and the magnetization temperature of 200-400 ℃, taking out and drying the alumina fiber cloth, and obtaining a fiber preform C subjected to surface modification of the carbon nano tubes;
step four: respectively coating solutions containing polyamide resin on the surfaces of the fiber preform A and the fiber preform C subjected to surface modification by the carbon nano tube, and placing the two fiber preforms in a laminated manner to obtain a fiber composite D;
step five: and pressing and forming the fiber composite D to obtain the layered fiber toughened resin-based composite material.
Preferably, the coating amounts of the solution containing polyamide resin on the surfaces of the fiber preform A and the fiber preform C surface-modified by the carbon nanotube are 6 to 10g/m, respectively 2 And 12 to 16g/m 2 。
Preferably, the solution containing ethylene glycol monomethyl ether in the first step is prepared by mixing 50-70% of ethylene glycol monomethyl ether, 10-30% of sodium tripolyphosphate and 20-40% of deionized water according to the mass ratio.
Preferably, the solution containing hydriodic acid in the first step is prepared by mixing 70-80% of hydriodic acid, 10-20% of ethyl orthosilicate and 10-20% of ethylene glycol according to the volume ratio.
Preferably, the solution containing silica sol in the second step is prepared by mixing 50-70% of silica sol, 10-20% of sodium tripolyphosphate and 20-40% of deionized water according to the mass ratio.
Preferably, the solution containing the isobutanolamine in the second step is formed by mixing 40-60% of isobutanolamine, 20-40% of potassium hydroxide and 20-40% of deionized water in percentage by mass.
Preferably, the temperature of the solution containing the polyamide resin in the fourth step is 80-100 ℃, and the solution is prepared by mixing 40-60% of the polyamide resin, 10-30% of polyvinyl alcohol and 30-50% of deionized water according to the volume ratio.
Preferably, the number of the laminated layers is 50-80; preferably, the fiber preforms A are placed in a lamination mode, and at least one layer of carbon nanotube surface modified fiber preform C is arranged between the adjacent fiber preforms A.
In a second aspect, the invention provides a laminated fiber toughened resin-based composite material obtained by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
according to the property difference of different fiber bodies, the invention creates a 'two-phase complementary' composite mode, and the surface modification and etching are carried out on the fibers in the aluminum silicate fiber cloth by introducing low-cost reagents such as hydroiodic acid, ethylene glycol monomethyl ether and the like, so that the interface bonding force and the dispersion performance between different fibers are improved, the lamination and the composition of the aluminum silicate fiber cloth with high melting point and poor thermal shock resistance and the aluminum oxide fiber cloth with low melting point and good thermal shock resistance are realized, the mechanical defect of single-phase fiber cloth is effectively avoided, and a three-dimensional fiber composite system of 'two-phase fibers-resin matrix' with excellent mechanical property is constructed. The preparation method disclosed by the invention is simple in production process, has the potential of realizing large-scale industrial production, is wide in raw material source, relatively low in cost and environment-friendly, and the prepared composite material is high in density, good in chemical stability, strong in thermal shock resistance, excellent in mechanical property and wide in application prospect.
Drawings
FIG. 1 is a sectional scanning electron microscope test chart of the modified layered fibrous body toughened resin-based composite material prepared in example 1 of the present invention.
FIG. 2 is a scanning electron microscope test chart of microcracks of the modified lamellar fiber toughened resin-based composite material prepared in example 2 of the present invention.
Detailed Description
The preparation method of the layered fibrous body toughened resin-based composite material of the present invention is exemplified as follows.
The aluminum silicate fiber cloth is prepared by mixing 3-6 parts by mass of liquid to solid: 1 is soaked in the mixed solution of ethylene glycol monomethyl ether. By way of example, the aluminum silicate fiber cloth is a combined needled felt body and comprises, by mass, 40-60% of chopped strand felt, 20-40% of untwisted roving cloth and 20-40% of chopped yarns. For example, the aluminum silicate fiber cloth comprises, by mass, 30 to 50% of aluminum silicate, 20 to 40% of zirconium oxide, 20 to 40% of titanium oxide, and 10 to 30% of beryllium oxide. In some embodiments, the ethylene glycol monomethyl ether mixed solution is formed by mixing 50-70% of ethylene glycol monomethyl ether, 10-30% of sodium tripolyphosphate and 20-40% of deionized water in a mass ratio. Compared with single surface modification of hydroxyl reagents such as ethanol and the like, the ethylene glycol monomethyl ether heterogeneous functional groups are rich in variety, the polyhydroxy group of the ethylene glycol monomethyl ether and the water molecule of the fiber surface structure are easily crosslinked in a hydrogen bond form, the wetting depth is deeper, the combination performance is more excellent, the breakthrough of the structural infiltration technology from the surface to the interior of a fibrous body is successfully realized, and the introduction efficiency of the modified functional groups is higher.
And dropwise adding the modified hydriodic acid mixed solution to adjust the pH value to 3-4. The hydriodic acid mixed solution can be prepared by mixing 70-80% of hydriodic acid, 10-20% of ethyl orthosilicate and 10-20% of ethylene glycol according to the volume ratio. And taking out the aluminum silicate fiber cloth after soaking for 2-3 h.
And (3) washing and drying the aluminum silicate fiber cloth to obtain the fiber preform A subjected to surface etching and modification treatment. Washing may be performed using a sodium perborate mixed solution. The sodium perborate solution releases nascent oxygen on the surface of the aluminum silicate fiber cloth as a protective layer in the washing process, and the attachment of the nascent oxygen also provides a binding space point for the introduction of hydroxyl and amino, so that the introduction efficiency of heterogeneous functional groups is improved. In addition, compared with acid washing reagents such as hydrochloric acid, sulfuric acid and the like, the sodium perborate solution has smaller damage to the fiber and does not damage the original two-dimensional structure of the fiber. And washing for 5-8 times until the fiber surface is fully soaked and cleaned. For example, the sodium perborate mixed solution is prepared by mixing 40-60% of sodium perborate, 20-40% of sodium hydroxide and 20-40% of polyvinyl alcohol according to the mass ratio. For example, washing with sodium perborate mixed solution for 5-8 times, and drying at 60-90 deg.C.
The steps adopt mixed solution of hydroiodic acid and ethylene glycol monomethyl ether to carry out integrated surface etching and hydroxylation treatment on the aluminum silicate fiber cloth. The hydroxylation treatment refers to "introduction of hydroxyl groups on the surface and inside of the aluminum silicate fibers". Hydroxyl is endowed on the surface of the aluminum silicate, which is beneficial to the interface combination between the modified aluminum silicate fiber cloth and the carbon nano tube modified alumina fiber cloth. The attachment of the hydroxyl and the multifunctional group on the fiber body can play a role in connecting the fiber body and the resin body, the fiber body has gradient concentration of heterogeneous functional groups from the surface to the inner layer, the gradient composite structure obtained after the fiber body is combined with the resin and formed is more compact, and the interlayer structure without surface modification is easy to fall off. The hydriodic acid solution realizes acidification treatment on the ethylene glycol monomethyl ether mixed solution while etching the fiber surface, the ethylene glycol monomethyl ether mixed solution is easy to decompose hydroxyl groups under the slightly acidic condition, the separation of the hydroxyl groups and the embedding rate at an etching interface are accelerated, and the group embedding space and the three-dimensional pore structure of a fiber body are optimized. The hydrofluoric acid etches a plurality of tiny holes on the surface of the fiber, increases the specific surface area and the roughness of the fiber body, is beneficial to the attachment of heterogeneous functional groups on the fiber body and the structural etching modification of the fiber body, improves the efficiency of interface reaction (the hydroxyl, amino and other groups are endowed through the interface modification), and effectively avoids the occurrence of side reaction. And the steps are distributed, so that the phenomenon that the compounding effect is seriously influenced due to uncontrollable side reaction caused by too complicated introduced components in a one-step method is avoided.
And (2) mixing alumina fiber cloth in a liquid-solid mass ratio of 4-8: 1 soaking the mixture in a silica sol mixed solution at the temperature of 60-80 ℃ for hot filling treatment for 1-2 h. The alumina fiber cloth is subjected to hot filling by using the silica sol, so that the exhaust of gas in the sol is accelerated by the hot filling, energy is provided for the combination of chemical bonds of groups and fiber bodies, the whole reaction process is accelerated, the curing time of the silica sol mixed solution is shortened, and the reaction period is shortened. For example, the alumina fiber cloth is a combined needled felt body, and is formed by combining 40-60% of chopped strand felt, 20-40% of untwisted roving cloth and 20-40% of chopped strand according to the mass ratio. For example, the alumina fiber comprises, by mass, 30 to 50% of alumina, 20 to 40% of magnesia, 20 to 40% of titania, and 10 to 30% of strontium oxide. In some embodiments, the silica sol mixed solution is prepared by mixing 50-70% of silica sol (the silica sol is from Nicotine Henxin chemical industry, model S-S30), 10-20% of sodium tripolyphosphate and 20-40% of deionized water according to the mass. The sodium tripolyphosphate is added into the silica sol mixed solution, so that the viscosity of the silica sol mixed solution can be adjusted, and the subsequent efficient infiltration of the silica sol is facilitated.
And then dropwise adding an isobutanolamine mixed solution into the mixed solution containing the alumina fiber cloth and the silica sol to adjust the pH value to 8-9, thereby obtaining a mixed precursor solution B. The purpose of using the isobutanolamine is to adjust the pH of the solution while introducing amine groups. The mixed solution of the isobutanolamine is formed by mixing 40-60% of isobutanolamine, 20-40% of potassium hydroxide and 20-40% of deionized water according to the mass ratio.
When the silica sol multi-component mixed solution is adopted to carry out preliminary densification filling on the alumina fiber cloth, the isobutanol amine modified solvent is uniformly permeated into the interior of the fiber body, the composite process of amino groups on the surface of the alumina fiber cloth is accelerated in an alkaline environment, the efficiency of interface reaction is improved, the distribution of multi-element groups in the fiber is adjusted, the tight combination with resin in subsequent steps is facilitated, and the three-dimensional space structure in the fiber body is optimized.
And (2) taking 80-120 g of the mixed precursor solution B, transferring the mixed precursor solution B to a magnetic induction reaction kettle, adding 5-15 g of carbon nano tubes, adding aluminum sheets with the length, width and height of 3cm, 2cm and 2cm respectively into the magnetic induction reaction kettle to serve as magnetic induction bodies, and treating for 8-10 hours at the magnetic induction frequency of 600-1220 KHz and the magnetization temperature of 200-400 ℃. And taking out the modified fiber body, and drying in an ultraviolet oven at the temperature of 80-100 ℃ to obtain the fiber preform C subjected to surface modification by the carbon nano tube.
According to the invention, the porous carbon nanotube is innovatively introduced to the surface and the interior of the fiber body to serve as a bearing body of a functional group, and the etching on the surface of the porous carbon nanotube is realized by means of magnetic induction solid-phase reaction. It is noted that magnetically induced solid phase reactions may not be replaced by simple "heating" or "hydrothermal reactions". Because the magnetic induction reaction has high heating efficiency, ultrasonic treatment can be assisted in the heating process, the uniform distribution of the carbon nano tubes on the surface and inside of the fiber body is favorably realized, and the rotary stirring of the hydrothermal reaction is uncontrollable and easily damages the original compact structure and mechanical property of the fiber. Meanwhile, the porous carbon nanotubes are uniformly introduced into the fiber body, so that more space points are provided for the introduction of organic functional groups while the specific surface area of the fiber body is increased, and the distribution of lattice defects in the fiber body can be effectively improved. Besides the enhancement and toughening, after the porous carbon nanotube is subjected to etching treatment, a plurality of multifunctional groups of attachment sites are generated inside the porous carbon nanotube, the porous carbon nanotube plays a role of serving as an excellent supporting body of heterogeneous functional groups, and compared with a mode of introducing functional groups by liquid infiltration, the efficiency is better, the comprehensive mechanical property of the fiber body is promoted, and the enhancement and toughening effects of the three-dimensional fiber body at high temperature are guaranteed.
Cutting the fiber preform A and the carbon nanotube surface modified fiber preform C into a specified shape, and combining the polyamide resin mixed solution with the two cut fiber preforms. For example, the polyamide resin mixed solution is coated on the surfaces of the two fiber preforms respectively by a hot brush coating method or a hot spray gun spraying method. In some embodiments, the temperature of the polyamide resin mixture is 80-100 ℃, and the polyamide resin mixture is prepared by mixing 40-60% of polyamide resin, 10-30% of polyvinyl alcohol and 30-50% of deionized water in volume ratio. The polyamide resin solution is sprayed on the surfaces of the aluminum silicate fiber cloth and the aluminum oxide fiber cloth, so that the connection effect is mainly achieved and a compact gradient structure is formed.
And (3) sequentially aligning and laminating the two fiber preforms coated with the polyamide resin mixed solution up and down to obtain a fiber composite body D. In some embodiments, the number of stacked layers is 50 to 80.
And (3) placing the fiber composite body D in a mould for compression molding. For example by means of a hot press. And after the mould and the material are physically separated, obtaining the modified layered fibrous body toughened resin matrix composite material. For example, the molding temperature is 80-120 ℃, the molding pressure is 120-160 MPa, and the molding period is 30-90 min.
The present invention will be described in further detail with reference to preferred embodiments thereof.
Example 1
The method comprises the following steps: aluminum silicate fiber cloth is prepared by mixing, by mass, 4: 1, soaking the fiber cloth in ethylene glycol monomethyl ether mixed solution, dropwise adding the modified hydroiodic acid mixed solution to adjust the pH value to 3, taking out the fiber cloth after soaking for 3 hours, washing the fiber cloth for 5 times by using sodium perborate mixed solution, and drying the fiber cloth at 60 ℃ to obtain a fiber preform A subjected to surface etching and hydroxylation treatment;
the aluminum silicate fiber cloth is a combined needled felt body and consists of 40% of chopped strand felt, 20% of untwisted roving gauze and 40% of chopped yarn in mass ratio, and the aluminum silicate fiber cloth comprises 50% of aluminum silicate, 20% of zirconium oxide, 20% of titanium oxide and 10% of beryllium oxide in mass ratio;
the ethylene glycol monomethyl ether mixed solution is formed by mixing 50% of ethylene glycol monomethyl ether, 30% of sodium tripolyphosphate and 20% of deionized water according to the mass ratio;
the hydriodic acid mixed solution is prepared by mixing 70% of hydriodic acid, 10% of ethyl orthosilicate and 20% of ethylene glycol according to the volume ratio;
the sodium perborate mixed solution is prepared by mixing 40% of sodium perborate, 20% of sodium hydroxide and 40% of polyvinyl alcohol according to the mass ratio;
step two: mixing alumina fiber cloth in a liquid-solid mass ratio of 4: 1, soaking the mixture in a silica sol mixed solution at the temperature of 60 ℃ for hot filling treatment for 1h, and then dropwise adding an isobutanolamine mixed solution to adjust the pH value to 8 to obtain a mixed precursor solution B;
the aluminum oxide fiber cloth is a combined needled felt body and is formed by combining 45% of chopped strand mats, 25% of untwisted roving and 30% of chopped yarns in mass ratio, and the aluminum oxide fiber cloth comprises 30% of aluminum oxide, 40% of magnesium oxide, 20% of titanium oxide and 10% of strontium oxide in mass ratio;
the silica sol mixed solution is formed by mixing 55% of silica sol, 15% of sodium tripolyphosphate and 30% of deionized water according to the mass ratio;
the isobutanolamine mixed solution is formed by mixing 45% of isobutanolamine, 25% of potassium hydroxide and 30% of deionized water in a mass ratio;
step three: taking 80g of the mixed precursor solution B, transferring the mixed precursor solution B into a magnetic induction reaction kettle, adding 5g of carbon nano tubes into the magnetic induction reaction kettle, adding aluminum sheets with the length, width and height of 3cm, 2cm and 2cm respectively into the magnetic induction reaction kettle as magnetic induction bodies, treating the magnetic induction bodies for 9 hours at the magnetic induction frequency of 600KHz and the magnetization temperature of 350 ℃, taking out the modified alumina fiber cloth, and drying the modified alumina fiber cloth in an ultraviolet oven at the temperature of 80 ℃ to obtain a fiber preform C with the surface modified by the carbon nano tubes;
step four: cutting the fiber preform A and the fiber preform C subjected to surface modification by the carbon nano tube into rectangles with the length of 10-15 cm and the width of 4-8 cm, combining polyamide resin mixed liquor and the two cut fiber preforms by adopting a hot brushing or hot spray gun spraying method, wherein the use amounts of the polyamide resin mixed liquor on the surfaces of the fiber preform A and the fiber preform C subjected to surface modification by the carbon nano tube are 8g/m 2 And 14g/m 2 Sequentially aligning the two fiber preforms up and down and superposing the two fiber preforms to 50 layers to obtain a fiber composite D;
wherein the temperature of the polyamide resin mixed solution is 80 ℃, and the polyamide resin mixed solution is prepared by mixing 40% of polyamide resin, 10% of polyvinyl alcohol and 50% of deionized water according to the volume ratio;
step five: and (3) putting the fiber composite body D into a mold for compression molding at the molding temperature of 80 ℃ and the molding pressure of 160MPa in a molding cycle of 50min by using a hot-pressing molding machine with the model number of SYD-0704, and physically separating the mold from the material to obtain the modified layered fiber body toughened resin-based composite material.
From fig. 1 it can be seen that the three-dimensional fibrous body is structurally dense, with two different fibers being tightly bonded. In the process of fiber fracture, the fracture opening position is uniformly extended, and partial fibers have a pull-out effect, which shows that the interface bonding force of the fibers and the resin matrix is proper, and the fibers effectively assist the matrix to share the stress action of an external load.
Example 2
The method comprises the following steps: aluminum silicate fiber cloth is prepared by mixing, by mass, 4: 1, soaking the fiber cloth in ethylene glycol monomethyl ether mixed solution, dropwise adding the modified hydriodic acid mixed solution to adjust the pH value to 3.5, taking out the fiber cloth after soaking for 2.5 hours, washing the fiber cloth for 6 times by using sodium perborate mixed solution, and drying the fiber cloth at 80 ℃ to obtain a fiber preform A subjected to surface etching and hydroxylation treatment;
the aluminum silicate fiber cloth is a combined needled felt body and consists of 60% of chopped strand felt, 20% of untwisted roving gauze and 20% of chopped yarn in mass ratio, and the aluminum silicate fiber cloth comprises 30% of aluminum silicate, 30% of zirconium oxide, 25% of titanium oxide and 15% of beryllium oxide in mass ratio;
the ethylene glycol monomethyl ether mixed solution is formed by mixing 70% of ethylene glycol monomethyl ether, 10% of sodium tripolyphosphate and 20% of deionized water according to the mass ratio;
the hydriodic acid mixed solution is formed by mixing 80% hydriodic acid, 10% ethyl orthosilicate and 10% ethylene glycol according to the volume ratio;
the sodium perborate mixed solution is prepared by mixing 60% of sodium perborate, 20% of sodium hydroxide and 20% of polyvinyl alcohol according to the mass ratio;
step two: mixing alumina fiber cloth in a liquid-solid mass ratio of 6: 1, soaking the mixture in a silica sol mixed solution at the temperature of 75 ℃ for hot filling treatment for 1.5h, and then dropwise adding an isobutanolamine mixed solution to adjust the pH value to 8.5 to obtain a mixed precursor solution B;
the aluminum oxide fiber cloth is a combined needled felt body and is formed by combining 40% of chopped strand mats, 30% of untwisted roving and 30% of chopped yarns in mass ratio, and the aluminum oxide fiber cloth comprises 30% of aluminum oxide, 30% of magnesium oxide, 25% of titanium oxide and 15% of strontium oxide in mass ratio;
the silica sol mixed solution is formed by mixing 50% of silica sol, 20% of sodium tripolyphosphate and 30% of deionized water according to the mass ratio;
the isobutanolamine mixed solution is formed by mixing 40% of isobutanolamine, 30% of potassium hydroxide and 30% of deionized water according to the mass ratio;
step three: taking 100g of the mixed precursor solution B, transferring the mixed precursor solution B into a magnetic induction reaction kettle, adding 10g of carbon nano tubes into the magnetic induction reaction kettle, adding aluminum sheets with the length, width and height of 3cm, 2cm and 2cm respectively into the magnetic induction reaction kettle as magnetic induction bodies, treating the magnetic induction bodies at the magnetic induction frequency of 800KHz and the magnetization temperature of 400 ℃ for 8 hours, taking out the modified alumina fiber cloth, and drying the modified alumina fiber cloth in an ultraviolet oven at the temperature of 90 ℃ to obtain a fiber preform C with the surface modified by the carbon nano tubes;
step four: cutting the fiber preform A and the carbon nano tube surface modified fiber preform C into rectangles with the length of 10-15 cm and the width of 4-8 cm, combining polyamide resin mixed liquor and the two cut fiber preforms by adopting a hot brushing or hot spray gun spraying method, wherein the use amounts of the polyamide resin mixed liquor on the surfaces of the fiber preform A and the carbon nano tube surface modified fiber preform C are 8g/m 2 And 14g/m 2 Sequentially placing the two fiber preforms in an up-down alignment manner and overlapping the two fiber preforms to 60 layers to obtain a fiber composite D;
wherein the temperature of the polyamide resin mixed solution is 90 ℃, and the polyamide resin mixed solution is prepared by mixing 60% of polyamide resin, 10% of polyvinyl alcohol and 30% of deionized water according to the volume ratio;
step five: and (3) putting the fiber composite body D into a mold for compression molding at the molding temperature of 100 ℃ and the molding pressure of 130MPa in the molding period of 30min by using a hot-pressing molding machine with the model number of SYD-0704, and physically separating the mold from the material to obtain the modified layered fiber body toughened resin-based composite material.
It can be seen from fig. 2 that the crack changes path direction as it propagates at the single fiber interface. Therefore, the crack is spread at the fiber interface, the fiber is expanded or broken along the fiber due to the blocking effect of the fiber, the material can be damaged only by external larger load and energy, macroscopically, the strength and toughness of the material are improved, the composite material can absorb more fracture energy and bear larger external stress, and the comprehensive mechanical property is excellent.
Example 3
The method comprises the following steps: aluminum silicate fiber cloth is prepared by mixing, by mass, 4: 1, soaking the fiber cloth in ethylene glycol monomethyl ether mixed solution, dropwise adding the modified hydroiodic acid mixed solution to adjust the pH value of the mixed solution to 4, taking out the fiber cloth after soaking for 3 hours, washing the fiber cloth for 8 times by using sodium perborate mixed solution, and drying the fiber cloth at 90 ℃ to obtain a fiber preform A subjected to surface etching and hydroxylation treatment;
the aluminum silicate fiber cloth is a combined needled felt body and consists of 40% of chopped strand felt, 40% of untwisted roving gauze and 20% of chopped yarn in mass ratio, and the aluminum silicate fiber cloth comprises 30% of aluminum silicate, 40% of zirconium oxide, 20% of titanium oxide and 10% of beryllium oxide in mass ratio;
the ethylene glycol monomethyl ether mixed solution is formed by mixing 50% of ethylene glycol monomethyl ether, 10% of sodium tripolyphosphate and 40% of deionized water according to the mass ratio;
the hydriodic acid mixed solution is formed by mixing 70% hydriodic acid, 20% ethyl orthosilicate and 10% ethylene glycol according to the volume ratio;
the sodium perborate mixed solution is prepared by mixing 50% of sodium perborate, 25% of sodium hydroxide and 25% of polyvinyl alcohol according to the mass ratio;
step two: and (2) mixing alumina fiber cloth in a liquid-solid mass ratio of 5: 1, soaking the mixture in a 65 ℃ silica sol mixed solution for hot filling treatment for 2 hours, and then dropwise adding an isobutanolamine mixed solution to adjust the pH value to 9 to obtain a mixed precursor solution B;
the aluminum oxide fiber cloth is a combined needled felt body and is formed by combining 50% of chopped strand mats, 25% of untwisted roving and 25% of chopped yarns in mass ratio, and the aluminum oxide fiber cloth comprises 50% of aluminum oxide, 20% of magnesium oxide, 20% of titanium oxide and 10% of strontium oxide in mass ratio;
the silica sol mixed solution is formed by mixing 60% of silica sol, 10% of sodium tripolyphosphate and 30% of deionized water according to the mass ratio;
the isobutanolamine mixed solution is formed by mixing 50% of isobutanolamine, 25% of potassium hydroxide and 25% of deionized water according to the mass ratio;
step three: taking 90g of the mixed precursor solution B, transferring the mixed precursor solution B into a magnetic induction reaction kettle, adding 8g of carbon nano tubes into the magnetic induction reaction kettle, adding aluminum sheets with the length, width and height of 3cm, 2cm and 2cm respectively into the magnetic induction reaction kettle as magnetic induction bodies, treating the magnetic induction bodies for 10 hours at the magnetic induction frequency of 1000KHz and the magnetization temperature of 200 ℃, taking out the modified fiber bodies, and drying the modified fiber bodies in an ultraviolet oven at the temperature of 100 ℃ to obtain a fiber preform C with the surface modified by the carbon nano tubes;
step four: cutting the fiber preform A and the carbon nano tube surface modified fiber preform C into rectangles with the length of 10-15 cm and the width of 4-8 cm, combining polyamide resin mixed liquor and the two cut fiber preforms by adopting a hot brushing or hot spray gun spraying method, wherein the use amounts of the polyamide resin mixed liquor on the surfaces of the fiber preform A and the carbon nano tube surface modified fiber preform C are 8g/m 2 And 14g/m 2 Sequentially aligning the two fiber preforms up and down and superposing the two fiber preforms to 70 layers to obtain a fiber composite D;
wherein the temperature of the polyamide resin mixed solution is 100 ℃, and the polyamide resin mixed solution is prepared by mixing 50% of polyamide resin, 15% of polyvinyl alcohol and 35% of deionized water according to the volume ratio;
step five: and (3) putting the fiber composite body D into a mold for compression molding at the molding temperature of 120 ℃ and the molding pressure of 150MPa in the molding period of 70min by using a hot-pressing molding machine with the model number of SYD-0704, and physically separating the mold from the material to obtain the modified layered fiber body toughened resin-based composite material.
The modified layered fibrous body toughened resin-based composite material prepared in example 3 was subjected to a physical property test, and a bending stress mechanical test was performed in a universal tensile testing machine. The water absorption is tested by a common boiling saturation method, the apparent density is tested by a liquid discharge method, and the shear strength and the bending strength are tested by a universal tensile testing machine.
TABLE 1 comparison of the mechanical properties of the two materials
The blank sample mentioned in the above table was obtained by hot press molding a resin matrix and a fibrous body without surface modification and densification in a mold according to the method of example 1. By comparing the data in table 1, it can be seen that in the invention, with the help of a series of surface treatment technologies, diversified functional groups are introduced on the surface of the three-dimensional fiber body and inside the three-dimensional fiber body after etching treatment, so that the comprehensive mechanical property of the fiber is effectively improved, the interface bonding force of the fiber reinforcement body and the resin matrix is improved, and the obtained modified laminated fiber body toughened resin-based composite material has a compact and compact structure and higher bending strength and shear strength. Meanwhile, the production process is simple, the potential of large-scale industrial production is realized, the raw materials are wide in source, the cost is low, the environment is protected, and the potential application prospect is wide.
Example 4
The method comprises the following steps: aluminum silicate fiber cloth is prepared by mixing, by mass, 4: 1, soaking in ethylene glycol monomethyl ether mixed solution, dropwise adding modified hydriodic acid mixed solution to adjust the pH value to 3.5, soaking for 2 hours, taking out fiber cloth, washing for 7 times by using sodium perborate mixed solution, and drying at 70 ℃ to obtain a fiber preform A subjected to surface etching and hydroxylation treatment;
the aluminum silicate fiber cloth is a combined needled felt body and consists of 50% of chopped strand felt, 25% of untwisted roving gauze and 25% of chopped yarn in mass ratio, and the aluminum silicate fiber cloth comprises 30% of aluminum silicate, 20% of zirconium oxide, 40% of titanium oxide and 10% of beryllium oxide in mass ratio;
the ethylene glycol monomethyl ether mixed solution is formed by mixing 55% of ethylene glycol monomethyl ether, 15% of sodium tripolyphosphate and 30% of deionized water according to the mass ratio;
the hydriodic acid mixed solution is formed by mixing 70% hydriodic acid, 10% ethyl orthosilicate and 20% ethylene glycol according to the volume ratio;
the sodium perborate mixed solution is prepared by mixing 40% of sodium perborate, 30% of sodium hydroxide and 30% of polyvinyl alcohol according to the mass ratio;
step two: mixing alumina fiber cloth in a liquid-solid mass ratio of 7: 1, soaking the mixture in a silica sol mixed solution at the temperature of 70 ℃ for hot filling treatment for 1h, and then dropwise adding an isobutanolamine mixed solution to adjust the pH value to 9 to obtain a mixed precursor solution B;
the aluminum oxide fiber cloth is a combined needled felt body and is formed by combining 40% of chopped strand mats, 40% of untwisted roving and 20% of chopped yarns in mass ratio, and the aluminum oxide fiber cloth comprises 30% of aluminum oxide, 20% of magnesium oxide, 40% of titanium oxide and 10% of strontium oxide in mass ratio;
the silica sol mixed solution is formed by mixing 50% of silica sol, 10% of sodium tripolyphosphate and 40% of deionized water according to the mass ratio;
the isobutanolamine mixed solution is formed by mixing 40% of isobutanolamine, 20% of potassium hydroxide and 40% of deionized water according to the mass ratio;
step three: taking 110g of the mixed precursor solution B, transferring the mixed precursor solution B into a magnetic induction reaction kettle, adding 12g of carbon nano tubes into the magnetic induction reaction kettle, adding aluminum sheets with the length, width and height of 3cm, 2cm and 2cm respectively into the magnetic induction reaction kettle as magnetic induction bodies, treating the magnetic induction bodies at the magnetic induction frequency of 900KHz and the magnetization temperature of 300 ℃ for 8.5 hours, taking out the modified alumina fiber cloth, and drying the alumina fiber cloth in an ultraviolet oven at 85 ℃ to obtain a fiber preform C with the surface modified by the carbon nano tubes;
step four: cutting the fiber preform A and the carbon nano tube surface modified fiber preform C into rectangles with the length of 10-15 cm and the width of 4-8 cm, combining polyamide resin mixed liquor and the two cut fiber preforms by adopting a hot brushing or hot spray gun spraying method, wherein the use amounts of the polyamide resin mixed liquor on the surfaces of the fiber preform A and the carbon nano tube surface modified fiber preform C are 8g/m 2 And 14g/m 2 Sequentially aligning the two fiber preforms up and down and superposing the two fiber preforms to 50 layers to obtain a fiber composite D;
wherein the temperature of the polyamide resin mixed solution is 85 ℃, and the polyamide resin mixed solution is prepared by mixing 45% of polyamide resin, 22% of polyvinyl alcohol and 33% of deionized water according to the volume ratio;
step five: and (3) putting the fiber composite body D into a mold for compression molding at the molding temperature of 90 ℃, the molding pressure of 120MPa and the molding period of 90min by using a hot-pressing molding machine with the model number of SYD-0704, and physically separating the mold from the material to obtain the modified layered fiber body toughened resin-based composite material.
Example 5
The method comprises the following steps: aluminum silicate fiber cloth is prepared by mixing, by mass, 4: 1, soaking the fiber cloth in ethylene glycol monomethyl ether mixed solution, dropwise adding the modified hydroiodic acid mixed solution to adjust the pH value to 3, taking out the fiber cloth after soaking for 2.5h, washing the fiber cloth for 8 times by using sodium perborate mixed solution, and drying the fiber cloth at 75 ℃ to obtain a fiber preform A subjected to surface etching and hydroxylation treatment;
the aluminum silicate fiber cloth is a combined needled felt body and consists of 40% of chopped strand felt, 30% of untwisted roving gauze and 30% of chopped yarn in mass ratio, and the aluminum silicate fiber cloth comprises 30% of aluminum silicate, 20% of zirconium oxide, 20% of titanium oxide and 30% of beryllium oxide in mass ratio;
the ethylene glycol monomethyl ether mixed solution is formed by mixing 50% of ethylene glycol monomethyl ether, 20% of sodium tripolyphosphate and 30% of deionized water according to the mass ratio;
the hydriodic acid mixed solution is prepared by mixing 75% of hydriodic acid, 15% of ethyl orthosilicate and 10% of ethylene glycol according to the volume ratio;
the sodium perborate mixed solution is prepared by mixing 45% of sodium perborate, 25% of sodium hydroxide and 30% of polyvinyl alcohol according to the mass ratio;
step two: mixing alumina fiber cloth in a liquid-solid mass ratio of 8: 1, soaking the mixture in a silica sol mixed solution at the temperature of 80 ℃ for hot filling treatment for 1h, and then dropwise adding an isobutanolamine mixed solution to adjust the pH value to 8 to obtain a mixed precursor solution B;
the aluminum oxide fiber cloth is a combined needled felt body and is formed by combining 60% of chopped strand mats, 20% of untwisted roving and 20% of chopped yarns in mass ratio, and the aluminum oxide fiber cloth comprises 30% of aluminum oxide, 20% of magnesium oxide, 20% of titanium oxide and 30% of strontium oxide in mass ratio;
the silica sol mixed solution is formed by mixing 70% of silica sol, 10% of sodium tripolyphosphate and 20% of deionized water according to the mass ratio;
the isobutanolamine mixed solution is formed by mixing 60% of isobutanolamine, 20% of potassium hydroxide and 20% of deionized water according to the mass ratio;
step three: taking 120g of the mixed precursor solution B, transferring the mixed precursor solution B into a magnetic induction reaction kettle, adding 15g of carbon nano tubes, adding aluminum sheets with the length, width and height of 3cm, 2cm and 2cm respectively into the magnetic induction reaction kettle as magnetic induction bodies, treating for 9.5 hours at the magnetic induction frequency of 1100KHz and the magnetization temperature of 350 ℃, taking out the modified alumina fiber cloth, and drying in an ultraviolet oven at 95 ℃ to obtain a fiber preform C with the surface modified by the carbon nano tubes;
step four: cutting the fiber preform A and the carbon nano tube surface modified fiber preform C into rectangles with the length of 10-15 cm and the width of 4-8 cm, combining polyamide resin mixed liquor and the two cut fiber preforms by adopting a hot brushing or hot spray gun spraying method, wherein the use amounts of the polyamide resin mixed liquor on the surfaces of the fiber preform A and the carbon nano tube surface modified fiber preform C are 8g/m 2 And 14g/m 2 Sequentially aligning the two fiber preforms up and down and superposing the two fiber preforms to 80 layers to obtain a fiber composite body D;
wherein the temperature of the polyamide resin mixed solution is 95 ℃, and the polyamide resin mixed solution is prepared by mixing 40% of polyamide resin, 20% of polyvinyl alcohol and 40% of deionized water according to the volume ratio;
step five: and (3) putting the fiber composite body D into a mold for compression molding at the molding temperature of 110 ℃, the molding pressure of 140MPa and the molding period of 60min by using a hot-pressing molding machine with the model number of SYD-0704, and physically separating the mold from the material to obtain the modified layered fiber body toughened resin-based composite material.
Example 6
The method comprises the following steps: aluminum silicate fiber cloth is prepared by mixing, by mass, 4: 1, soaking in ethylene glycol monomethyl ether mixed solution, dropwise adding modified hydriodic acid mixed solution to adjust the pH value to 4, taking out fiber cloth after soaking for 2 hours, washing for 6 times by using sodium perborate mixed solution and drying at 85 ℃ to obtain a fiber preform A subjected to surface etching and hydroxylation treatment;
the aluminum silicate fiber cloth is a combined needled felt body and consists of 45% of chopped strand mats, 25% of untwisted roving cloths and 30% of chopped yarns in mass ratio, and the aluminum silicate fiber cloth comprises 40% of aluminum silicate, 22% of zirconium oxide, 25% of titanium oxide and 13% of beryllium oxide in mass ratio;
the ethylene glycol monomethyl ether mixed solution is formed by mixing 60% of ethylene glycol monomethyl ether, 15% of sodium tripolyphosphate and 25% of deionized water according to the mass ratio;
the hydriodic acid mixed solution is formed by mixing 75% hydriodic acid, 10% ethyl orthosilicate and 15% ethylene glycol according to the volume ratio;
the sodium perborate mixed solution is prepared by mixing 40% of sodium perborate, 40% of sodium hydroxide and 20% of polyvinyl alcohol according to the mass ratio;
step two: mixing alumina fiber cloth in a liquid-solid mass ratio of 6: 1, soaking the mixture in a silica sol mixed solution at the temperature of 70 ℃ for hot filling treatment for 2 hours, and then dropwise adding an isobutanolamine mixed solution to adjust the pH value to 8.5 to obtain a mixed precursor solution B;
the alumina fiber cloth is a combined needled felt body, is formed by combining 40% of chopped strand mats, 20% of untwisted roving gauzes and 40% of chopped yarns according to the mass ratio, and comprises 40% of alumina, 22% of magnesium oxide, 25% of titanium oxide and 13% of strontium oxide according to the mass ratio of the components;
the silica sol mixed solution is formed by mixing 50% of silica sol, 15% of sodium tripolyphosphate and 35% of deionized water according to the mass ratio;
the isobutanolamine mixed solution is formed by mixing 40% of isobutanolamine, 40% of potassium hydroxide and 20% of deionized water according to the mass ratio;
step three: taking 100g of the mixed precursor solution B, transferring the mixed precursor solution B into a magnetic induction reaction kettle, adding 10g of carbon nano tubes into the magnetic induction reaction kettle, adding aluminum sheets with the length, width and height of 3cm, 2cm and 2cm respectively into the magnetic induction reaction kettle as magnetic induction bodies, treating the magnetic induction bodies for 9 hours at the magnetic induction frequency of 1220KHz and the magnetization temperature of 400 ℃, taking out the modified alumina fiber cloth, and drying the modified alumina fiber cloth in an ultraviolet oven at the temperature of 90 ℃ to obtain a fiber preform C subjected to surface modification of the carbon nano tubes;
step four: cutting the fiber preform A and the carbon nano tube surface modified fiber preform C into rectangles with the length of 10-15 cm and the width of 4-8 cm, combining polyamide resin mixed liquor and the two cut fiber preforms by adopting a hot brushing or hot spray gun spraying method, wherein the use amounts of the polyamide resin mixed liquor on the surfaces of the fiber preform A and the carbon nano tube surface modified fiber preform C are 8g/m 2 And 14g/m 2 Sequentially placing the two fiber preforms in an up-down alignment manner and overlapping the two fiber preforms to 60 layers to obtain a fiber composite D;
wherein the temperature of the polyamide resin mixed solution is 90 ℃, and the polyamide resin mixed solution is prepared by mixing 40% of polyamide resin, 30% of polyvinyl alcohol and 30% of deionized water according to the volume ratio;
step five: and (3) putting the fiber composite body D into a mold for compression molding at the molding temperature of 100 ℃ and the molding pressure of 160MPa for a molding period of 80min by using a hot-pressing molding machine with the model number of SYD-0704, and physically separating the mold from the material to obtain the modified layered fiber body toughened resin-based composite material.
Comparative example 1
The method comprises the following steps: aluminum silicate fiber cloth is prepared by mixing, by mass, 4: 1, soaking the fiber cloth in ethylene glycol monomethyl ether mixed solution, dropwise adding the modified hydroiodic acid mixed solution to adjust the pH value of the mixed solution to 4, taking out the fiber cloth after soaking for 3 hours, washing the fiber cloth for 8 times by using sodium perborate mixed solution, and drying the fiber cloth at 90 ℃ to obtain a fiber preform A subjected to surface etching and hydroxylation treatment;
the aluminum silicate fiber cloth is a combined needled felt body and consists of 40% of chopped strand felt, 40% of untwisted roving gauze and 20% of chopped yarn in mass ratio, and the aluminum silicate fiber cloth comprises 30% of aluminum silicate, 40% of zirconium oxide, 20% of titanium oxide and 10% of beryllium oxide in mass ratio;
the ethylene glycol monomethyl ether mixed solution is formed by mixing 50% of ethylene glycol monomethyl ether, 10% of sodium tripolyphosphate and 40% of deionized water according to the mass ratio;
the hydriodic acid mixed solution is formed by mixing 70% hydriodic acid, 20% ethyl orthosilicate and 10% ethylene glycol according to the volume ratio;
the sodium perborate mixed solution is prepared by mixing 50% of sodium perborate, 25% of sodium hydroxide and 25% of polyvinyl alcohol according to the mass ratio;
step two: and (2) mixing alumina fiber cloth in a liquid-solid mass ratio of 5: 1, soaking the mixture in a 65 ℃ silica sol mixed solution for hot filling treatment for 2 hours, and then dropwise adding an isobutanolamine mixed solution to adjust the pH value to 9 to obtain a mixed precursor solution B;
the aluminum oxide fiber cloth is a combined needled felt body, is formed by combining 50% of chopped strand mats, 25% of untwisted roving gauzes and 25% of chopped strands according to the mass ratio, and comprises 50% of aluminum oxide, 20% of magnesium oxide, 20% of titanium oxide and 10% of strontium oxide according to the mass ratio of the components;
the silica sol mixed solution is formed by mixing 60% of silica sol, 10% of sodium tripolyphosphate and 30% of deionized water according to the mass ratio;
the isobutanolamine mixed solution is formed by mixing 50% of isobutanolamine, 25% of potassium hydroxide and 25% of deionized water according to the mass ratio;
step three: taking 90g of the mixed precursor solution B, transferring the mixed precursor solution B into a magnetic induction reaction kettle, adding 8g of carbon nano tubes into the magnetic induction reaction kettle, adding aluminum sheets with the length, width and height of 3cm, 2cm and 2cm respectively into the magnetic induction reaction kettle as magnetic induction bodies, treating the magnetic induction bodies for 10 hours at the magnetic induction frequency of 1000KHz and the magnetization temperature of 200 ℃, taking out the modified fiber bodies, and drying the modified fiber bodies in an ultraviolet oven at the temperature of 100 ℃ to obtain a fiber preform C with the surface modified by the carbon nano tubes;
step four: cutting the fiber preform A and the carbon nano tube surface modified fiber preform C into rectangles with the length of 10-15 cm and the width of 4-8 cm, combining polyamide resin mixed liquor and the two cut fiber preforms by adopting a hot brushing or hot spray gun spraying method, wherein the use amounts of the polyamide resin mixed liquor on the surfaces of the fiber preform A and the carbon nano tube surface modified fiber preform C are 8g/m 2 And 14g/m 2 Sequentially aligning the two fiber preforms up and down and superposing the two fiber preforms to 70 layers to obtain a fiber composite D;
wherein the temperature of the polyamide resin mixed solution is 100 ℃, and the polyamide resin mixed solution is prepared by mixing 50% of polyamide resin, 15% of polyvinyl alcohol and 35% of deionized water according to the volume ratio;
step five: and (3) putting the fiber composite body D into a mold for compression molding at the molding temperature of 120 ℃ and the molding pressure of 150MPa in the molding period of 70min by using a hot-pressing molding machine with the model number of SYD-0704, and physically separating the mold from the material to obtain the modified layered fiber body toughened resin-based composite material.
Comparative example 1
The method comprises the following steps: aluminum silicate fiber cloth is prepared by mixing, by mass, 4: 1, soaking the fiber cloth in ethylene glycol monomethyl ether mixed solution, dropwise adding the modified hydroiodic acid mixed solution to adjust the pH value of the mixed solution to 4, taking out the fiber cloth after soaking for 3 hours, washing the fiber cloth for 8 times by using sodium perborate mixed solution, and drying the fiber cloth at 90 ℃ to obtain a fiber preform A subjected to surface etching and hydroxylation treatment;
the aluminum silicate fiber cloth is a combined needled felt body and consists of 40% of chopped strand felt, 40% of untwisted roving gauze and 20% of chopped yarn in mass ratio, and the aluminum silicate fiber cloth comprises 30% of aluminum silicate, 40% of zirconium oxide, 20% of titanium oxide and 10% of beryllium oxide in mass ratio;
the ethylene glycol monomethyl ether mixed solution is formed by mixing 50% of ethylene glycol monomethyl ether, 10% of sodium tripolyphosphate and 40% of deionized water according to the mass ratio;
the hydriodic acid mixed solution is formed by mixing 70% hydriodic acid, 20% ethyl orthosilicate and 10% ethylene glycol according to the volume ratio;
the sodium perborate mixed solution is prepared by mixing 50% of sodium perborate, 25% of sodium hydroxide and 25% of polyvinyl alcohol according to the mass ratio;
step two: cutting the fiber preform A and the alumina fiber cloth which is not modified to be rectangular with the length of 10-15 cm and the width of 4-8 cm, combining polyamide resin mixed liquor and the two cut fiber preforms by adopting a hot brushing or hot spray gun spraying method, wherein the use amounts of the polyamide resin mixed liquor on the surfaces of the fiber preform A and the alumina fiber cloth which is not modified are 8g/m 2 And 14g/m 2 Sequentially aligning the two fiber preforms up and down and superposing the two fiber preforms to 70 layers to obtain a fiber composite D;
wherein the temperature of the polyamide resin mixed solution is 100 ℃, and the polyamide resin mixed solution is prepared by mixing 50% of polyamide resin, 15% of polyvinyl alcohol and 35% of deionized water according to the volume ratio;
step three: and (3) putting the fiber composite body D into a mold for compression molding at the molding temperature of 120 ℃ and the molding pressure of 150MPa in the molding period of 70min by using a hot-pressing molding machine with the model number of SYD-0704, and physically separating the mold from the material to obtain the modified layered fiber body toughened resin-based composite material.
Comparative example 2
The method comprises the following steps: and (2) mixing alumina fiber cloth in a liquid-solid mass ratio of 5: 1, soaking the mixture in a silica sol mixed solution at the temperature of 65 ℃ for hot filling treatment for 2 hours, and then dropwise adding an isobutanolamine mixed solution to adjust the pH value to 9 to obtain a mixed precursor solution B;
the aluminum oxide fiber cloth is a combined needled felt body and is formed by combining 50% of chopped strand mats, 25% of untwisted roving and 25% of chopped yarns in mass ratio, and the aluminum oxide fiber cloth comprises 50% of aluminum oxide, 20% of magnesium oxide, 20% of titanium oxide and 10% of strontium oxide in mass ratio;
the silica sol mixed solution is formed by mixing 60% of silica sol, 10% of sodium tripolyphosphate and 30% of deionized water according to the mass ratio;
the isobutanolamine mixed solution is formed by mixing 50% of isobutanolamine, 25% of potassium hydroxide and 25% of deionized water according to the mass ratio;
step two: taking 90g of the mixed precursor solution B, transferring the mixed precursor solution B into a magnetic induction reaction kettle, adding 8g of carbon nano tubes into the magnetic induction reaction kettle, adding aluminum sheets with the length, width and height of 3cm, 2cm and 2cm respectively into the magnetic induction reaction kettle as magnetic induction bodies, treating the magnetic induction bodies for 10 hours at the magnetic induction frequency of 1000KHz and the magnetization temperature of 200 ℃, taking out the modified fiber bodies, and drying the modified fiber bodies in an ultraviolet oven at the temperature of 100 ℃ to obtain a fiber preform C with the surface modified by the carbon nano tubes;
step three: cutting the aluminum silicate fiber cloth which is not modified and the fiber preform C with the surface modified by the carbon nano tube into a rectangle with the length of 10-15 cm and the width of 4-8 cm, combining the polyamide resin mixed solution and the two cut fiber preforms by adopting a hot brush coating or hot spray gun spraying method, wherein the dosage of the polyamide resin mixed solution on the surfaces of the aluminum silicate fiber cloth which is not modified and the fiber preform C with the surface modified by the carbon nano tube is 8g/m 2 And 14g/m 2 Sequentially aligning the two fiber preforms up and down and superposing the two fiber preforms to 70 layers to obtain a fiber composite D;
wherein the temperature of the polyamide resin mixed solution is 100 ℃, and the polyamide resin mixed solution is prepared by mixing 50% of polyamide resin, 15% of polyvinyl alcohol and 35% of deionized water according to the volume ratio;
step four: and (3) putting the fiber composite body D into a mold for compression molding at the molding temperature of 120 ℃ and the molding pressure of 150MPa in the molding period of 70min by using a hot-pressing molding machine with the model number of SYD-0704, and physically separating the mold from the material to obtain the modified layered fiber body toughened resin-based composite material.
The physical property test of the layered fibrous body toughened resin-based composite material prepared in the comparative example 1 and the comparative example 2 is carried out, and the bending stress mechanical experiment is carried out on a universal tensile testing machine. It was found through testing that the samples of comparative examples 1-2 had higher shear strength and bending strength than the blank sample, but significantly lower than example 3. The method adopts a mode of laminating and combining the resin and the surface modified fiber body, can produce the three-dimensional resin matrix composite material at low temperature, solves the problem of fiber mechanical property reduction caused by high-temperature treatment of the traditional fiber composite material, reduces the production cost, greatly improves the comprehensive mechanical property of the material, and has better market application prospect. Particularly, the porous carbon nanotube is introduced as a carrier of functional groups to improve the bonding force of resin and fiber; the concentration gradient structure from the surface to the inside is designed by means of the driving force of diffusion, so that the compact combination between the outer fiber layers is realized, and the influence of the toughness of the damaged inner fibers is reduced.
Claims (10)
1. A preparation method of a layered fibrous toughened resin-based composite material comprises the following steps:
the method comprises the following steps: aluminum silicate fiber cloth is prepared by mixing 3-6 parts by mass of liquid to solid: 1, placing the fiber preform A in a solution containing ethylene glycol monomethyl ether, then using a solution containing hydroiodic acid to adjust the pH value to 3-4, soaking for 2-3 h, taking out the aluminum silicate fiber cloth, washing and drying to obtain a fiber preform A subjected to surface etching and hydroxylation treatment;
step two: mixing alumina fiber cloth in a liquid-solid mass ratio of 4-8: 1, soaking in a solution containing silica sol at the temperature of 60-80 ℃ for hot filling treatment for 1-2 h, and then adjusting the pH value to 8-9 by using a solution containing isobutanolamine to obtain a mixed precursor solution B;
step three: taking 80-120 g of the mixed precursor liquid B, transferring the mixed precursor liquid B into a magnetic induction reaction kettle, adding 5-15 g of carbon nano tubes, then adding aluminum sheets into the magnetic induction reaction kettle to serve as magnetic induction bodies, treating for 8-10 hours at the magnetic induction frequency of 600-1220 KHz and the magnetization temperature of 200-400 ℃, taking out and drying the alumina fiber cloth, and obtaining a fiber preform C subjected to surface modification of the carbon nano tubes;
step four: respectively coating solutions containing polyamide resin on the surfaces of the fiber preform A and the fiber preform C subjected to surface modification by the carbon nano tube, and placing the two fiber preforms in a laminated manner to obtain a fiber composite D;
step five: and pressing and forming the fiber composite D to obtain the layered fiber toughened resin-based composite material.
2. The method according to claim 1, wherein the coating amounts of the solution containing the polyamide resin on the surfaces of the fiber preform A and the fiber preform C surface-modified with the carbon nanotubes are 6 to 10g/m, respectively 2 And 12 to 16g/m 2 。
3. The preparation method according to claim 1, wherein the solution containing ethylene glycol monomethyl ether in the first step is prepared by mixing 50-70% of ethylene glycol monomethyl ether, 10-30% of sodium tripolyphosphate and 20-40% of deionized water in a mass ratio.
4. The preparation method according to claim 1, wherein the solution containing hydroiodic acid in the first step is prepared by mixing 70-80% hydroiodic acid, 10-20% tetraethoxysilane and 10-20% ethylene glycol in a volume ratio.
5. The preparation method according to claim 1, wherein the solution containing silica sol in the second step is prepared by mixing 50-70% of silica sol, 10-20% of sodium tripolyphosphate and 20-40% of deionized water in percentage by mass.
6. The preparation method of claim 1, wherein the solution containing the isobutanolamine in the second step is prepared by mixing 40-60% of isobutanolamine, 20-40% of potassium hydroxide and 20-40% of deionized water in percentage by mass.
7. The preparation method of claim 1, wherein the solution containing the polyamide resin in the fourth step has a temperature of 80-100 ℃, and is prepared by mixing 40-60% of the polyamide resin, 10-30% of polyvinyl alcohol and 30-50% of deionized water by volume ratio.
8. The method according to claim 1, wherein the number of layers of the laminate is 50 to 80.
9. The method according to claim 8, wherein the adjacent fiber preforms A are separated by at least one layer of carbon nanotube surface modified fiber preform C when the stacked fiber preforms A are placed.
10. The layered fibrous body toughened resin-based composite material obtained by the production method according to any one of claims 1 to 9.
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