WO2017016435A1 - 纤维金属层合板及其制备方法 - Google Patents

纤维金属层合板及其制备方法 Download PDF

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Publication number
WO2017016435A1
WO2017016435A1 PCT/CN2016/090900 CN2016090900W WO2017016435A1 WO 2017016435 A1 WO2017016435 A1 WO 2017016435A1 CN 2016090900 W CN2016090900 W CN 2016090900W WO 2017016435 A1 WO2017016435 A1 WO 2017016435A1
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Prior art keywords
fiber
layer
resin
parts
metal laminate
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PCT/CN2016/090900
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English (en)
French (fr)
Inventor
毛定文
崔静娜
罗文海
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BYD Co Ltd
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BYD Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance

Definitions

  • the present disclosure relates to fiber metal laminates and methods of making same.
  • Fiber-metal laminate material in which metal materials and fibers are composited, namely fiber metal laminates.
  • Fiber-reinforced metal laminates are a new class of hybrid reinforced structural composites that combine not only the advantages of metal and fiber composites, but also overcome most of their shortcomings. They are found in high-tech fields such as aerospace, military, and automotive. Structural materials for great application prospects.
  • the fiber metal laminate has a series of excellent properties, the bonding force between the metal layer and the fiber cloth is weak.
  • the metal layer of the fiber metal laminate has a strong bonding force with the fiber cloth.
  • An embodiment of an aspect of the present disclosure provides a fiber metal laminate comprising a laminated metal layer, a resin bonding layer, and a fiber layer, wherein the resin bonding layer and the fiber layer are embedded with chopped fibers, And the chopped fibers have a length of 50 ⁇ m to 2 mm.
  • An embodiment of another aspect of the present disclosure also provides a method of preparing the above-described fiber metal laminate, comprising: applying a binder to a surface of a metal layer to form a resin bonding layer on a surface of the metal layer; The resin bonding layer; and hot pressing to integrate the fiber layer, the resin layer and the metal layer to obtain the fiber metal laminate, wherein the fiber metal laminate comprises a laminated body a metal layer, the resin bonding layer, and the fiber layer, wherein the binder is formed of a resin composition containing a thermosetting binder resin and chopped fibers, wherein the length of the chopped fibers is 50 ⁇ m-2mm.
  • An embodiment of another aspect of the present disclosure further provides a fiber metal laminate comprising: a first metal layer; a first resin bonding layer disposed on the first metal layer; and a fiber layer disposed on the first a resin bonding layer; a second resin bonding a layer disposed on the fiber layer; and a second metal layer disposed on the second resin bonding layer, wherein the first resin bonding layer and the fiber layer and the second resin are bonded A chopped fiber is embedded between the layer and the fibrous layer, and the chopped fiber has a length of 50 ⁇ m to 2 mm.
  • the bonding force between the metal layer and the fiber cloth is strong.
  • first and second are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated.
  • features defining “first” and “second” may include one or more of the features either explicitly or implicitly.
  • the meaning of "a plurality” is two or more unless specifically and specifically defined otherwise.
  • the first feature "on” or “under” the second feature may include direct contact of the first and second features, and may also include first and second features, unless otherwise specifically defined and defined. It is not in direct contact but through additional features between them.
  • the first feature “above”, “above” and “above” the second feature includes the first feature directly above and above the second feature, or merely indicating that the first feature level is higher than the second feature.
  • the first feature “below”, “below” and “below” the second feature includes the first feature directly above and above the second feature, or merely the first feature level being less than the second feature.
  • the fiber metal laminate provided by the present disclosure comprises a laminated metal layer 1, a resin bonding layer 2 and a fiber layer 3, and the chopped fiber 4 is embedded between the resin bonding layer 2 and the fiber layer 3, and the short The length of the cut fiber 4 is 50 ⁇ m to 2 mm.
  • the length of the chopped fiber 4 is optionally 75 ⁇ m - 1 mm.
  • the diameter of the chopped fiber 4 may vary over a wide range, and optionally the chopped fiber 4 has a cross-sectional diameter of 0.5 ⁇ m to 20 ⁇ m, for example, 1 ⁇ m to 10 ⁇ m.
  • the chopped strands 4 are one or more of glass fibers, carbon fibers, and aramid fibers.
  • the fiber layer 3 is not particularly limited, and the material thereof may be various conventional materials, for example,
  • the fiber layer 3 may be a fiber cloth woven from one or more of glass fibers, carbon fibers, and aramid fibers.
  • the mass per unit area of the fiber layer 3 is not particularly limited, and may specifically vary over a wide range.
  • the fiber layer 3 has a mass per unit area of 50 g/cm 2 to 650 g/cm 2 , for example. It is from 150 g/cm 2 to 300 g/cm 2 .
  • the resin adhesive layer 2 may be a layer obtained by curing a resin composition containing a thermosetting binder resin and chopped fibers.
  • thermosetting binder resin is one or more of an acrylic resin, an epoxy resin, a polyurethane resin, a polyester resin, a benzoxazine resin, a phenol resin, a urea resin, and a melamine resin.
  • epoxy resin epoxy resin.
  • the resin composition further contains a reactive diluent.
  • the reactive diluent is contained in an amount of 10 to 55 parts by weight with respect to 100 parts by weight of the thermosetting binder resin; alternatively, with respect to 100 parts by weight of the thermosetting binder resin, The reactive diluent is contained in an amount of from 13 to 53 parts by weight.
  • the reactive diluent is used for dissolving and dispersing a film-forming substance, and has a function of participating in a film-forming reaction during film formation of the coating material to form a component which does not exhibit a component remaining in the coating film.
  • a reactive diluent propylene glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, resorcinol diglycidyl ether, hexanediol diglycidyl ether, butylene glycol may be selected.
  • the reactive diluent is butyl glycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl One or more of an ether and an alkyl polyglycidyl ether.
  • a reactive diluent of the type SM678 of Jiangsu Sanmu Group Co., Ltd. (the composition is neopentyl glycol diglycidyl ether) can be used.
  • the resin composition further contains a curing agent.
  • the curing agent is contained in an amount of 1-55 parts by weight relative to 100 parts by weight of the thermosetting binder resin; alternatively, relative to 100 parts by weight of the thermosetting binder resin, The curing agent is contained in an amount of 2 to 50 parts by weight.
  • the curing agent may be various curing agents for curing which are commonly used in the art.
  • it is diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone adipate dihydrazide, dicyandiamide, triethylenediamine, triethylenetetramine, tetraethylenepentamine, two Ethylaminopropylamine, montanyldiamine, isophoronediamine, N-aminoethylpiperazine, bis(4-amino-3-methylcyclohexyl)methane and bis(4-aminocyclohexyl)methane One or more.
  • dicyandiamide is diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone adipate dihydrazide, dicyandiamide, triethylenediamine, triethylenetetramine, t
  • the resin composition may further contain a curing accelerator.
  • the curing accelerator is contained in an amount of 0 to 10 parts by weight with respect to 100 parts by weight of the thermosetting binder resin; alternatively, with respect to 100 parts by weight of the thermosetting binder resin, The curing accelerator is contained in an amount of from 0.9 to 8.8 parts by weight.
  • the curing accelerator may be various curing accelerators commonly used in the art.
  • it may be one or more of an organic quinone compound, an imidazole compound, and a urea compound; for example, an imidazole compound; for example, 1-methylimidazole.
  • the resin composition may further contain one or more of an antifoaming agent, a leveling agent, and a wetting agent.
  • an antifoaming agent e.g., a foaming agent, a leveling agent, and a wetting agent.
  • the foaming agent, the leveling agent, and the wetting agent are relative to 100 parts by weight of the thermosetting binder resin.
  • the content is 0 to 12 parts by weight, for example, 1.5 to 11 parts by weight.
  • the antifoaming agent, leveling agent and wetting agent can be various antifoaming agents, leveling agents and wetting agents commonly used in the art.
  • the antifoaming agent is one of a polyacrylic acid-polyether copolymer defoaming agent, a silicone defoaming agent, an organic modified silicone antifoaming agent, and a fluorosilicone defoaming agent.
  • the leveling agent is one or more of an acrylate, a polyether siloxane copolymer, and an organic modified polysiloxane
  • the wetting agent is a nonionic organic surfactant.
  • DEGO Airex 932 defoamer fluorosilicone defoamer
  • the resin bonding layer has a thickness of from 0.02 mm to 0.5 mm, for example, from 0.02 mm to 0.2 mm.
  • the metal layer may be a conventional metal plate having various materials and structures.
  • the metal layer is one of an aluminum alloy plate, a titanium alloy plate, and a steel plate.
  • a conventional aluminum alloy plate is optionally employed.
  • the thickness of the metal layer is not particularly limited in the present disclosure, and may be varied within a wide range. Those skilled in the art may adjust according to actual conditions.
  • the thickness of the metal layer is 0.1 mm to 3 mm.
  • the chopped fiber 4 is coated with a silane coupling agent.
  • a silane coupling agent By coating the surface of the chopped fiber with a silane coupling agent and having a reactive group capable of chemically bonding to the surface of the fiber, the bridge effect can be enhanced between the fiber and the prepreg resin, thereby further improving the interlayer bonding force. .
  • the method of coating the surface of the chopped fiber 4 with a silane coupling agent may be a method known in the art, for example, spraying a solution obtained by mixing a silane coupling agent with a dispersing agent and a solvent on the surface of the chopped fiber. dry.
  • the silane coupling agent may be various silane coupling agents commonly used in the art.
  • the silane coupling agent is one or more of an aminosilane, an epoxysilane, a thiosilane, a methacryloxysilane, a vinylsilane, a ureidosilane, and an isocyanatosilane.
  • the silane coupling agent is one or more of an aminosilane and an epoxysilane.
  • the dispersing agent may be various dispersing agents commonly used in the art, and is optionally water glass, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, triethylhexylphosphoric acid, sodium lauryl sulfate, One or more of methylpentanol, a cellulose derivative, a polyacrylamide, a guar gum, an aliphatic polyethylene glycol ester, and a modified polyalkoxide.
  • the solvent may be any one of the silane coupling agent and the dispersant solvent, and may be, for example, ethanol, xylene, n-butanol, ethylene glycol butyl ether, butyl acetate, isopropanol or cyclohexane.
  • ethanol xylene
  • n-butanol ethylene glycol butyl ether
  • butyl acetate isopropanol or cyclohexane.
  • One or more of a ketone and a methyl isobutyl ketone isobutyl ketone.
  • the mixing mass ratio of the silane coupling agent, the dispersing agent and the solvent may be selected from 1:0.5 to 5:50 to 200; for example, 1:3 to 100:100.
  • a conventional fiber metal laminate includes a fiber layer, two of the metal layers, and two of the resin bonding layers; the two resin bonding layers are located between the two metal layers, the fiber cloth Located between the two resin bonding layers.
  • the fiber metal laminate comprises a fiber layer, two of the metal layers, and two of the resin bonding layers, the two resin bonding layers and the fiber cloth are embedded with the short Cut the fiber.
  • the present disclosure also provides a method of preparing a fiber metal laminate, comprising: applying a binder to a surface of the metal layer 1 to form a resin bonding layer 2 on a surface of the metal layer; and disposing the fiber layer 3 on the resin On the bonding layer 2; and hot pressing to integrate the fiber layer 3, the resin layer 2 and the metal layer 1 to obtain the fiber metal laminate, wherein the fiber metal laminate comprises a laminate The metal layer 1, the resin bonding layer 2, and the fiber layer 3, wherein the binder is formed of a resin composition containing a thermosetting binder resin and chopped fibers 4, wherein the short The length of the cut fiber 4 is 50 ⁇ m to 2 mm.
  • the method of producing a fiber metal laminate according to the present disclosure in order to obtain a fiber metal laminate excellent in bonding strength between the metal layer 1 and the fiber layer 3, optionally, with respect to 100 parts by weight of the thermosetting binder resin
  • the chopped fiber 4 is contained in an amount of 5 to 50 parts by weight; alternatively, the chopped fiber is contained in an amount of 8 to 38 parts by weight relative to 100 parts by weight of the thermosetting binder resin.
  • the length is optionally from 75 ⁇ m to 1 mm.
  • the diameter of the chopped fiber 4 may vary over a wide range, and optionally the chopped fiber 4 has a cross-sectional diameter of 0.5 ⁇ m to 20 ⁇ m, for example, 1 ⁇ m to 10 ⁇ m. .
  • the chopped fiber is one or more of glass fiber, carbon fiber, and aramid fiber.
  • the resin composition contains the thermosetting binder resin.
  • the thermosetting binder resin may be selected from one or more of an acrylic resin, an epoxy resin, a polyurethane resin, a polyester resin, a benzoxazine resin, a phenol resin, a urea resin, and a melamine resin.
  • epoxy resin for example, epoxy resin.
  • the resin composition further contains a reactive diluent.
  • the reactive diluent may be used in an amount conventionally used in the art, and the reactive diluent is contained in an amount of 10 to 55 parts by weight based on 100 parts by weight of the thermosetting binder resin; alternatively, relative to 100
  • the heat-curable binder resin is contained in an amount of from 13 to 53 parts by weight based on parts by weight.
  • the reactive diluent is used for dissolving and dispersing a film-forming substance, and has a function of participating in a film-forming reaction during film formation of the coating material to form a component which does not exhibit a component remaining in the coating film.
  • the reactive diluent may be selected from the group consisting of propylene glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, resorcinol diglycidyl ether, hexanediol diglycidyl ether, and butanediol dihydrate.
  • the reactive diluent is one or more of butyl glycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and alkyl polyglycidyl ether.
  • the reactive diluent may be a reactive diluent of the type SM678 of Jiangsu Sanmu Group Co., Ltd. (the composition is neopentyl glycol diglycidyl ether).
  • the resin composition further contains a curing agent.
  • the amount of the curing agent may be a conventional amount in the art, and optionally, relative to 100 parts by weight of the thermosetting binder.
  • the resin, the curing agent is contained in an amount of 1 to 55 parts by weight; alternatively, the curing agent is contained in an amount of 2 to 50 parts by weight based on 100 parts by weight of the thermosetting binder resin.
  • the curing agent may be various curing agents commonly used in the art for curing, optionally diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone adipate dihydrazide, dicyandiamide Amine, triethylenediamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, montan diamine, isophoronediamine, N-aminoethylpiperazine, bis(4-amino-3- One or more of methylcyclohexyl)methane and bis(4-aminocyclohexyl)methane.
  • dicyandiamide for example, dicyandiamide.
  • the resin composition further contains a curing accelerator.
  • the curing accelerator may be used in an amount conventionally used in the art, and optionally, the curing accelerator is contained in an amount of from 0 to 10 parts by weight, based on 100 parts by weight of the thermosetting binder resin;
  • the content of the curing accelerator is from 0.9 to 8.8 parts by weight based on 100 parts by weight of the thermosetting binder resin.
  • the curing accelerator may be various curing accelerators commonly used in the art.
  • it may be one or more of an organic quinone compound, an imidazole compound, and a urea compound; for example, an imidazole compound; for example, 1-methylimidazole.
  • the resin composition may further contain one or more of an antifoaming agent, a leveling agent, and a wetting agent.
  • an antifoaming agent e.g., a leveling agent, and a wetting agent.
  • the foaming agent, the leveling agent, and the wetting agent are each contained in an amount of 0 to 12 parts by weight, for example, 1.5 to 11 parts by weight, per 100 parts by weight of the thermosetting binder resin.
  • the antifoaming agent, leveling agent and wetting agent can be various antifoaming agents, leveling agents and wetting agents commonly used in the art.
  • the antifoaming agent is, for example, one of a polyacrylic acid-polyether copolymer defoaming agent, a silicone-based antifoaming agent, an organic modified silicone antifoaming agent, and a fluorosilicone antifoaming agent.
  • the leveling agent is, for example, one or more of an acrylate, a polyether siloxane copolymer, and an organically modified polysiloxane
  • the wetting agent is, for example, a nonionic organic surface active One or more of the agents.
  • the antifoaming agent may be DEGO Airex 932 defoamer (fluorosilicone antifoaming agent).
  • the prepreg fiber cloth is commercially available, and can also be produced by a method conventional in the art.
  • the prepreg composition contains a thermosetting binder resin, a reactive diluent, a curing agent, a curing accelerator, and an antifoaming agent.
  • the thermosetting binder resin, reactive diluent, curing agent, curing accelerator, and antifoaming agent contained in the prepreg composition are well known in the art.
  • thermosetting binder resin, the reactive diluent, the curing agent, the curing accelerator, and the antifoaming agent contained in the prepreg composition may each contain a thermosetting binder resin in the above resin composition.
  • the reactive diluent, curing agent, curing accelerator and antifoaming agent are the same.
  • the material of the fiber cloth is not particularly limited, and the material thereof may be various materials of conventional materials.
  • one or more of glass fiber cloth, carbon fiber cloth, and aramid fiber cloth may be used, or the above glass fiber may be used.
  • the mass per unit area of the fiber cloth is not particularly limited, and may be specifically varied within a wide range.
  • the mass per unit area of the fiber cloth is 50 g/cm 2 to 650 g/cm 2 , for example, 150 g. /cm 2 -300g/cm 2 .
  • the above metal layer may be a metal plate having various materials and structures, for example, the metal layer is one of an aluminum alloy plate, a titanium alloy plate, and a steel plate. .
  • a conventional aluminum alloy plate is optionally employed.
  • the thickness of the metal layer is not particularly limited in the present disclosure, and may be varied within a wide range. Those skilled in the art may adjust according to actual conditions.
  • the thickness of the metal layer is 0.1 mm to 3 mm.
  • the metal is subjected to a degreasing treatment of the metal before lamination with the prepreg fiber cloth.
  • the method of degreasing and decontaminating is well known in the art, for example, by soaking the above metal with an acid and then soaking it with an alkali.
  • the above metal may be placed in a 5% by weight aqueous solution of nitric acid for 30 seconds, and then immersed in a 10% by weight aqueous sodium hydroxide solution for 30 seconds.
  • the chopped fiber surface is coated with a silane coupling agent.
  • a silane coupling agent By coating the surface of the chopped fiber with a silane coupling agent and having a reactive group capable of chemically bonding to the surface of the fiber, the bridge effect can be enhanced between the fiber and the prepreg resin, thereby further improving the interlayer bonding force.
  • the method of coating the surface of the chopped fiber with a silane coupling agent may be a method known in the art, for example, a solution obtained by mixing a silane coupling agent with a dispersing agent and a solvent is sprayed on the surface of the chopped fiber.
  • the silane coupling agent may be various silane coupling agents commonly used in the art.
  • the silane coupling agent is one or more of aminosilane, epoxysilane, thiosilane, methacryloxysilane, vinylsilane, ureidosilane, and isocyanatosilane;
  • the silane coupling agent is an aminosilane and/or an epoxysilane.
  • dispersing agent various dispersing agents commonly used in the art may be used, and water glass, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, triethylhexylphosphoric acid, sodium lauryl sulfate, One or more of methylpentanol, a cellulose derivative, a polyacrylamide, a guar gum, an aliphatic polyethylene glycol ester, and a modified polyalkoxide.
  • the silane coupling agent and the dispersant solvent may be preferably used, and may be, for example, ethanol, xylene, n-butanol, ethylene glycol butyl ether, butyl acetate, isopropanol or a ring.
  • One or more of ketone and methyl isobutyl ketone may be used, for example, ethanol, xylene, n-butanol, ethylene glycol butyl ether, butyl acetate, isopropanol or a ring.
  • One or more of ketone and methyl isobutyl ketone isobutyl ketone.
  • the mixing mass ratio of the silane coupling agent, the dispersing agent and the solvent may be selected from 1:0.5 to 5:50 to 200; for example, 1:3 to 100:100.
  • a binder is obtained by mixing and dispersing the components in the resin composition.
  • the order of mixing the components in the resin composition may be any.
  • the heat-curable binder resin and the reactive diluent are mixed and dispersed, and then the chopped fibers are added for dispersion mixing, and then A curing agent, a curing accelerator, and an antifoaming agent are added, followed by dispersion and mixing to obtain a binder.
  • a binder is applied to the surface of the metal layer to form a resin bonding layer on the surface of the metal layer, and the coating thickness of the binder may be 0.02 mm - 0.5 mm, for example, 0.05 mm to 0.2 mm.
  • hot pressing causes the fiber layer, the resin layer, and the metal layer to be integrated to obtain the fiber metal laminate, wherein the fiber metal laminate includes the laminated metal layer, The resin bonding layer and the fibrous layer.
  • the hot pressing method is: hot pressing at 120 ° C - 140 ° C, 0.1 MPa - 10 MPa pressure for 30 min - 120 min, and then depressurizing after cooling.
  • pretreatment agent on the surface of 4kg glass fiber chopped fiber (glass chopped fiber, length 200 ⁇ m, cross-sectional diameter 10 ⁇ m), and drying to obtain pretreated fiber yarn X;
  • step 2) The pretreated filament X obtained in step 2) is added to the mixture A, and dispersed by a high speed disperser to obtain a mixture B;
  • the metal of the aluminum alloy is cut into a size of 200 mm ⁇ 100 mm (2 pieces), placed in a 5% by weight aqueous solution of nitric acid for 30 s, and then immersed in a 10% by weight aqueous sodium hydroxide solution for 30 s;
  • step 7) Applying the step 5) to the surface of the two pieces of metal to obtain the binder (coating thickness is approximately 0.2 mm), and then laminating the metal, the prepreg fiber cloth (size: 200 mm ⁇ 100 mm), and the metal in this order (metal
  • the surface coated with the binder was opposed to the prepreg fiber cloth, and then hot pressed at 140 ° C for 30 min at a pressure of 0.5 MPa. Then, it was cooled and pressure-reduced to obtain a fiber-metal laminate A1.
  • the cross section of the fiber metal laminate is observed by a microscope, and the fiber metal laminate is composed of a metal layer, a resin bonding layer, a fiber layer, a resin bonding layer, and a metal layer which are sequentially laminated, and bonded in the resin.
  • the chopped fibers are embedded between the layer and the fiber cloth, and the thickness of the adhesive layer is approximately 0.05 mm.
  • pretreatment agent on the surface of 8kg chopped fiber (glass chopped fiber, length 200 ⁇ m cross section diameter 10 ⁇ m), drying to obtain pretreated fiber filament X;
  • step 2) The pretreated filament X obtained in step 2) is added to the mixture A, and dispersed by a high speed disperser to obtain a mixture B;
  • the metal of the aluminum alloy is cut into a size of 200 mm ⁇ 100 mm (2 pieces), placed in a 5% by weight aqueous solution of nitric acid for 30 s, and then immersed in a 10% by weight aqueous sodium hydroxide solution for 30 s;
  • step 7) Applying the step 5) to the surface of the two pieces of metal to obtain a binder (coating thickness is approximately 0.3 mm), and then sequentially laminating the metal, prepreg fiber cloth (size: 200 mm ⁇ 100 mm), metal (metal The surface coated with the binder was opposed to the prepreg fiber cloth, and then hot pressed at 140 ° C for 90 min at a pressure of 0.5 MPa. Then, it was cooled and pressure-reduced to obtain a fiber-metal laminate A2.
  • the cross section of the fiber metal laminate is observed by a microscope, and the fiber metal laminate is composed of a metal layer, a resin bonding layer, a fiber cloth, a resin bonding layer, and a metal layer which are sequentially laminated, and bonded in the resin.
  • the chopped fibers are embedded between the layer and the fiber cloth, and the thickness of the adhesive layer is approximately 0.2 mm.
  • Preparing a pretreatment agent according to a ratio (mass ratio) of a silane coupling agent: a dispersing agent: ethanol 1:3:100;
  • step 2) The pretreated filament X obtained in step 2) is added to the mixture A, and dispersed by a high speed disperser to obtain a mixture B;
  • the metal of the aluminum alloy is cut into a size of 200 mm ⁇ 100 mm (2 pieces), placed in a 5% by weight aqueous solution of nitric acid for 30 s, and then immersed in a 10% by weight aqueous sodium hydroxide solution for 30 s;
  • step 7) Applying the step 5) to the surface of the two pieces of metal to obtain the binder (coating thickness is approximately 0.2 mm), and then laminating the metal, the prepreg fiber cloth (size: 200 mm ⁇ 100 mm), and the metal in this order (metal
  • the surface coated with the binder was opposed to the prepreg fiber cloth, and then heat-pressed at 140 ° C for 60 min at a pressure of 0.5 MPa. Then, it was cooled and pressure-reduced to obtain a fiber-metal laminate A3.
  • the cross section of the fiber metal laminate is observed by a microscope, and the fiber metal laminate is composed of a metal layer, a resin bonding layer, a fiber cloth, a resin bonding layer, and a metal layer which are sequentially laminated, and bonded in the resin.
  • the layer and the fiber cloth have chopped fibers, and the thickness of the adhesive layer is approximately 0.15 mm.
  • Example 1 The procedure of Example 1 was carried out except that the length of the glass chopped fibers was 75 ⁇ m and the cross-sectional diameter was 3 ⁇ m, and the fiber metal laminate A4 was obtained in the same manner.
  • the cross section of the fiber metal laminate is observed by a microscope, and the fiber metal laminate is composed of a metal layer, a resin bonding layer, a fiber cloth, a resin bonding layer, and a metal layer which are sequentially laminated, and bonded in the resin.
  • the layer and the fiber cloth have chopped fibers, and the thickness of the adhesive layer is approximately 0.05 mm.
  • Example 1 The procedure of Example 1 was carried out except that the length of the glass chopped fibers was 500 ⁇ m and the cross-sectional diameter was 5 ⁇ m, and the fiber metal laminate A5 was obtained in the same manner.
  • the cross section of the fiber metal laminate is observed by a microscope, and the fiber metal laminate is composed of a metal layer, a resin bonding layer, a fiber cloth, a resin bonding layer, and a metal layer which are sequentially laminated, and bonded in the resin.
  • the layer and the fiber cloth have chopped fibers, and the thickness of the adhesive layer is approximately 0.05 mm.
  • Example 1 The method of Example 1 was carried out except that the length of the glass chopped fibers was 800 ⁇ m and the cross-sectional diameter was 8 ⁇ m.
  • the fiber metal laminate A6 was obtained in the same manner.
  • the cross section of the fiber metal laminate is observed by a microscope, and the fiber metal laminate is composed of a metal layer, a resin bonding layer, a fiber cloth, a resin bonding layer, and a metal layer which are sequentially laminated, and bonded in the resin.
  • the layer and the fiber cloth have chopped fibers, and the thickness of the adhesive layer is approximately 0.05 mm.
  • Example 1 The procedure of Example 1 was carried out except that the length of the glass chopped fibers was 1000 ⁇ m and the cross-sectional diameter was 10 ⁇ m, and the fiber metal laminate A7 was obtained in the same manner.
  • the cross section of the fiber metal laminate is observed by a microscope, and the fiber metal laminate is composed of a metal layer, a resin bonding layer, a fiber cloth, a resin bonding layer, and a metal layer which are sequentially laminated, and bonded in the resin.
  • the layer and the fiber cloth have chopped fibers, and the thickness of the adhesive layer is approximately 0.05 mm.
  • Example 1 The procedure of Example 1 was carried out except that the surface of the chopped fiber in step 1 was not sprayed with a pretreatment agent to obtain a fiber metal laminate A8.
  • the cross section of the fiber metal laminate is observed by a microscope, and the fiber metal laminate is composed of a metal layer, a resin bonding layer, a fiber cloth, a resin bonding layer, and a metal layer which are sequentially laminated, and bonded in the resin.
  • the layer and the fiber cloth have chopped fibers, and the thickness of the adhesive layer is approximately 0.05 mm.
  • Example 1 The procedure of Example 1 was carried out except that the chopped fibers were not added in the step 1, and the fiber metal laminate D1 was obtained.
  • Example 1 The procedure of Example 1 was carried out except that the length of the chopped fibers in step 1 was 2.5 mm, and a fiber metal laminate D2 was obtained.
  • the fiber metal laminates A1-A8 and D1-D2 obtained in Examples 1-8 and Comparative Examples 1-2 were respectively cut into splines having a size of 100 mm ⁇ 20 mm (in which the fiber direction is the length direction of the splines); The spline was peeled off at a peeling speed of 10 mm/min on a universal material testing machine, and the metal on the peeling side was completely peeled off, and the data was recorded. This value is the peeling strength.

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Abstract

一种纤维金属层合板及其制备方法，纤维金属层合板包括依次层叠的金属层（1）、树脂粘结层（2）和纤维层（3），树脂粘结层（2）和纤维层（3）之间包埋有短切纤维（4），且短切纤维（4）的长度为50μm-2mm。

Description

纤维金属层合板及其制备方法
相关申请的交叉引用
本申请主张在2015年7月27日在中国提交的中国专利申请号No.201510444674.5的优先权，其全部内容通过引用包含于此。
技术领域
本公开涉及纤维金属层合板及其制备方法。
背景技术
为了克服广泛应用于航空航天领域的铝合金材料和纤维复合材料存在的一些缺点，荷兰代尔夫特理工大学研制出了金属材料与纤维复合的纤维金属层合板材料，即纤维金属层合板。纤维金属层合板是一类新型的混杂增强结构复合材料，不仅结合了金属与纤维复合材料的优点，还克服了其大部分的缺点，是一种在航空航天、军事、汽车等高科技领域有巨大应用前景的结构材料。虽然纤维金属层合板具有一系列优异的性能，但是其金属层与纤维布之间的结合力较弱。
因此，纤维金属层合板有待于进一步的研究。
发明内容
本公开的目的是提供一种纤维金属层合板及其制备方法。所述纤维金属层合板的金属层与纤维布之间具有较强的结合力。
本公开一方面的实施例提供了一种纤维金属层合板，包括层叠的金属层、树脂粘结层和纤维层，所述树脂粘结层和所述纤维层之间包埋有短切纤维，且所述短切纤维的长度为50μm-2mm。
本公开另一方面的实施例还提供了制备上述纤维金属层合板的方法，包括：将粘结剂涂布于金属层表面以便在所述金属层表面形成树脂粘结层；将纤维层设置在所述树脂粘结层上；以及热压使所述纤维层、所述树脂层和所述金属层结合为一体，从而获得所述纤维金属层合板，其中所述纤维金属层合板包括层叠的所述金属层、所述树脂粘结层和所述纤维层,其中所述粘结剂由含有热固化性粘结剂树脂及短切纤维的树脂组合物形成，其中所述短切纤维的长度为50μm-2mm。
本公开另一方面的实施例还提供了一种纤维金属层合板，包括：第一金属层；第一树脂粘结层，设置在所述第一金属层上；纤维层，设置在所述第一树脂粘结层上；第二树脂粘结 层，设置在所述纤维层上；和第二金属层，设置在所述第二树脂粘结层上，其中所述第一树脂粘结层和所述纤维层以及所述第二树脂粘结层和所述纤维层之间包埋有短切纤维，且所述短切纤维的长度为50μm-2mm。
根据本公开的纤维金属层合板，其金属层与纤维布之间的结合力强。
本公开的其它特征和优点将在随后的具体实施方式部分予以详细说明。
具体实施方式
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本发明，而不能理解为对本发明的限制。下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本发明，而不能理解为对本发明的限制。
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本发明的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。
在本发明中，除非另有明确的规定和限定，第一特征在第二特征之“上”或之“下”可以包括第一和第二特征直接接触，也可以包括第一和第二特征不是直接接触而是通过它们之间的另外的特征接触。而且，第一特征在第二特征“之上”、“上方”和“上面”包括第一特征在第二特征正上方和斜上方，或仅仅表示第一特征水平高度高于第二特征。第一特征在第二特征“之下”、“下方”和“下面”包括第一特征在第二特征正上方和斜上方，或仅仅表示第一特征水平高度小于第二特征。
本公开提供的纤维金属层合板包括层叠的金属层1、树脂粘结层2和纤维层3，所述树脂粘结层2和纤维层3之间包埋有短切纤维4，且所述短切纤维4的长度为50μm-2mm。
根据本公开，为进一步提高金属层1与纤维层3之间的结合力，可选地，所述短切纤维4的长度为75μm-1mm。
另外，在本公开中，所述短切纤维4的直径可以在较大范围内变动，可选地所述短切纤维4的截面直径为0.5μm-20μm，例如为1μm-10μm。
在本公开中，可选地，所述短切纤维4为玻璃纤维、碳纤维和芳纶纤维中的一种或多种。
在本公开中，对于所述纤维层3没有特殊限制，其材质可以为常规的各种材质，例如， 所述纤维层3可以为玻璃纤维、碳纤维和芳纶纤维中的一种或多种编织而成的纤维布。
本公开中，对于上述纤维层3的单位面积质量没有特殊限制，具体可以在较大范围内变动，可选地所述纤维层3的单位面积质量为50g/cm2-650g/cm2，例如为150g/cm2-300g/cm2。
上述树脂粘结层2可以为由含有热固化性粘结剂树脂及短切纤维的树脂组合物固化而得到层。
可选地，所述热固化性粘结剂树脂为丙烯酸树脂、环氧树脂、聚氨酯树脂、聚酯树脂、苯丙噁嗪树脂、酚醛树脂、尿素树脂和三聚氰胺树脂中一种或多种。例如为环氧树脂。
可选地，所述树脂组合物还含有活性稀释剂。可选地，相对于100重量份的热固化性粘结剂树脂，所述活性稀释剂的含量为10-55重量份；可选地，相对于100重量份的热固化性粘结剂树脂，所述活性稀释剂的含量为13-53重量份。
所述活性稀释剂用于溶解和分散成膜物质，具有在涂料成膜过程中参与成膜反应，形成不发挥组分留在涂膜中的作用。作为上述所述活性稀释剂可选为丙烯基缩水甘油醚、丁基缩水甘油醚、乙二醇双缩水甘油醚、间苯二酚双缩水甘油醚、己二醇二缩水甘油醚、丁二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、新戊二醇二缩水甘油醚和烷基多缩水甘油醚中的一种或多种。从降低粘度效果更优，对纤维预浸效果更好的方面来考虑，可选地，所述活性稀释剂为丁基缩水甘油醚、丁二醇二缩水甘油醚、新戊二醇二缩水甘油醚和烷基多缩水甘油醚中的一种或多种。具体地，作为所述活性稀释剂可以使用江苏三木集团有限公司的型号为SM678的活性稀释剂(成分为新戊二醇二缩水甘油醚)。
根据本公开，可选地，所述树脂组合物还含有固化剂。可选地，相对于100重量份的热固化性粘结剂树脂，所述固化剂的含量为1-55重量份；可选地，相对于100重量份的热固化性粘结剂树脂，所述固化剂的含量为2-50重量份。
所述固化剂可以为本领域常用的各种用于固化的固化剂。可选地，为二氨基二苯基甲烷、间苯二胺、二氨基二苯基砜己二酸二酰肼、双氰胺、三乙烯二胺、三乙烯四胺、四乙烯五胺、二乙氨基丙胺、孟烷二胺、异佛尔酮二胺、N-氨乙基哌嗪、双(4-氨基-3-甲基环己基)甲烷和双(4-胺基环己基)甲烷中的一种或多种。例如为双氰胺。
根据本公开，可选地，所述树脂组合物还可以含有固化促进剂。可选地，相对于100重量份的热固化性粘结剂树脂，所述固化促进剂的含量为0-10重量份；可选地，相对于100重量份的热固化性粘结剂树脂，所述固化促进剂的含量为0.9-8.8重量份。
所述固化促进剂可以本领域常用的各种固化促进剂。例如可以为有机胍类化合物、咪唑类化合物和脲类化合物中的一种或多种；例如为咪唑类化合物；例如为1-甲基咪唑。
根据本公开，可选地，所述树脂组合物还可以含有消泡剂、流平剂和润湿剂中的一种或多种。可选地，相对于100重量份的热固化性粘结剂树脂，所述泡剂、流平剂和润湿剂的 含量分别为0-12重量份，例如为1.5-11重量份。
所述消泡剂、流平剂和润湿剂可以本领域常用的各种消泡剂、流平剂和润湿剂。可选地，所述消泡剂为聚丙烯酸-聚醚共聚物消泡剂、有机硅类消泡剂、有机改性聚硅氧烷消泡剂和氟硅氧烷消泡剂中的一种或多种；所述流平剂为丙烯酸酯、聚醚硅氧烷共聚物和有机改性聚硅氧烷中的一种或多种；所述润湿剂为非离子有机表面活性剂。具体地，作为所述消泡剂可以使用DEGO Airex 932消泡剂(氟硅氧烷消泡剂)
另外，本公开中，可选地所述树脂粘结层的厚度为0.02mm-0.5mm，例如为0.02mm-0.2mm。
本公开中，上述金属层可采用现有的具有各种材质和结构的金属板，例如，所述金属层为铝合金板、钛合金板和钢板中的一种。本公开中，可选地采用常规的铝合金板。对于上述金属层的厚度，本公开中没有特殊限制，具体可以在较大范围内变动，本领域技术人员可根据实际情况进行调整，可选地所述金属层的厚度为0.1mm-3mm。
根据本公开，可选地，所述短切纤维4表面包覆有硅烷偶联剂。通过在所述短切纤维表面包覆有硅烷偶联剂，具有能和纤维表面化学结合的反应基团，可以在纤维和预浸树脂间起来桥梁作用的效果，从而能够进一步提高层间结合力。
在所述短切纤维4表面包覆硅烷偶联剂的方法可以为本领域所公知的方法，例如将硅烷偶联剂与分散剂和溶剂混合后的溶液喷洒在所述短切纤维的表面后干燥。
所述硅烷偶联剂可以为本领域所常用的各种硅烷偶联剂。可选地，所述硅烷偶联剂为氨基硅烷、环氧基硅烷、硫基硅烷、甲基丙烯酰氧基硅烷、乙烯基硅烷、脲基硅烷和异氰酸酯基硅烷中的一种或多种。可选地，所述硅烷偶联剂为氨基硅烷和环氧基硅烷中的一种或多种。所述分散剂可以为本领域所常用的各种分散剂，可选地为水玻璃、三聚磷酸钠、六偏磷酸钠、焦磷酸钠、三乙基己基磷酸、十二烷基硫酸钠、甲基戊醇、纤维素衍生物、聚丙烯酰胺、古尔胶、脂肪族聚乙二醇酯和改性聚烷氧化物中的一种或多种。所述溶剂只要能够很好地将所述硅烷偶联剂和分散剂溶剂即可，例如可以为乙醇、二甲苯、正丁醇、乙二醇丁醚、乙酸丁酯、异丙醇、环己酮和甲基异丁基酮中的一种或多种。
对于硅烷偶联剂、分散剂和溶剂的混合质量比例可选为1：0.5-5：50-200；例如为＝1：3：100。
另外，如本领域技术人员知晓的，纤维金属层合板的层数根据不同的实际情况可以相应增减。例如，常用的纤维金属层合板包括纤维层、两个所述金属层和两个所述树脂粘结层；所述两个树脂粘结层位于所述两个金属层之间，所述纤维布位于所述两个树脂粘结层之间。本公开中，当纤维金属层合板包括纤维层、两个所述金属层和两个所述树脂粘结层时，所述两个树脂粘结层和纤维布之间均包埋有所述短切纤维。
本公开还提供一种制备纤维金属层合板的方法，包括：将粘结剂涂布于金属层1表面以便在所述金属层表面形成树脂粘结层2；将纤维层3设置在所述树脂粘结层2上；以及热压使所述纤维层3、所述树脂层2和所述金属层1结合为一体，从而获得所述纤维金属层合板，其中所述纤维金属层合板包括层叠的所述金属层1、所述树脂粘结层2和所述纤维层3，其中所述粘结剂由含有热固化性粘结剂树脂及短切纤维4的树脂组合物形成，其中所述短切纤维4的长度为50μm-2mm。
根据本公开的制备纤维金属层合板的方法，为了得到金属层1与纤维层3之间的结合力优良的纤维金属层合板，可选地，相对于100重量份的热固化性粘结剂树脂，所述短切纤维4的含量为5-50重量份；可选地，相对于100重量份的热固化性粘结剂树脂，所述短切纤维的含量为8-38重量份。
对于上述短切纤维4，可选地其长度为75μm-1mm。
在本公开的制备纤维金属层合板的方法中，短切纤维4的直径可以在较大范围内变动，可选地所述短切纤维4的截面直径为0.5μm-20μm，例如为1μm-10μm。
在本公开的制备纤维金属层合板的方法中，可选地，所述短切纤维为玻璃纤维、碳纤维和芳纶纤维中的一种或多种。
根据本公开的制备纤维金属层合板的方法，所述树脂组合物含有所述热固化性粘结剂树脂。所述热固化性粘结剂树脂可选为丙烯酸树脂、环氧树脂、聚氨酯树脂、聚酯树脂、苯丙噁嗪树脂、酚醛树脂、尿素树脂和三聚氰胺树脂中一种或多种。例如为环氧树脂。
根据本公开的制备纤维金属层合板的方法，可选地，所述树脂组合物还含有活性稀释剂。所述活性稀释剂的用量可以为本领域的常规用量，相对于100重量份的热固化性粘结剂树脂，所述活性稀释剂的含量为10-55重量份；可选地，相对于100重量份的热固化性粘结剂树脂，所述活性稀释剂的含量为13-53重量份。
所述活性稀释剂用于溶解和分散成膜物质，具有在涂料成膜过程中参与成膜反应，形成不发挥组分留在涂膜中的作用。所述活性稀释剂可选为丙烯基缩水甘油醚、丁基缩水甘油醚、乙二醇双缩水甘油醚、间苯二酚双缩水甘油醚、己二醇二缩水甘油醚、丁二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、新戊二醇二缩水甘油醚和烷基多缩水甘油醚中的一种或多种；从降低粘度效果更优，对纤维预浸效果更好的方面来考虑，可选地，所述活性稀释剂为丁基缩水甘油醚、丁二醇二缩水甘油醚、新戊二醇二缩水甘油醚和烷基多缩水甘油醚中的一种或多种。具体地，所述活性稀释剂可以使用江苏三木集团有限公司的型号为SM678的活性稀释剂(成分为新戊二醇二缩水甘油醚)。
根据本公开的制备纤维金属层合板的方法，可选地，所述树脂组合物还含有固化剂。所述固化剂的用量可以为本领域的常规用量，可选地，相对于100重量份的热固化性粘结剂 树脂，所述固化剂的含量为1-55重量份；可选地，相对于100重量份的热固化性粘结剂树脂，所述固化剂的含量为2-50重量份。
所述固化剂可以为本领域常用的各种用于固化的固化剂，可选地为二氨基二苯基甲烷、间苯二胺、二氨基二苯基砜己二酸二酰肼、双氰胺、三乙烯二胺、三乙烯四胺、四乙烯五胺、二乙氨基丙胺、孟烷二胺、异佛尔酮二胺、N-氨乙基哌嗪、双(4-氨基-3-甲基环己基)甲烷和双(4-胺基环己基)甲烷中的一种或多种。例如为双氰胺。
根据本公开的制备纤维金属层合板的方法，可选地，所述树脂组合物还含有固化促进剂。所述固化促进剂的用量可以为本领域的常规用量，可选地，相对于100重量份的热固化性粘结剂树脂，所述固化促进剂的含量为0-10重量份；可选地，相对于100重量份的热固化性粘结剂树脂，所述固化促进剂的含量为0.9-8.8重量份。
所述固化促进剂可以本领域常用的各种固化促进剂。例如可以为有机胍类化合物、咪唑类化合物和脲类化合物中的一种或多种；例如为咪唑类化合物；例如为1-甲基咪唑。
所述树脂组合物还可以含有消泡剂、流平剂和润湿剂中的一种或多种。可选地，相对于100重量份的热固化性粘结剂树脂，所述泡剂、流平剂和润湿剂的含量分别为0-12重量份，例如为1.5-11重量份。
所述消泡剂、流平剂和润湿剂可以本领域常用的各种消泡剂、流平剂和润湿剂。可选地，所述消泡剂例如为聚丙烯酸-聚醚共聚物消泡剂、有机硅类消泡剂、有机改性聚硅氧烷消泡剂和氟硅氧烷消泡剂中的一种或多种；所述流平剂例如为丙烯酸酯、聚醚硅氧烷共聚物和有机改性聚硅氧烷中的一种或多种；所述润湿剂例如为非离子有机表面活性剂中的一种或多种。具体地，所述消泡剂可以为DEGO Airex 932消泡剂(氟硅氧烷消泡剂)。
根据本公开的制备纤维金属层合板的方法，所述预浸纤维布可以商购获得，也可以采用本领域常规的方法制备得到。例如可以通过将纤维布与预浸料组合物接触而得到；所述预浸料组合物含有热固化性粘结剂树脂、活性稀释剂、固化剂、固化促进剂以及消泡剂。所述预浸料组合物含有的热固化性粘结剂树脂、活性稀释剂、固化剂、固化促进剂和消泡剂为本领域所公知。另外，所述预浸料组合物含有的热固化性粘结剂树脂、活性稀释剂、固化剂、固化促进剂和消泡剂也可以分别与上述树脂组合物中含有热固化性粘结剂树脂、活性稀释剂、固化剂、固化促进剂和消泡剂相同。
对于上述纤维布的材质没有特殊限制，其材质可以为常规的各种材质，例如，具体可以为玻璃纤维布、碳纤维布和芳纶纤维布中的一种或多种，也可以为上述玻璃纤维、碳纤维和芳纶纤维中的一种或多种形成的混纺布。
另外，对于上述纤维布的单位面积的质量没有特殊限制，具体可以在较大范围内变动，可选地所述纤维布的单位面积的质量为50g/cm2-650g/cm2，例如为150g/cm2-300g/cm2。
根据本公开的制备纤维金属层合板的方法，上述金属层可采用现有的具有各种材质和结构的金属板，例如，所述金属层为铝合金板、钛合金板和钢板中的一种。本公开中，可选地采用常规的铝合金板。对于上述金属层的厚度，本公开中没有特殊限制，具体可以在较大范围内变动，本领域技术人员可根据实际情况进行调整，可选地所述金属层的厚度为0.1mm-3mm。
另外，可选地，上述金属在与预浸纤维布层叠之前，将金属进行除油去污处理。所述除油去污的方法为本领域所公知，例如将上述金属用酸浸泡后再用碱浸泡。具体地，例如可以将上述金属放入到5重量％的硝酸水溶液中浸泡30s，然后再在10重量％的氢氧化钠水溶液中浸泡30s。
根据本公开的制备纤维金属层合板的方法，可选地，所述短切纤维表面包覆有硅烷偶联剂。通过在所述短切纤维表面包覆有硅烷偶联剂，具有能和纤维表面化学结合的反应基团，可以在纤维和预浸树脂间起来桥梁作用的效果，从而能够进一步提高层间结合力。
在所述短切纤维表面包覆硅烷偶联剂的方法可以为本领域所公知的方法，例如将硅烷偶联剂与分散剂和溶剂混合后的溶液喷洒在所述短切纤维的表面。
所述硅烷偶联剂可以为本领域所常用的各种硅烷偶联剂。可选地，所述硅烷偶联剂为氨基硅烷、环氧基硅烷、硫基硅烷、甲基丙烯酰氧基硅烷、乙烯基硅烷、脲基硅烷和异氰酸酯基硅烷中的一种或多种；可选地，所述硅烷偶联剂为氨基硅烷和/或环氧基硅烷。作为所述分散剂可以为本领域所常用的各种分散剂，可选为水玻璃、三聚磷酸钠、六偏磷酸钠、焦磷酸钠、三乙基己基磷酸、十二烷基硫酸钠、甲基戊醇、纤维素衍生物、聚丙烯酰胺、古尔胶、脂肪族聚乙二醇酯和改性聚烷氧化物中的一种或多种。作为所述溶剂只要能够很好地将所述硅烷偶联剂和分散剂溶剂即可，例如可以为乙醇、二甲苯、正丁醇、乙二醇丁醚、乙酸丁酯、异丙醇、环己酮和甲基异丁基酮中的一种或多种。
对于硅烷偶联剂、分散剂和溶剂的混合质量比例可选为1：0.5-5：50-200；例如为＝1：3：100。
根据本公开的制备纤维金属层合板的方法，通过将树脂组合物中的各成分混合分散后得到粘结剂。对于树脂组合物中各成分的混合顺序没有特别的要求，可以是任意的。但是，从进一步提高金属层和纤维布之间的层间结合力上来考虑，可选地，将热固化性粘结剂树脂和活性稀释剂混合分散后，再加入短切纤维进行分散混合，然后加入固化剂、固化促进剂和消泡剂后进行分散混合，从而得到粘结剂。
根据本公开的制备纤维金属层合板的方法，将粘结剂涂布于金属层表面以便在所述金属层表面形成树脂粘结层，所述粘结剂的涂覆厚度可选为0.02mm-0.5mm，例如为0.05mm-0.2mm。
根据本公开，热压使所述纤维层、所述树脂层和所述金属层结合为一体，从而获得所述纤维金属层合板，其中所述纤维金属层合板包括层叠的所述金属层、所述树脂粘结层和所述纤维层。
具体热压方法为本领域所常用的，可选地所述热压方法为：在120℃-140℃、0.1MPa-10MPa压力下热压30min-120min，然后冷却后卸压。
以下将通过实施例对本公开进行详细描述。
以下实施例和对比例中，原料为以下公司的市售品。
Figure PCTCN2016090900-appb-000001
实施例1
1、粘结剂的制备
1)按照硅烷偶联剂：分散剂：乙醇＝1：3：100的比例(质量比)配制预处理剂；
2)在4kg玻纤短切纤维(玻璃短切纤维，长度为200μm，截面直径为10μm)表面喷洒预处理剂，烘干得到预处理纤维丝X；
3)称取环氧树脂48kg、活性稀释剂25kg，用高速分散机(购于上海法孚莱能源有限公司，以下相同)分散，得到混合物A；
4)将步骤2)中得到的预处理纤维丝X加入混合物A中，用高速分散机分散，得到混合物B；
5)称取双氰胺15kg(固化剂)、1-甲基咪唑5kg(固化促进剂)、消泡剂3kg，加入混合物B中，用高速分散机分散，得到粘结剂；
6)将铝合金的金属裁剪成长宽为200mm×100mm的尺寸(2片)，放入到5重量％的硝酸水溶液中浸泡30s，然后再在10重量％的氢氧化钠水溶液中浸泡30s；
7)分别在两片金属的表面涂覆步骤5)得到粘结剂(涂覆厚度大致为0.2mm)，然后再将金属、预浸纤维布(尺寸：200mm×100mm)、金属依次层叠(金属涂覆有粘结剂的表面与预浸纤维布相对)，然后在140℃下，以0.5MPa的压力热压30min。然后冷却、卸压，得到纤维金属层合板A1。
将该纤维金属层合板的横截面通过显微镜观察可知，该纤维金属层合板由依次层叠的金属层、树脂粘结层、纤维层、树脂粘结层和金属层构成，且在所述树脂粘结层和纤维布之间包埋有短切纤维，另外，粘着剂层的厚度大致为0.05mm。
实施例2
1)按照硅烷偶联剂：分散剂：乙醇＝1：3：100的比例(质量比)配制预处理剂；
2)在8kg短切纤维(玻璃短切纤维，长度为200μm截面直径为10μm)表面喷洒预处理剂，烘干得到预处理纤维丝X；
3)称取环氧树脂75kg、活性稀释剂10kg，用高速分散机分散，得到混合物A；
4)将步骤2)中得到的预处理纤维丝X加入混合物A中，用高速分散机分散，得到混合物B；
5)称取双氰胺5kg(固化剂)、1-甲基咪唑0.7kg(固化促进剂)、消泡剂1.3kg，加入混合物B中，用高速分散机分散，得到粘结剂；
6)将铝合金的金属裁剪成长宽为200mm×100mm的尺寸(2片)，放入到5重量％的硝酸水溶液中浸泡30s，然后再在10重量％的氢氧化钠水溶液中浸泡30s；
7)分别在两片金属的表面涂覆步骤5)得到粘结剂(涂覆厚度大致为0.3mm)，然后再将金属、预浸纤维布(尺寸：200mm×100mm)、金属依次层叠(金属涂覆有粘结剂的表面与预浸纤维布相对)，然后在140℃下，以0.5MPa的压力热压90min。然后冷却、卸压，得到纤维金属层合板A2。
将该纤维金属层合板的横截面通过显微镜观察可知，该纤维金属层合板由依次层叠的金属层、树脂粘结层、纤维布、树脂粘结层和金属层构成，且在所述树脂粘结层和纤维布之间包埋有短切纤维，另外，粘着剂层的厚度大致为0.2mm。
实施例3
按照硅烷偶联剂：分散剂：乙醇＝1：3：100的比例(质量比)配制预处理剂；
2)在15kg短切纤维(玻璃短切纤维，长度为200μm，截面直径为10μm)表面喷洒预 处理剂，烘干得到预处理纤维丝X；
3)称取环氧树脂40.5kg、活性稀释剂18kg，用高速分散机分散，得到混合物A；
4)将步骤2)中得到的预处理纤维丝X加入混合物A中，用高速分散机分散，得到混合物B；
5)称取双氰胺20kg(固化剂)、1-甲基咪唑3.5kg(固化促进剂)、消泡剂3kg，加入混合物B中，用高速分散机分散，得到粘结剂；
6)将铝合金的金属裁剪成长宽为200mm×100mm的尺寸(2片)，放入到5重量％的硝酸水溶液中浸泡30s，然后再在10重量％的氢氧化钠水溶液中浸泡30s；
7)分别在两片金属的表面涂覆步骤5)得到粘结剂(涂覆厚度大致为0.2mm)，然后再将金属、预浸纤维布(尺寸：200mm×100mm)、金属依次层叠(金属涂覆有粘结剂的表面与预浸纤维布相对)，然后在140℃下，以0.5MPa的压力热压60min。然后冷却、卸压，得到纤维金属层合板A3。
将该纤维金属层合板的横截面通过显微镜观察可知，该纤维金属层合板由依次层叠的金属层、树脂粘结层、纤维布、树脂粘结层和金属层构成，且在所述树脂粘结层和纤维布之间具有短切纤维，另外，粘着剂层的厚度大致为0.15mm。
实施例4
按照实施例1的方法进行，不同的是玻璃短切纤维的长度为75μm，截面直径为3μm，相同地得到纤维金属层合板A4。
将该纤维金属层合板的横截面通过显微镜观察可知，该纤维金属层合板由依次层叠的金属层、树脂粘结层、纤维布、树脂粘结层和金属层构成，且在所述树脂粘结层和纤维布之间具有短切纤维，另外，粘着剂层的厚度大致为0.05mm。
实施例5
按照实施例1的方法进行，不同的是玻璃短切纤维的长度为500μm，截面直径为5μm，相同地得到纤维金属层合板A5。
将该纤维金属层合板的横截面通过显微镜观察可知，该纤维金属层合板由依次层叠的金属层、树脂粘结层、纤维布、树脂粘结层和金属层构成，且在所述树脂粘结层和纤维布之间具有短切纤维，另外，粘着剂层的厚度大致为0.05mm。
实施例6
按照实施例1的方法进行，不同的是玻璃短切纤维的长度为800μm，截面直径为8μm， 相同地得到纤维金属层合板A6。
将该纤维金属层合板的横截面通过显微镜观察可知，该纤维金属层合板由依次层叠的金属层、树脂粘结层、纤维布、树脂粘结层和金属层构成，且在所述树脂粘结层和纤维布之间具有短切纤维，另外，粘着剂层的厚度大致为0.05mm。
实施例7
按照实施例1的方法进行，不同的是玻璃短切纤维的长度为1000μm，截面直径为10μm，相同地得到纤维金属层合板A7。
将该纤维金属层合板的横截面通过显微镜观察可知，该纤维金属层合板由依次层叠的金属层、树脂粘结层、纤维布、树脂粘结层和金属层构成，且在所述树脂粘结层和纤维布之间具有短切纤维，另外，粘着剂层的厚度大致为0.05mm。
实施例8
按照实施例1的方法进行，不同的是步骤1中短切纤维表面未喷洒预处理剂，得到纤维金属层合板A8。
将该纤维金属层合板的横截面通过显微镜观察可知，该纤维金属层合板由依次层叠的金属层、树脂粘结层、纤维布、树脂粘结层和金属层构成，且在所述树脂粘结层和纤维布之间具有短切纤维，另外，粘着剂层的厚度大致为0.05mm。
对比例1
按照实施例1的方法进行，不同的是步骤1中未加入短切纤维，得到纤维金属层合板D1。
对比例2
按照实施例1的方法进行，不同的是步骤1中短切纤维的长度为2.5mm，得到纤维金属层合板D2。
测试例1(剥离强度测试)
将实施例1-8和对比例1-2得到的纤维金属层合板A1-A8和D1-D2分别裁剪为尺寸为100mm×20mm的样条(其中纤维方向是样条长度方向)；将得到的样条在万能材料试验机上，以剥离速度为10mm/min进行剥离，使剥离侧的金属完全脱落，记录下数据，该值即为剥离强度。
其结果如表1所示。
表1
序号 剥离强度(N)
A1 235
A2 280
A3 256
A4 230
A5 242
A6 248
A7 260
A8 200
D1 150
D2 170
以上详细描述了本公开的可选实施方式，但是，本公开并不限于上述实施方式中的具体细节，在本公开的技术构思范围内，可以对本公开的技术方案进行多种简单变型，这些简单变型均属于本公开的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合为了避免不必要的重复，本公开对各种可能的组合方式不再另行说明。
此外，本公开的各种不同的实施方式之间也可以进行任意组合，只要其不违背本公开的思想，其同样应当视为本公开所公开的内容。

Claims (38)

  1. 一种纤维金属层合板，包括层叠的金属层、树脂粘结层和纤维层，其中所述树脂粘结层和所述纤维层之间包埋有短切纤维，且所述短切纤维的长度为50μm-2mm。
  2. 根据权利要求1所述的纤维金属层合板，其中所述短切纤维的长度为75μm-1mm。
  3. 根据权利要求1或2所述的纤维金属层合板，其中所述短切纤维的截面直径为0.5μm-20μm。
  4. 根据权利要求1-3中任一项所述的纤维金属层合板，其中所述短切纤维的截面直径为1μm-10μm。
  5. 根据权利要求1-4中任一项所述的纤维金属层合板，其中所述短切纤维为玻璃纤维、碳纤维和芳纶纤维中的一种或多种。
  6. 根据权利要求1-5中任一项所述的纤维金属层合板，其中所述纤维层为玻璃纤维、碳纤维和芳纶纤维中的一种或多种编织而成的纤维布。
  7. 根据权利要求1-6中任一项所述的纤维金属层合板，其中所述纤维层的单位面积质量为50g/m2-650g/m2。
  8. 根据权利要求1-7中任一项所述的纤维金属层合板，其中所述树脂粘结层为由含有热固化性粘结剂树脂及短切纤维的树脂组合物固化而得到层。
  9. 根据权利要求1-8中任一项所述的纤维金属层合板，其中所述树脂粘结层的厚度为0.02mm-0.5mm。
  10. 根据权利要求1-9中任一项所述的纤维金属层合板，其中所述金属层为铝合金板、钛合金板和钢板中的一种。
  11. 根据权利要求1-10中任一项所述的纤维金属层合板，其中所述金属层的厚度为0.1mm-3mm。
  12. 根据权利要求1-11中任一项所述的纤维金属层合板，其中所述短切纤维表面包覆有硅烷偶联剂。
  13. 一种制备纤维金属层合板的方法，包括：
    将粘结剂涂布于金属层表面以便在所述金属层表面形成树脂粘结层；
    将纤维层设置在所述树脂粘结层上；以及
    热压使所述纤维层、所述树脂层和所述金属层结合为一体，从而获得所述纤维金属层合板，其中所述纤维金属层合板包括层叠的所述金属层、所述树脂粘结层和所述纤维层,
    其中所述粘结剂由含有热固化性粘结剂树脂及短切纤维的树脂组合物形成，
    其中所述短切纤维的长度为50μm-2mm。
  14. 根据权利要求13所述的方法，其中相对于100重量份的所述热固化性粘结剂树脂，所述短切纤维的含量为5-50重量份。
  15. 根据权利要求13或14所述的方法，其中相对于100重量份的所述热固化性粘结剂树脂，所述短切纤维的含量为8-38重量份。
  16. 根据权利要求13-15中任一项所述的方法，其中所述树脂组合物还含有活性稀释剂。
  17. 根据权利要求16中所述的方法，其中相对于100重量份的所述热固化性粘结剂树脂，所述活性稀释剂的含量为10-55重量份。
  18. 根据权利要求16或17所述的方法，其中相对于100重量份的所述热固化性粘结剂树脂，所述活性稀释剂的含量为13-53重量份。
  19. 根据权利要求16-18中任一项所述的方法，其中所述活性稀释剂为丙烯基缩水甘油醚、丁基缩水甘油醚、乙二醇双缩水甘油醚、间苯二酚双缩水甘油醚、己二醇二缩水甘油醚、丁二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、新戊二醇二缩水甘油醚和烷基多缩水甘油醚中的一种或多种。
  20. 根据权利要求13-19中任一项所述的方法，其中所述树脂组合物还含有固化剂。
  21. 根据权利要求20中所述的方法，其中相对于100重量份的所述热固化性粘结剂树脂，所述固化剂的含量为1-55重量份。
  22. 根据权利要求20或21所述的方法，其中相对于100重量份的所述热固化性粘结剂树脂，所述固化剂的含量为2-50重量份。
  23. 根据权利要求20-22中任一项所述的方法，其中所述固化剂为二氨基二苯基甲烷、间苯二胺、二氨基二苯基砜己二酸二酰肼、双氰胺、三乙烯二胺、三乙烯四胺、四乙烯五胺、二乙氨基丙胺、孟烷二胺、异佛尔酮二胺、N-氨乙基哌嗪、双(4-氨基-3-甲基环己基)甲烷和双(4-胺基环己基)甲烷中的一种或多种。
  24. 根据权利要求13-23中任一项所述的方法，其中所述树脂组合物还含有固化促进剂。
  25. 根据权利要求24所述的方法，其中相对于100重量份的所述热固化性粘结剂树脂，所述固化促进剂的含量为0-10重量份。
  26. 根据权利要求24或25所述的方法，其中相对于100重量份的所述热固化性粘结剂树脂，所述固化促进剂的含量为0.9-8.8重量份。
  27. 根据权利要求24-26中任一项所述的方法，其中所述树脂组合物还含有消泡剂、流平剂和润湿剂中的一种或多种。
  28. 根据权利要求13-27中任一项所述的方法，其中所述短切纤维的长度为75μm-1mm。
  29. 根据权利要求13-28中任一项所述的方法，其中所述短切纤维的截面直径为0.5μm-20μm。
  30. 根据权利要求13-29中任一项所述的方法，其中所述短切纤维的截面直径为1-10μm。
  31. 根据权利要求13-30中任一项所述的方法，其中所述短切纤维为玻璃纤维、碳纤维和芳纶纤维中的一种或多种。
  32. 根据权利要求13-31中任一项所述的方法，其中所述纤维层中的纤维布为玻璃纤维布、碳纤维布和芳纶纤维布中的一种或多种。
  33. 根据权利要求13-32中任一项所述的方法，其中所述纤维布的单位面积的质量为50g/m2-650g/m2。
  34. 根据权利要求13-33中任一项所述的方法，其中所述热固化性粘结剂树脂为丙烯酸树脂、环氧树脂、聚氨酯树脂、聚酯树脂、苯丙噁嗪树脂、酚醛树脂、尿素树脂和三聚氰胺树脂中一种或多种。
  35. 根据权利要求13-34中任一项所述的方法，其中所述短切纤维表面包覆有硅烷偶联剂。
  36. 根据权利要求13-35中任一项所述的方法，其中所述金属层为铝合金板、钛合金板和钢板中的一种。
  37. 根据权利要求13-36中任一项所述的方法，其中所述金属层的厚度为0.1mm-3mm。
  38. 一种纤维金属层合板，包括：
    第一金属层；
    第一树脂粘结层，设置在所述第一金属层上；
    纤维层，设置在所述第一树脂粘结层上；
    第二树脂粘结层，设置在所述纤维层上；和
    第二金属层，设置在所述第二树脂粘结层上，
    其中所述第一树脂粘结层和所述纤维层以及所述第二树脂粘结层和所述纤维层之间包埋有短切纤维，且所述短切纤维的长度为50μm-2mm。
PCT/CN2016/090900 2015-07-27 2016-07-21 纤维金属层合板及其制备方法 Ceased WO2017016435A1 (zh)

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Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107187130A (zh) * 2017-06-13 2017-09-22 北京航空航天大学 一种钛基超混杂复合材料层板及其制备方法
CN107187131A (zh) * 2017-06-13 2017-09-22 北京航空航天大学 一种铝基超混杂复合材料层板及其制备方法
CN107187124A (zh) * 2017-06-13 2017-09-22 北京航空航天大学 一种镁基超混杂复合材料层板及其制备方法
CN108312684A (zh) * 2017-12-11 2018-07-24 姜文明 一种铝合金与碳纤维固化上色工艺
CN110576646B (zh) * 2019-09-24 2023-09-29 华侨大学 一种自锁式多孔结构复合板
CN111013982A (zh) * 2019-11-06 2020-04-17 苏州胜禹材料科技股份有限公司 一种抗高温耐腐蚀镀铝锌板材及其生产方法
CN111186146A (zh) * 2020-01-14 2020-05-22 上海交通大学 Cfrp/高强钢烘烤硬化热冲压共固化一体化成形方法
CN111391421A (zh) * 2020-02-25 2020-07-10 长安大学 一种碳纤维与金属复合结构及其制备方法
CN111559137A (zh) * 2020-05-21 2020-08-21 燕山大学 一种硅烷表面改性的纤维增强金属复合板制备工艺
CN114074462A (zh) * 2020-08-05 2022-02-22 华为技术有限公司 一种壳体结构、其备制备方法及电子设备
CN112848544B (zh) * 2021-01-14 2023-03-31 中车青岛四方机车车辆股份有限公司 一种纤维金属层合板及其制备方法
CN112937062A (zh) * 2021-02-03 2021-06-11 沈阳中钛装备制造有限公司 胶粘式钛合金复合防护板的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1568255A (zh) * 2001-11-01 2005-01-19 多法斯科公司 层压板和其生产方法
CN1743398A (zh) * 2004-09-02 2006-03-08 陈金海 无机树脂
JP2011255669A (ja) * 2010-05-10 2011-12-22 Jfe Galvanizing & Coating Co Ltd 植毛鋼板
CN105522788A (zh) * 2014-11-24 2016-04-27 比亚迪股份有限公司 一种纤维金属层合板及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1746021A (zh) * 2004-09-09 2006-03-15 航天特种材料及应用研究所 纤维增强金属层压复合材料及其制作方法
CN101096822A (zh) * 2006-06-29 2008-01-02 四川省三台县固锐实业有限责任公司 纤维织物层叠材料的生产方法
WO2010144444A2 (en) * 2009-06-08 2010-12-16 Saint-Gobain Performance Plastics Corporation Articles containing silicone compositions and methods of making such articles
DE102012106206A1 (de) * 2012-07-10 2014-01-16 Thyssenkrupp Steel Europe Ag Sandwichblech und Verfahren zu dessen Herstellung

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1568255A (zh) * 2001-11-01 2005-01-19 多法斯科公司 层压板和其生产方法
CN1743398A (zh) * 2004-09-02 2006-03-08 陈金海 无机树脂
JP2011255669A (ja) * 2010-05-10 2011-12-22 Jfe Galvanizing & Coating Co Ltd 植毛鋼板
CN105522788A (zh) * 2014-11-24 2016-04-27 比亚迪股份有限公司 一种纤维金属层合板及其制备方法

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