CN111875944A - Composite material and preparation method and application thereof - Google Patents
Composite material and preparation method and application thereof Download PDFInfo
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- CN111875944A CN111875944A CN202010793776.9A CN202010793776A CN111875944A CN 111875944 A CN111875944 A CN 111875944A CN 202010793776 A CN202010793776 A CN 202010793776A CN 111875944 A CN111875944 A CN 111875944A
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- 239000002131 composite material Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 239000003365 glass fiber Substances 0.000 claims abstract description 63
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 53
- 239000000758 substrate Substances 0.000 claims abstract description 49
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 43
- 239000002086 nanomaterial Substances 0.000 claims abstract description 30
- 229910001338 liquidmetal Inorganic materials 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000004417 polycarbonate Substances 0.000 claims abstract description 23
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 23
- 230000009467 reduction Effects 0.000 claims abstract description 21
- 230000004048 modification Effects 0.000 claims abstract description 17
- 238000012986 modification Methods 0.000 claims abstract description 17
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical group [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000009413 insulation Methods 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 30
- -1 rare earth ions Chemical class 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 15
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 7
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 239000012760 heat stabilizer Substances 0.000 claims description 5
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 2
- 229960004011 methenamine Drugs 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 16
- 230000001603 reducing effect Effects 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000011056 performance test Methods 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000006011 modification reaction Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- WQXKGOOORHDGFP-UHFFFAOYSA-N 1,2,4,5-tetrafluoro-3,6-dimethoxybenzene Chemical compound COC1=C(F)C(F)=C(OC)C(F)=C1F WQXKGOOORHDGFP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- SXSVTGQIXJXKJR-UHFFFAOYSA-N [Mg].[Ti] Chemical compound [Mg].[Ti] SXSVTGQIXJXKJR-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002110 nanocone Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- JQBILSNVGUAPMM-UHFFFAOYSA-K terbium(3+);triacetate Chemical compound [Tb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JQBILSNVGUAPMM-UHFFFAOYSA-K 0.000 description 2
- SNMVVAHJCCXTQR-UHFFFAOYSA-K thulium(3+);triacetate Chemical compound [Tm+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SNMVVAHJCCXTQR-UHFFFAOYSA-K 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Abstract
The invention provides a composite material and a preparation method and application thereof, wherein the composite material comprises a substrate layer and a modified metal layer; the substrate layer comprises polycarbonate, modified glass fiber, a compatilizer and acrylate; the modified metal layer is a fluorosilane modified metal oxide modification layer, and the metal oxide modification layer is a liquid metal oxide layer modified by a nano structure; through the matching effect of the substrate layer and the modified metal layer, the composite material has better impact toughness resistance, mechanical strength, drag reduction and heat insulation performance; the substrate layer modifies the glass fiber, and a compatilizer is added, so that the polycarbonate and glass fiber blending material has better comprehensive performance; the modified metal layer is used for oxidizing liquid metal to form metal oxide, forming a nano structure on the surface of the metal oxide and modifying the metal oxide with the nano structure by adopting fluorosilane, thereby achieving the effects of reducing drag and obstructing heat transfer.
Description
Technical Field
The invention belongs to the field of materials, and relates to a composite material and a preparation method and application thereof.
Background
Polycarbonate (PC) is an engineering plastic with excellent performance, has good heald platform performance, high mechanical strength, good impact toughness, stable size, better heat resistance, good electrical insulation and very wide application. Glass Fiber (Glass Fiber) is an inorganic non-metallic material with excellent performance, has the advantages of good insulativity, strong heat resistance, good corrosion resistance, high mechanical strength and the like, and is widely used for plastic filling modification. The PC/GF blended material can retain the impact toughness and heat resistance of PC resin to some extent and has excellent mechanical strength of glass fiber, so that it has wide application foreground.
Although the PC/GF blended material has better impact toughness, heat resistance and mechanical strength, the resistance reducing effect is not obvious and has no heat insulation effect, and in the using process, media on two sides of the blended material are easy to generate heat conduction, so that energy loss is caused, and the application range of the blended material is influenced.
Therefore, it is necessary to provide a composite material with high mechanical strength, good resistance-reducing effect and excellent heat-insulating effect.
Disclosure of Invention
The invention aims to provide a composite material and a preparation method and application thereof, wherein the composite material comprises a base material layer and a modified metal layer, and the composite material has better impact toughness, mechanical strength, resistance reduction and heat insulation effects through the cooperation effect of the base material layer and the modified metal layer; the base material layer is modified by the glass fiber, and the compatilizer is added, so that the PC and GF blending material has better comprehensive performance and wide application field, and the base material layer and the modified metal layer are both added with the acrylate, and the base material layer and the modified metal layer are weakly polymerized to a certain degree in the preparation process of the composite material, so that the bonding strength of the base material layer and the modified metal layer is increased; the modified metal layer is used for sequentially oxidizing the liquid metal, forming a nano structure on the surface and modifying by adopting fluorosilane, so that the drag reduction performance and the barrier performance of the composite material are improved, and the application range of the composite material is further widened.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to provide a composite material, which comprises a base material layer and a modified metal layer;
the substrate layer comprises polycarbonate, modified glass fiber, a compatilizer and acrylate;
the modified metal layer is a fluorosilane modified metal oxide modification layer, and the metal oxide modification layer is a liquid metal oxide layer modified by a nano structure.
The composite material comprises the base material layer and the modified metal layer, and has good impact toughness, mechanical strength, resistance reduction and heat insulation effects through the cooperation effect of the base material layer and the modified metal layer.
The base material layer is modified by the glass fiber, and the compatilizer is added, so that the PC and GF blending material has better comprehensive performance and wide application field, and the acrylate is added in the base material layer and the modified metal layer, so that the two layers are weakly polymerized to a certain degree in the preparation process of the composite material, and the bonding strength of the two layers is increased; the modified metal layer is used for sequentially oxidizing the liquid metal, forming a nano structure on the surface and modifying by adopting fluorosilane, so that the drag reduction performance and the barrier performance of the composite material are improved, and the application range of the composite material is further widened.
The base material layer comprises polycarbonate, modified glass fiber, a compatilizer and acrylate, and the PC and GF blending material has better mechanical strength, impact toughness resistance and heat resistance through the cooperation of all substances; because the polarity difference of the PC and GF is large, the compatibility is poor, the blending material is difficult to have strong two-phase interface bonding strength through simple blending, the impact resistance of the blending material is poor, the use of the material is influenced, the glass fiber is modified, and the compatilizer is added, so that the two-phase interface bonding strength is reduced, and the good blending performance is realized; the acrylate is added into the blending material, so that in the subsequent preparation process, the acrylate in the substrate layer and the acrylate in the modified metal layer can be weakly polymerized, and the bonding strength of the acrylate and the acrylate is improved.
In the present invention, the substrate layer comprises 60 to 80 mass% (e.g., 60%, 62%, 65%, 67%, 70%, 72%, 75%, 77%, 80%, etc.) of polycarbonate, 10 to 30 mass% (e.g., 10%, 12%, 15%, 17%, 20%, 22%, 25%, 27%, 30%, etc.) of modified glass fibers, 1 to 8 mass% (e.g., 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, etc.) of a compatibilizer, and 1 to 5 mass% (e.g., 1%, 2%, 3%, 4%, 5%, etc.) of an acrylate.
In the invention, the modified glass fiber is a hollow glass fiber which is filled with olefin copolymer in a hollow pore channel and the outer surface of which is modified by silane coupling agent and rare earth ions.
Preferably, the modified glass fiber is a hollow glass fiber, wherein the hollow pore channel is filled with an ethylene-octene copolymer, and the outer surface of the hollow glass fiber is subjected to modification treatment by a silane coupling agent and rare earth ions.
Preferably, the rare earth ions in the hollow glass fiber, in which the olefin copolymer is filled in the hollow pore channels and the outer surface of the hollow glass fiber is subjected to modification treatment by the silane coupling agent and the rare earth ions, are any one or a mixture of at least two of thulium, dysprosium or terbium ions.
According to the invention, the olefin copolymer is filled in the hollow pore canal of the glass fiber, and the outer surface of the hollow pore canal is modified by the silane coupling agent and the rare earth ions, so that the compatibility of the glass fiber and the polycarbonate can be improved, and the mechanical strength and the heat resistance of the polycarbonate and glass fiber blending material can be further improved; further preferably, the kind of olefin and the kind of rare earth ion are selected, so that the compatibility, the mechanical strength and the heat resistance of the blending material can be further improved.
In the invention, the preparation method of the modified glass fiber comprises the following steps:
s1, mixing the hollow glass fiber, 1-octene, a first organic solvent, a catalyst and a cocatalyst to obtain a mixed solution in which the hollow glass fiber is soaked, filling the mixed solution in a hollow pore of the hollow glass fiber, introducing ethylene gas into the mixed solution to perform a polymerization reaction, adding a terminator into a reaction product after the polymerization reaction is finished, taking out the hollow glass fiber, and performing aftertreatment to obtain the hollow glass fiber in which an ethylene-octene copolymer is filled in the hollow pore;
s2, mixing the hollow glass fiber filled with the ethylene-octene copolymer in the hollow pore channel obtained in the S1 with a second organic solvent to obtain a suspension mixed solution, then adding a silane coupling agent into the suspension mixed solution to perform a coupling reaction, and separating insoluble substances after the reaction is finished, wherein the obtained insoluble substances are the hollow glass fiber filled with the ethylene-octene copolymer in the hollow pore channel and subjected to silane coupling agent modification treatment on the surface;
and S3, dispersing the hollow glass fiber which is obtained in the S2, filled with the ethylene-octene copolymer in the hollow pore channel and subjected to the modification treatment of the silane coupling agent on the surface in the aqueous solution of rare earth salt for modification reaction, wherein the insoluble substance obtained after the reaction is the modified glass fiber.
The preparation method of the modified glass fiber is simple, the raw materials are easy to obtain, the price is low, the realization is easy, and the industrial production and application are facilitated.
Preferably, the first organic solvent of S1 is n-hexane.
Preferably, the catalyst of S1 is a magnesium titanium mixture.
Preferably, the catalyst of S1 is Ti/MgCl2。
Preferably, the cocatalyst of S1 is triethylaluminum.
Preferably, the polymerization reaction of S1 has a reaction pressure of 0.1 to 0.12 MPa.
Preferably, the terminating agent of S1 is glycolate.
Preferably, the post-treatment of S1 is to soak the hollow glass fiber in ethanol for 12h, followed by boiling toluene extraction and deionized water rinsing.
Preferably, the second organic solvent described in S2 is toluene.
Preferably, the silane coupling agent of S2 is a KH-550 type silane coupling agent.
Preferably, the mixing of S2 is achieved by sonication.
Preferably, the time of the ultrasonic treatment is 30-60min, such as 30min, 33min, 36min, 39min, 41min, 44min, 47min, 50min, 53min, 56min, 60min and the like.
Preferably, the coupling reaction described in S2 is carried out under sonication conditions.
Preferably, the temperature of the coupling reaction described in S2 is 80-100 deg.C, such as 80 deg.C, 82 deg.C, 84 deg.C, 86 deg.C, 88 deg.C, 90 deg.C, 92 deg.C, 94 deg.C, 96 deg.C, 98 deg.C, 100 deg.C, etc.
Preferably, the coupling reaction time described in S2 is 6-8h, such as 6h, 6.1h, 6.3h, 6.5h, 6.7h, 6.9h, 7.1h, 7.3h, 7.5h, 7.7h, 8h, and the like.
Preferably, the separation described in S2 is centrifugation.
Preferably, the aqueous solution of the rare earth salt described in S3 has a concentration of 1 to 5 wt%, such as 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, etc.
Preferably, the rare earth salt described in S3 is an acetate of a rare earth metal.
Preferably, the rare earth salt in S3 is any one or a mixture of at least two of thulium acetate, dysprosium acetate or terbium acetate.
Preferably, the modification reaction described in S3 is a reaction carried out by standing.
Preferably, the reaction temperature of the modification reaction described in S3 is room temperature, and the reaction time of the modification reaction is 24-36h, such as 24h, 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 36h, and the like.
In the present invention, the compatibilizer is polyolefin elastomer (POE) grafted with maleic anhydride.
In the invention, the substrate layer further comprises 0.5-2% (for example, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, etc.) of a functional assistant by mass.
In the invention, the functional auxiliary agent is any one or a mixture of at least two of an antioxidant, an ultraviolet absorbent, a heat stabilizer or a lubricant.
In the present invention, the liquid metal oxide layer is formed by oxidizing the liquid metal.
In the present invention, the thickness of the modified metal layer is 1 to 100. mu.m, for example, 1 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, etc.
In the present invention, the thickness of the substrate layer is 1 μm to 100cm, for example, 1 μm, 10 μm, 50 μm, 100 μm, 500 μm, 1000 μm, 5000 μm, 1cm, 10cm, 50cm, 100cm and the like.
A second object of the present invention is to provide a method for preparing a composite material according to the first object, comprising the steps of:
(1) coating the mixture of liquid metal and acrylic ester on the surface of a base material layer, and oxidizing to form a metal oxide layer;
(2) carrying out hydrothermal reaction on the metal oxide layer formed in the step (1) to form a metal oxide layer with a nano structure;
(3) and (3) evaporating fluorosilane on the surface of the metal oxide layer with the nano structure formed in the step (2) for modification to obtain the composite material.
In the invention, the preparation method of the substrate layer in the step (1) comprises the following steps: and mixing the polycarbonate, the modified glass fiber, the compatilizer and optional functional auxiliary agents to obtain a mixture, and then mixing and extruding the mixture to obtain the substrate layer.
In the present invention, the mixing temperature is 240-260 ℃, such as 240 ℃, 245 ℃, 250 ℃, 255 ℃, 260 ℃ and the like.
In the present invention, the screw rotation speed of the extruder is 400-500r/min, such as 400r/min, 410r/min, 420r/min, 430r/min, 440r/min, 450r/min, 460r/min, 470r/min, 480r/min, 490r/min, 500r/min, etc.
In the present invention, eleven extrusion sections are provided in the extruder, and the temperature setting of each extrusion section includes:
the temperature of the first section is 240 ℃, the temperature of the second section is 250 ℃, the temperature of the third section is 260 ℃, the temperature of the fourth section is 260 ℃, the temperature of the fifth section is 260 ℃, the temperature of the sixth section is 260 ℃, the temperature of the seventh section is 260 ℃, the temperature of the eighth section is 260 ℃, the temperature of the ninth section is 260 ℃, the temperature of the tenth section is 260 ℃ and the temperature of the eleventh section is 255 ℃.
In the invention, the liquid metal in the step (1) is gallium indium zinc alloy.
In the invention, the liquid metal has better fluidity and easy oxidation performance, an oxide film can be quickly formed at room temperature, and the oxide film is used as a seed for crystal growth, so that the damage of external factors to the substrate layer can be effectively avoided.
In the invention, the thickness of the mixture of the liquid metal and the acrylic ester coated on the surface of the substrate layer is 1-100 microns, so that the fluidity of the liquid metal film can be reduced, and the stability of the nano structure is facilitated.
In the present invention, the mixture of the liquid metal and the acrylate in step (1) comprises 97-99% (e.g. 97%, 97.5%, 98%, 98.5%, 99%, etc.) of the liquid metal and 1-3% (1%, 1.2%, 1.5%, 1.7%, 2%, 2.2%, 2.5%, 2.7%, 3%, etc.) of the acrylate by mass percentage.
In the present invention, the oxidation in step (1) is carried out under normal temperature conditions.
In the present invention, the hydrothermal reaction in step (2) is carried out in an activating solution.
In the present invention, the activating solution includes an aqueous solution containing hexamethylenetetramine and zinc nitrate.
In the present invention, the amount of hexamethylenetetramine added is 0.2 to 0.4g (e.g., 0.2g, 0.22g, 0.25g, 0.27g, 0.3g, 0.33g, 0.35g, 0.37g, 0.4g, etc.) and the amount of zinc nitrate added is 0.2 to 0.7g (e.g., 0.2g, 0.3g, 0.4g, 0.5g, 0.6g, 0.7g, etc.) based on 100mL of water added.
In the present invention, the temperature of the hydrothermal reaction in step (2) is 85 to 90 ℃ (e.g., 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃ and the like), and the time of the hydrothermal reaction is 3 to 24 hours (e.g., 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 17g, 20g, 24g and the like).
The formed metal oxide layer is processed into a nano structure through a hydrothermal reaction, so that the effect of resistance reduction can be achieved.
In the present invention, the evaporation in the step (3) is performed under a vacuum condition having a degree of vacuum of-0.2 to-0.1 MPa, for example, -0.2MPa, -0.18MPa, -0.15MPa, -0.12MPa, -0.1MPa, etc.
In the present invention, the temperature of the vapor deposition in the step (3) is 50 to 120 ℃ (e.g., 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, etc.), and the time of the vapor deposition is 3 to 10 hours (e.g., 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, etc.).
In the invention, the metal oxide layer with the nano structure is modified by fluorosilane, so that the surface of the metal oxide with the nano structure can be changed from a hydrophilic state to a super-hydrophobic state, the surface energy is effectively reduced, and the effects of reducing resistance and blocking heat transfer are achieved.
The third object of the present invention is to provide a use of the composite material according to the second object in the field of drag reduction or thermal insulation.
Compared with the prior art, the invention has the following beneficial effects:
the composite material comprises the base material layer and the modified metal layer, and has good impact toughness, mechanical strength, resistance reduction and heat insulation effects through the matching effect of the base material layer and the modified metal layer; the glass fiber is modified in the substrate layer, and the compatilizer is added, so that the PC and GF blending material has better comprehensive performance and wide application field, and the acrylate is added in the substrate layer and the modified metal layer, so that the two layers are weakly polymerized to a certain degree in the preparation process of the composite material, and the bonding strength of the two layers is increased; the modified metal layer is used for oxidizing liquid metal to form metal oxide, and forming a nano structure on the surface of the metal oxide, so that the effect of drag reduction can be achieved, fluorosilane is used for modifying the metal oxide with the nano structure, the hydrophilic state of the surface of the metal oxide with the nano structure is changed into the super-hydrophobic state, the surface energy is effectively reduced, and the effects of drag reduction and heat transfer blocking are achieved.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In a specific embodiment, there is provided a method of making a modified fiber comprising:
s1, performing vacuum-pumping drying on 100kg of hollow glass fiber at 110 ℃ for 5h, cooling to normal temperature under vacuum condition, adding the dried and cooled hollow glass fiber into a reaction kettle, introducing nitrogen into the kettle, then placing the reaction kettle in a water bath, heating to 70 ℃, vacuumizing, then injecting 20kg of mixed solution of 1-octene and n-hexane (wherein the weight ratio of 1-octene to n-hexane is 1:7), 0.01kg of main catalyst magnesium-titanium mixture and 0.005kg of cocatalyst triethyl aluminum into a conical flask, introducing ethylene gas after the mixed solution is sucked into glass fiber pore channels, keeping the pressure in the kettle at 0.1MPa, performing polymerization reaction for 2h, after the reaction is finished, adding 10% (volume fraction) of glycolate into the reaction kettle to terminate the reaction, soaking the glass fiber in ethanol for 12h, and then washing with water, Drying and extracting with boiling toluene for 8h to obtain hollow glass fiber with hollow pore channels filled with ethylene-octene copolymer;
s2, adding 0.8kg of the modified glass fiber obtained in the step S1 into 20L of toluene, ultrasonically dispersing for 40min at room temperature to obtain a uniform suspension, then adding 0.364kg of KH-550 type silane coupling agent into the suspension, ultrasonically treating the suspension for 8min, carrying out coupling reaction for 8h at 90 ℃, centrifugally separating the reaction liquid at normal temperature at 12000 r/min to obtain insoluble substances, namely the hollow glass fiber which is filled with the ethylene-octene copolymer in the hollow pore channel and the surface of which is subjected to silane coupling agent modification treatment;
s3, dispersing 10kg of the glass fiber obtained in the step S2 in 1 wt% dysprosium acetate aqueous solution, standing for 24h at room temperature for modification reaction, and obtaining insoluble substances after the reaction is finished, namely the modified glass fiber.
Preparation example 1
The preparation example provides a composite material, and the preparation method comprises the following steps:
(1) mixing 70% by mass of polycarbonate (TN-3800B), 20% by mass of the prepared modified glass fiber, 5% by mass of a compatilizer (POE HD-800E with maleic anhydride grafted on the main chain), 3% by mass of acrylic ester, 1% by mass of an ultraviolet absorbent (UV-1164) and 1% by mass of a heat stabilizer (WT-103), and putting the mixture into an extruder for kneading and extruding to obtain a substrate layer;
the rotating speed of a screw of the extruder is 450r/min, eleven extrusion sections are arranged in the extruder, and the temperature of each extrusion section is set as follows:
the temperature of the first section is 240 ℃, the temperature of the second section is 250 ℃, the temperature of the third section is 260 ℃, the temperature of the fourth section is 260 ℃, the temperature of the fifth section is 260 ℃, the temperature of the sixth section is 260 ℃, the temperature of the seventh section is 260 ℃, the temperature of the eighth section is 260 ℃, the temperature of the ninth section is 260 ℃, the temperature of the tenth section is 260 ℃ and the temperature of the eleventh section is 255 ℃.
Preparation example 2
The preparation example provides a composite material, and the preparation method comprises the following steps:
(1) mixing 60 mass percent of polycarbonate (TN-3800B), 30 mass percent of the prepared modified glass fiber, 4 mass percent of compatilizer (POE HD-800E with maleic anhydride grafted on the main chain), 4 mass percent of acrylate, 1 mass percent of ultraviolet absorbent (UV-1164) and 1 mass percent of heat stabilizer (WT-103), putting the mixture into an extruder, and kneading and extruding the mixture to obtain a substrate layer;
the rotating speed of a screw of the extruder is 400r/min, eleven extrusion sections are arranged in the extruder, and the temperature of each extrusion section is set as follows:
the temperature of the first section is 240 ℃, the temperature of the second section is 250 ℃, the temperature of the third section is 260 ℃, the temperature of the fourth section is 260 ℃, the temperature of the fifth section is 260 ℃, the temperature of the sixth section is 260 ℃, the temperature of the seventh section is 260 ℃, the temperature of the eighth section is 260 ℃, the temperature of the ninth section is 260 ℃, the temperature of the tenth section is 260 ℃ and the temperature of the eleventh section is 255 ℃.
Preparation example 3
The preparation example provides a composite material, and the preparation method comprises the following steps:
(1) mixing 80% by mass of polycarbonate (TN-3800B), 10% by mass of the modified glass fiber prepared above, 8% by mass of a compatibilizer (POE HD-800E with maleic anhydride grafted on the main chain), 1% by mass of acrylic ester, 0.5% by mass of an ultraviolet absorber (UV-1164) and 0.5% by mass of a heat stabilizer (WT-103), putting the mixture in an extruder, kneading and extruding to obtain a substrate layer;
the screw rotating speed of the extruder is 500r/min, eleven extrusion sections are arranged in the extruder, and the temperature of each extrusion section is set as follows:
the temperature of the first section is 240 ℃, the temperature of the second section is 250 ℃, the temperature of the third section is 260 ℃, the temperature of the fourth section is 260 ℃, the temperature of the fifth section is 260 ℃, the temperature of the sixth section is 260 ℃, the temperature of the seventh section is 260 ℃, the temperature of the eighth section is 260 ℃, the temperature of the ninth section is 260 ℃, the temperature of the tenth section is 260 ℃ and the temperature of the eleventh section is 255 ℃.
Preparation example 4
Except that dysprosium acetate was replaced with terbium acetate in preparation example 1, the remaining preparation methods were the same as in preparation example 1.
Preparation example 5
The only difference from preparation example 1 is that dysprosium acetate is replaced with thulium acetate, and the other preparation methods are the same as those of preparation example 1.
Example 1
The embodiment provides a preparation method of a composite material, which comprises a substrate layer and a modified metal layer positioned on the surface of one side of the substrate layer, wherein the thickness of the substrate layer is 1000 microns, and the thickness of the modified metal layer is 10 microns.
The embodiment provides a preparation method of a composite material, which comprises the following steps:
(1) coating a mixture of 99 mass percent of liquid metal (gallium indium zinc alloy) and 1 mass percent of acrylate on the surface of a base material layer (the base material layer prepared in preparation example 1), and oxidizing in air to form a metal oxide layer;
(2) placing the substrate layer with the metal oxide layer in 100mL of growth solution (0.3g of hexamethylenetetramine, 0.7g of zinc nitrate and 100mL of deionized water), heating to 90 ℃ under a closed condition, and reacting for 10 hours to form a nano structure on the surface of the metal oxide layer;
(3) and (3) dropwise adding fluorosilane to the surface of the metal oxide layer nanostructure, placing the metal oxide layer nanostructure in a closed container, heating the metal oxide layer to 90 ℃ under the vacuum degree of-0.1 MPa, and reacting for 6 hours to obtain the composite material.
And (3) scanning the nano structure formed in the step (2) by using a scanning electron microscope, so that the surface of the metal oxide layer is modified by the nano cone structure.
The composite material obtained in example 1 was subjected to the following performance tests:
(1) and (3) testing tensile strength: according to the American standard ASTM D638-14 "Standard test method for tensile Properties of plastics", it can be seen that the tensile strength of the composite material obtained in this example is 100.3 MPa;
(2) elongation at break test: when tested according to the standard test methods for breaking strength and elongation at break (grab method) of ASTM D5034-95 in the U.S. standard, the elongation at break of the composite material obtained in this example was found to be 20.2%;
(3) flexural modulus: according to the test of American standard ASTM D7264 Standard method for testing the bending property of resin-based composite materials, the bending modulus of the composite material obtained in the embodiment is 4568 MPa;
(4) notched impact strength: according to the American Standard ASTM D256-97 "Plastic impact test method", the notched impact strength of the composite material obtained in this example was 396J/m;
(5) and (3) testing the adhesive force: according to the Chinese standard GB/T1720-1979 paint film adhesion test, the adhesion grade of the composite material obtained in the embodiment is 5B;
(6) and (3) heat insulation test: manufacturing the composite material into a pipeline, wherein the pipeline comprises a modified metal layer and a base material layer from inside to outside, injecting hot water at 80 ℃ into one side of the modified metal layer, keeping the temperature for 2 hours, and testing the temperature of the surface of one side of the base material layer at intervals of 30min, wherein the temperature is 31 ℃ at 0min, 38 ℃ at 30min, 39 ℃ at 60min, 39 ℃ at 90min and 40 ℃ at 120 ℃, and the composite material has better barrier property;
(7) and (3) resistance reduction test: the composite material is made into a pipeline, wherein the pipeline comprises the modified metal layer and the substrate layer from inside to outside, water is introduced into the pipeline, the flowing of the pipeline is found to be in a turbulent flow mode, fluid is easy to separate from the surface, and the viscous force is small.
Example 2
The embodiment provides a preparation method of a composite material, which comprises a substrate layer and a modified metal layer located on the surface of one side of the substrate layer, wherein the thickness of the substrate layer is 500 micrometers, and the thickness of the modified metal layer is 2 micrometers.
The embodiment provides a preparation method of a composite material, which comprises the following steps:
(1) coating a mixture of 97 mass percent of liquid metal (gallium indium zinc alloy) and 3 mass percent of acrylate on the surface of a base material layer (the base material layer prepared in preparation example 2), and oxidizing in air to form a metal oxide layer;
(2) placing the substrate layer with the metal oxide layer in 100mL of growth solution (0.3g of hexamethylenetetramine, 0.7g of zinc nitrate and 100mL of deionized water), heating to 85 ℃ under a closed condition, and reacting for 24 hours to form a nano structure on the surface of the metal oxide layer;
(3) and (3) dropwise adding fluorosilane to the surface of the metal oxide layer nanostructure, placing the metal oxide layer nanostructure in a closed container, heating the metal oxide layer to 120 ℃ under the vacuum degree of-0.2 MPa, and reacting for 3 hours to obtain the composite material.
The composite material obtained in this example was tested by the same test method as in example 1, and it was found that the composite material had a tensile strength of 82.5MPa, an elongation at break of 28.8%, a flexural modulus of 3816MPa, a notched impact strength of 352J/m, and an adhesion of 4B.
The composite material in the embodiment is made into a pipeline as in embodiment 1, wherein the composite material comprises a modified metal layer and a substrate layer from inside to outside, hot water of 80 ℃ is injected into one side of the modified metal layer, the temperature is kept for 2 hours, and the temperature of one side surface of the substrate layer is tested once every 30 minutes, so that the temperature is 30 ℃ at 0min, 43 ℃ at 30min, 45 ℃ at 60min, 45 ℃ at 90min and 44 ℃ at 120 ℃, which shows that the composite material has better barrier property.
The composite material in this example was made into the same pipe as in example 1, and drag reduction tests were conducted to find that the flow of water was a turbulent flow, the fluid easily separated from the surface, and the viscous force was small.
Example 3
The embodiment provides a preparation method of a composite material, which comprises a substrate layer and a modified metal layer located on the surface of one side of the substrate layer, wherein the thickness of the substrate layer is 100 micrometers, and the thickness of the modified metal layer is 5 micrometers.
The embodiment provides a preparation method of a composite material, which comprises the following steps:
(1) coating a mixture of 98 mass percent of liquid metal (gallium indium zinc alloy) and 2 mass percent of acrylate on the surface of a base material layer (the base material layer prepared in preparation example 3), and oxidizing in air to form a metal oxide layer;
(2) placing the substrate layer with the metal oxide layer in 100mL of growth solution (0.3g of hexamethylenetetramine, 0.7g of zinc nitrate and 100mL of deionized water), heating to 90 ℃ under a closed condition, and reacting for 5 hours to form a nano structure on the surface of the metal oxide layer;
(3) and (3) dropwise adding fluorosilane to the surface of the metal oxide layer nanostructure, placing the metal oxide layer nanostructure in a closed container, heating the metal oxide layer to 50 ℃ under the vacuum degree of-0.2 MPa, and reacting for 10 hours to obtain the composite material.
The composite material obtained in this example was tested by the same test method as in example 1, and it was found that the composite material had a tensile strength of 79.5MPa, an elongation at break of 20.8%, a flexural modulus of 3016MPa, a notched impact strength of 331J/m, and an adhesion of 5B.
The composite material in the embodiment is made into a pipeline as in embodiment 1, wherein the pipeline comprises a modified metal layer and a substrate layer from inside to outside, hot water at 80 ℃ is injected into one side of the modified metal layer, the temperature is kept for 2 hours, and the temperature of one side surface of the substrate layer is tested once every 30 minutes, so that the temperature is 31 ℃ at 0min, 39 ℃ at 30min, 41 ℃ at 60min, 42 ℃ at 90min and 42 ℃ at 120 ℃, which shows that the composite material has better barrier property.
The composite material in this example was made into the same pipe as in example 1, and drag reduction tests were conducted to find that the flow of water was a turbulent flow, the fluid easily separated from the surface, and the viscous force was small.
Preparation example 4
The only difference from example 1 is that the substrate layer in example 1 was replaced with the substrate layer in preparation example 4.
The composite material obtained in this example was tested by the same test method as in example 1, and it was found that the composite material had a tensile strength of 100.4MPa, an elongation at break of 22.7%, a flexural modulus of 3019MPa, a notched impact strength of 387J/m, and an adhesion of 4B.
The composite material in the embodiment is made into a pipeline as in embodiment 1, wherein the composite material comprises a modified metal layer and a substrate layer from inside to outside, hot water of 80 ℃ is injected into one side of the modified metal layer, the temperature is kept for 2 hours, and the temperature of one side surface of the substrate layer is tested once every 30 minutes, so that the temperature is 30 ℃ at 0min, 40 ℃ at 30min, 39 ℃ at 60min, 42 ℃ at 90min and 42 ℃ at 120 ℃, which shows that the composite material has better barrier property.
The composite material in this example was made into the same pipe as in example 1, and drag reduction tests were conducted to find that the flow of water was a turbulent flow, the fluid easily separated from the surface, and the viscous force was small.
Preparation example 5
The only difference from example 1 is that the substrate layer in example 1 was replaced with the substrate layer in preparation example 5.
The composite material obtained in this example was tested by the same test method as in example 1, and it was found that the composite material had a tensile strength of 94.0MPa, an elongation at break of 25%, a flexural modulus of 3455MPa, a notched impact strength of 397J/m, and an adhesion of 4B.
The composite material in the embodiment is made into a pipeline as in embodiment 1, wherein the composite material comprises a modified metal layer and a substrate layer from inside to outside, hot water of 80 ℃ is injected into one side of the modified metal layer, the temperature is kept for 2 hours, and the temperature of one side surface of the substrate layer is tested once every 30 minutes, so that the temperature is 30 ℃ at 0min, 44 ℃ at 30min, 43 ℃ at 60min, 43 ℃ at 90min and 45 ℃ at 120 ℃, and the composite material has better barrier property.
The composite material in this example was made into the same pipe as in example 1, and drag reduction tests were conducted to find that the flow of water was a turbulent flow, the fluid easily separated from the surface, and the viscous force was small.
Comparative example 1
The only difference from example 1 is that no modified glass fiber is included, and the rest of the composition and the preparation method are the same as those of example 1.
By using the composite material obtained in this example and the same test method as in example 1, it can be seen that the tensile strength of the composite material is 50.2MPa, the elongation at break is 2.9%, the flexural modulus is 3150MPa, the notched impact strength is 190J/m, and the adhesion test, the drag reduction test and the heat insulation performance test are similar to those of example 1.
Comparative example 2
The only difference from example 1 is that the modified glass fiber in example 1 is replaced with a hollow glass fiber having hollow cells filled with an ethylene-octene copolymer, and the rest of the composition and the preparation method are the same as those of example 1.
The composite material obtained in this example was tested by the same test method as in example 1, and it was found that the composite material had a tensile strength of 56.4MPa, an elongation at break of 18.3%, a flexural modulus of 3559MPa, a notched impact strength of 307J/m, and adhesion, drag reduction and thermal insulation properties similar to those of example 1.
Comparative example 3
The only difference from example 1 is that the modified fiber in example 1 is replaced by a hollow glass fiber, the hollow channels of which are filled with ethylene-octene copolymer and the surface of which is modified by silane coupling agent, and the rest composition and preparation method are the same as those of example 1.
The composite material obtained in the comparative example is tested by the same test method as that of example 1, and the composite material has the tensile strength of 63.8MPa, the elongation at break of 23.9%, the flexural modulus of 3717MPa, the notch impact strength of 348J/m, and the adhesion test, the drag reduction test and the heat insulation performance test which are similar to those of example 1.
Comparative example 4
The difference from example 1 is only that the substrate layer does not include the added acrylate, and the rest of the composition and the preparation method are the same as those of example 1.
The composite material obtained by the comparative example is subjected to performance test, and the adhesive force is 3B, and other performances are similar to the performance test result of the example 1.
Comparative example 5
The only difference from example 1 is that no acrylate is added during the preparation of the modified metal layer, and the rest of the composition and preparation method are the same as example 1.
The composite material obtained in the comparative example is subjected to the same performance test as that in example 1, and the adhesion is 3B, and the other performances are similar to the performance test result in example 1.
Comparative example 6
The only difference from example 1 is that the modified metal layer formation process does not include hydrothermal treatment of the metal oxide layer, and the rest of the composition and the preparation method are the same as those of example 1.
The composite material obtained by the comparative example is subjected to the performance test same as that of the example 1, and the result that the resistance reduction performance is inferior to that of the example 1 is known, and other performances are similar to those of the example 1.
It can be seen from the comparison between example 1 and comparative example 6 that the resistance-reducing performance of the composite material is affected when the metal oxide layer is not hydrothermally treated to form a nanocone structure on the surface of the metal oxide layer.
Comparative example 7
The only difference from example 1 is that the modified metal layer formation process does not include evaporation of fluorosilane, and the rest of the composition and the preparation method are the same as those of example 1.
The composite material obtained by the comparative example is subjected to the same performance test as that of example 1, and it is found that both the resistance reduction performance and the heat insulation performance are inferior to those of example 1, and the other performances are similar to those of example 1.
It can be seen from the comparison between example 1 and comparative example 7 that, when the surface of the metal oxide layer with the nanostructure is not modified with the fluorosilane, the hydrophilic state of the surface of the metal oxide layer with the nanostructure cannot achieve the effects of reducing drag and blocking heat transfer.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The composite material is characterized by comprising a base material layer and a modified metal layer;
the substrate layer comprises polycarbonate, modified glass fiber, a compatilizer and acrylate;
the modified metal layer is a fluorosilane modified metal oxide modification layer, and the metal oxide modification layer is a liquid metal oxide layer modified by a nano structure.
2. The composite material of claim 1, wherein the substrate layer comprises 60-80% by mass of polycarbonate, 10-30% by mass of modified glass fiber, 1-8% by mass of a compatibilizer, and 1-5% by mass of acrylate;
preferably, the modified glass fiber is a hollow glass fiber, wherein the inside of a hollow pore channel is filled with an olefin copolymer, and the outer surface of the hollow glass fiber is subjected to modification treatment by a silane coupling agent and rare earth ions;
preferably, the modified glass fiber is a hollow glass fiber, wherein the hollow pore is filled with an ethylene-octene copolymer, and the outer surface of the hollow glass fiber is subjected to modification treatment by a silane coupling agent and rare earth ions;
preferably, the rare earth ions in the hollow glass fiber, in which the olefin copolymer is filled in the hollow pore channels and the outer surface of the hollow glass fiber is subjected to modification treatment by the silane coupling agent and the rare earth ions, are any one or a mixture of at least two of thulium, dysprosium or terbium ions.
3. The composite material according to claim 2, characterized in that the compatibilizer is a polyolefin elastomer grafted with maleic anhydride;
preferably, the base material layer further comprises 0.5-2% by mass of a functional auxiliary agent;
preferably, the functional auxiliary agent is any one or a mixture of at least two of an antioxidant, an ultraviolet absorber, a heat stabilizer or a lubricant.
4. The composite material according to claim 1, wherein the liquid metal oxide layer is formed by oxidation of a liquid metal;
preferably, the thickness of the modified metal layer is 1-100 μm;
preferably, the thickness of the substrate layer is 1 μm to 100 cm.
5. A method for the preparation of a composite material according to any one of claims 1 to 4, characterized in that it comprises the following steps:
(1) coating the mixture of liquid metal and acrylic ester on the surface of a base material layer, and oxidizing to form a metal oxide layer;
(2) carrying out hydrothermal reaction on the metal oxide layer formed in the step (1) to form a metal oxide layer with a nano structure;
(3) and (3) evaporating fluorosilane on the surface of the metal oxide layer with the nano structure formed in the step (2) for modification to obtain the composite material.
6. The production method according to claim 5, wherein the production method of the substrate layer of step (1) comprises: mixing polycarbonate, modified glass fiber, a compatilizer and an optional functional auxiliary agent to obtain a mixture, then mixing and extruding the mixture to obtain the substrate layer;
preferably, the temperature of the mixing is 240-260 ℃;
preferably, the screw rotating speed of the extruding extruder is 400-500 r/min;
preferably, eleven extrusion sections are arranged in the extruder, and the temperature setting of each extrusion section comprises:
the temperature of the first section is 240 ℃, the temperature of the second section is 250 ℃, the temperature of the third section is 260 ℃, the temperature of the fourth section is 260 ℃, the temperature of the fifth section is 260 ℃, the temperature of the sixth section is 260 ℃, the temperature of the seventh section is 260 ℃, the temperature of the eighth section is 260 ℃, the temperature of the ninth section is 260 ℃, the temperature of the tenth section is 260 ℃ and the temperature of the eleventh section is 255 ℃.
7. The composite material of claim 5, wherein the liquid metal of step (1) is a gallium indium zinc alloy;
preferably, the mixture of the liquid metal and the acrylate in the step (1) comprises 97-99% of the liquid metal and 1-3% of the acrylate by mass percentage;
preferably, the oxidation in step (1) is carried out under normal temperature conditions.
8. The composite material according to claim 5, wherein the hydrothermal reaction of step (2) is carried out in an activating solution;
preferably, the activating solution comprises an aqueous solution containing hexamethylenetetramine and zinc nitrate;
preferably, the addition amount of the hexamethylene tetramine is 0.2-0.4g, and the addition amount of the zinc nitrate is 0.2-0.7g, wherein the addition amount of the water is 100 mL;
preferably, the temperature of the hydrothermal reaction in the step (2) is 85-90 ℃, and the time of the hydrothermal reaction is 3-24 h.
9. The composite material according to claim 5, wherein the evaporation of step (3) is performed under vacuum condition, and the vacuum degree under vacuum condition is-0.2 to-0.1 MPa;
preferably, the temperature of evaporation in the step (3) is 50-120 ℃, and the time of evaporation is 3-10 h.
10. Use of a composite according to any one of claims 1 to 4 for the field of thermal insulation or drag reduction.
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