CN112976720A - Honeycomb composite board and preparation method and application thereof - Google Patents

Honeycomb composite board and preparation method and application thereof Download PDF

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Publication number
CN112976720A
CN112976720A CN201911280826.7A CN201911280826A CN112976720A CN 112976720 A CN112976720 A CN 112976720A CN 201911280826 A CN201911280826 A CN 201911280826A CN 112976720 A CN112976720 A CN 112976720A
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CN
China
Prior art keywords
fiber
layer
adhesive film
prepreg
honeycomb
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CN201911280826.7A
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Chinese (zh)
Inventor
唐磊
王勇
张力存
李枝芳
李修成
刁兆银
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Shandong Shengquan New Material Co Ltd
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Shandong Shengquan New Material Co Ltd
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Priority to CN201911280826.7A priority Critical patent/CN112976720A/en
Publication of CN112976720A publication Critical patent/CN112976720A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
    • B32B3/12—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a layer of regularly- arranged cells, e.g. a honeycomb structure
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/08—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B32B2262/0269—Aromatic polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres

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  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a honeycomb core composite board and a preparation method and application thereof, wherein the honeycomb core composite board comprises a honeycomb core material, and a first adhesive film layer and a second adhesive film layer which are bonded on the upper surface and the lower surface of the honeycomb core material, wherein a first fiber layer is arranged on the surface of the first adhesive film layer, and a second fiber layer is arranged on the surface of the second adhesive film layer; the second fiber layer includes aramid prepreg and fiber prepreg. The honeycomb composite board has the effects of light weight, sound insulation, heat insulation and pressure resistance, and high-strength stable bonding is formed between layers, so that the honeycomb composite board has good stability and mechanical strength, and the introduction of aramid prepreg in the second fiber layer enables the honeycomb composite board to have excellent corrosion resistance, impact resistance and compression-resistant tensile strength, and can fully meet the application of the honeycomb composite board in transportation materials.

Description

Honeycomb composite board and preparation method and application thereof
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a honeycomb core composite board and a preparation method and application thereof.
Background
The honeycomb composite board is a composite material formed by sandwiching a honeycomb core between two layers of panel materials, has excellent performances of light weight, high specific strength, high specific rigidity, earthquake resistance, heat insulation, sound insulation and the like, and is favored in the automobile, aerospace, railway and ship manufacturing industries. The honeycomb composite board is divided into two major types of metal and nonmetal according to the material of the honeycomb core, the metal honeycomb composite board comprises an aluminum honeycomb composite board, a titanium honeycomb composite board, a stainless steel honeycomb composite board and the like, and the honeycomb composite board is mainly suitable for the ship manufacturing industry, the transportation industry and the airplane manufacturing industry; nonmetal honeycomb composite sheet divide into fibre class and paper class, and wherein fibre class honeycomb composite sheet is comparatively common in interior decoration and furniture, and paper class honeycomb composite sheet is applied to in the packaging material mostly. With the wide application of the honeycomb composite board in various fields, people have higher performance requirements on the honeycomb composite board, and the development of more various and higher-performance honeycomb composite boards becomes a hot problem in the material field.
CN109367141A discloses an aluminum honeycomb composite sheet for boats and ships, aluminum honeycomb composite sheet includes the sandwich layer, the sandwich layer is the honeycomb board that the combination of form formed that is parallel by the little shape aluminum pipe of cross section for the hexagon, and its two sides is the complex in proper order has first glue film, aluminum plate, second glue film and high pressure to decorate the flame retardant coating, and wherein first glue film is PAPU-30 type high viscosity glue, and the second glue film is 3012 type epoxy glue, and the high pressure is decorated the flame retardant coating and is fluorocarbon roll coating or PVC film. The aluminum honeycomb composite board has the advantages of light weight, moisture resistance, high strength, difficult deformation and long service life.
CN108527972A discloses an aluminium honeycomb composite sheet and method for producing aluminium honeycomb composite sheet, the composite sheet includes corrosion resistant plate, welt, aluminium matter honeycomb core, first aluminium alloy plate and two aluminium alloy frameworks, the lower surface of corrosion resistant plate and the upper surface connection of welt, two aluminium alloy frameworks horizontal branch put in the both sides of first aluminium alloy plate upper surface, the top surface and the lower surface of welt of two aluminium alloy frameworks are connected, welt, first aluminium alloy plate and two aluminium alloy frameworks form the frame construction that the vertical section is the rectangle, aluminium matter honeycomb core sets up in the frame construction, the both sides of aluminium matter honeycomb core are connected with two aluminium alloy frameworks respectively, the upper surface and the lower surface of welt of aluminium matter honeycomb core are connected, the lower surface and the upper surface connection of first aluminium alloy plate of aluminium honeycomb core. The composite board has the advantages of light weight, stable structure, stronger mechanical strength, good impact resistance and impact resistance, and stronger wind pressure resistance.
CN102774052A discloses a honeycomb composite board and a manufacturing method thereof, the honeycomb composite board comprises a honeycomb layer and a fiber layer coated with an adhesive layer on at least one side, the two sides of the honeycomb layer are bonded with the fiber layer through the adhesive layer, and a part of the adhesive layer extends into the holes of the honeycomb core material and is bonded with the same. The honeycomb composite board adopts a structure that fibers are directly bonded with the honeycomb cells, and in the processes of heating, foaming and mould pressing of the honeycomb composite board, the fiber materials are partially sunk between the honeycomb cells except for being firmly combined with the honeycomb cells, so that the possibility of displacement, dislocation and virtual adhesion of the honeycomb cells in the use process is avoided, and the strength of the material is greatly enhanced.
The existing honeycomb composite board generally uses metal as a surface layer material, the surface layer is difficult to prevent fire and resist corrosion, and the application environment of the composite board is greatly limited; and the metal has poor oxidation resistance, so that the service life of the honeycomb composite plate is short. The surface layer of the honeycomb composite board taking the fiber material as the surface layer material has poor mechanical property, low impact resistance, tensile resistance and bending strength, and difficult maintenance of long service life and stable performance in the environment of strong wind and sundry impact.
Therefore, it is an important research in the art to develop a honeycomb composite panel having good fire resistance and corrosion resistance, high mechanical strength, and particularly high surface mechanical strength.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a honeycomb composite board and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a honeycomb composite board, which includes a honeycomb core material, and a first adhesive film layer and a second adhesive film layer bonded to the upper and lower surfaces of the honeycomb core material, wherein a first fiber layer is disposed on the surface of the first adhesive film layer, and a second fiber layer is disposed on the surface of the second adhesive film layer.
The second fiber layer includes aramid prepreg and fiber prepreg.
The honeycomb composite board provided by the invention comprises a first fiber layer, a first adhesive film layer, a honeycomb core material, a second adhesive film layer and a second fiber layer which are sequentially stacked. The honeycomb core material is used for supporting the whole plate structure, and has a firm hexagonal honeycomb structure inside, so that the effects of sound insulation, heat insulation and pressure resistance can be achieved; the first adhesive film layer and the second adhesive film are bonded on two surfaces of the honeycomb core material and are respectively bonded with the first fiber layer and the second fiber layer, so that high-strength stable bonding among the first fiber layer, the second fiber layer and the honeycomb core material is realized, and the honeycomb composite board has good stability and mechanical strength; the first fiber layer and the second fiber layer are used as surface layer materials of the honeycomb composite board, have the characteristics of good fire resistance, oxidation resistance and light weight, and are endowed with the characteristics on the premise of not increasing the weight of the composite board.
In the honeycomb composite board provided by the invention, the second fiber layer comprises the aramid fiber prepreg and the fiber prepreg, the whole strength, the fire resistance and the corrosion resistance of the honeycomb composite board are improved by introducing the aramid fiber prepreg, particularly, the mechanical properties such as impact resistance, tensile resistance and bending strength of the surface of the material are obviously enhanced, and the honeycomb composite board can resist strong wind and impact of impurities when being used for transportation materials.
Preferably, the first fibre layer is a fibre prepreg, or is the same as the second fibre layer.
In the honeycomb composite board provided by the invention, the first fiber layer is the fiber prepreg or is the same as the second fiber layer (namely comprises the aramid prepreg and the fiber prepreg). When the honeycomb composite board is used as a transportation material, one surface of the board is in contact with the equipment cabin, and the other surface of the board faces the ground; the surface material facing the ground is a second fiber layer, and has high mechanical strength capable of resisting strong wind and sundry impact; the first fibre layer in contact with the device compartment may be of the same material and construction as the second fibre layer, or may not comprise aramid prepreg for cost reasons.
Preferably, the second fiber layer is a composite layer formed by laminating an aramid prepreg and a fiber prepreg, and the fiber prepreg is bonded with the second glue film layer, that is, the aramid prepreg is used as the outermost layer material of the honeycomb composite board.
In the first fiber layer and the second fiber layer of the present invention, the number of layers of the fiber prepreg is 1 to 4, for example, 1, 2, 3, or 4, preferably 2 to 3, layers.
Preferably, the aramid prepreg includes aramid fabric and epoxy resin.
Preferably, the mass percentage of the epoxy resin in the aramid prepreg is 20-50%, for example, 22%, 24%, 26%, 28%, 30%, 33%, 35%, 38%, 40%, 41%, 43%, 45%, 47% or 49%, and the specific values therebetween are limited to space and for brevity, the invention is not exhaustive of the specific values included in the range.
Preferably, the honeycomb core material is selected from a metal honeycomb core or a non-metal honeycomb core, and is further preferably a metal honeycomb core.
Preferably, the metal honeycomb core is an aluminum honeycomb core.
Preferably, the first adhesive film layer and the second adhesive film layer are each independently selected from an epoxy adhesive film layer or a polyurethane adhesive film layer, and more preferably an epoxy adhesive film layer.
As a preferred embodiment of the present invention, the first adhesive film layer and the second adhesive film layer are both epoxy adhesive film layers, and the epoxy resin contains a highly active epoxy group, and can respectively produce high-strength adhesion with the honeycomb core material (especially the metal honeycomb core) and the fiber layer, and the resin has large cohesion and small internal stress, and can provide high strength and high dimensional stability as the adhesive film layers.
Preferably, the fiber prepreg includes a fiber fabric and a resin composition attached thereto after being dried by coating.
Preferably, the resin composition is contained in the fiber prepreg in an amount of 50 to 60% by mass, for example, 51%, 5%, 53%, 54%, 55%, 56%, 57%, 58% or 59%, and specific values therebetween are limited to space and for the sake of brevity, and the present invention is not intended to be exhaustive to list the specific values included in the range.
Preferably, the fiber fabric is glass fiber or carbon fiber, and further preferably glass fiber.
Preferably, the resin composition comprises the following components in parts by weight: 30-90 parts of phenolic resin, 5-60 parts of toughening resin and 1-20 parts of filler.
The content of the phenol resin in the resin composition may be 32 parts by weight, 35 parts by weight, 38 parts by weight, 40 parts by weight, 43 parts by weight, 45 parts by weight, 48 parts by weight, 50 parts by weight, 53 parts by weight, 55 parts by weight, 58 parts by weight, 60 parts by weight, 62 parts by weight, 65 parts by weight, 68 parts by weight, 70 parts by weight, 72 parts by weight, 75 parts by weight, 78 parts by weight, 80 parts by weight, 82 parts by weight, 85 parts by weight, 87 parts by weight, 89 parts by weight, or the like.
The content of the toughening resin may be 6 parts by weight, 8 parts by weight, 10 parts by weight, 13 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 33 parts by weight, 35 parts by weight, 37 parts by weight, 40 parts by weight, 42 parts by weight, 45 parts by weight, 47 parts by weight, 50 parts by weight, 52 parts by weight, 55 parts by weight, 57 parts by weight, 59 parts by weight, or the like.
The filler may be included in an amount of 2 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 1 part by weight, 15 parts by weight, 17 parts by weight, 19 parts by weight, or the like.
Preferably, the toughening resin comprises the following components in percentage by mass: 50 to 90% of a polyvinyl alcohol resin (e.g., 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, 85%, 87%, or 89%), and 10 to 50% of a polyvinyl butyral resin (e.g., 12%, 15%, 18%, 20%, 23%, 25%, 28%, 30%, 32%, 35%, 37%, 40%, 42%, 45%, 47%, or 49%).
Preferably, the filler is selected from any one of or a combination of at least two of aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, melamine salt, red phosphorus or triaryl phosphate ester.
According to the preferable technical scheme, the mass percentage of the resin composition in the fiber prepreg is 50-60%; if the content exceeds the above range, the content of the resin composition is too low, which may result in a honeycomb composite panel having a reduced overall strength and toughness and having poor mechanical properties; an excessively high content of the resin composition may cause the resin composition to overflow during processing, which may affect subsequent processing.
The resin composition is a combination of a phenol resin, a polyvinyl alcohol resin (PVA), a polyvinyl butyral resin (PVB), and a filler. Wherein, the phenolic resin has good fireproof and flame-retardant properties; PVA and PVB are used as toughening resins, and the toughening resins and the PVB are compounded cooperatively to improve the toughness and the strength of the resin composition and contribute to improving the interlayer peeling strength of the honeycomb composite board; the filler has flame retardant properties and can further enhance the overall mechanical properties of the honeycomb composite panel.
Preferably, the thickness of the first fiber layer is 0.4 to 1.2mm, such as 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1.0mm or 1.1mm, and the specific values therebetween are not exhaustive for the sake of brevity and clarity.
Preferably, the thickness of the second fibrous layer is 0.8 to 1.2mm, such as 0.85mm, 0.9mm, 0.95mm, 1.0mm, 1.05mm, 1.1mm or 1.15mm, and the specific values therebetween are not exhaustive for the sake of brevity and clarity.
In another aspect, the present invention provides a method for preparing a honeycomb composite panel, the method comprising the steps of:
(1) carrying out hot pressing on the aramid fiber prepreg and the fiber prepreg to obtain a second fiber layer;
(2) and sequentially stacking the first fiber layer, the first adhesive film layer, the honeycomb core material, the second adhesive film layer and the second fiber layer in a mould, carrying out hot pressing, and opening the mould to obtain the honeycomb composite board.
Preferably, the hot pressing temperature in step (1) is 140 to 160 ℃, such as 141 ℃, 143 ℃, 145 ℃, 147 ℃, 149 ℃, 150 ℃, 152 ℃, 154 ℃, 155 ℃, 157 ℃ or 159 ℃.
Preferably, the hot pressing time in step (1) is 1-3 h, such as 1.2h, 1.5h, 1.8h, 2h, 2.2h, 2.5h, 2.7h or 2.9 h.
Preferably, the pressure of the hot pressing in step (1) is 3 to 7MPa, such as 3.3MPa, 3.5MPa, 3.8MPa, 4MPa, 4.2MPa, 4.5MPa, 4.8MPa, 5MPa, 5.2MPa, 5.5MPa, 5.8MPa, 6MPa, 6.3MPa, 6.5MPa, 6.7MPa or 6.9MPa, etc.
Preferably, the hot pressing temperature in step (2) is 140 to 160 ℃, such as 141 ℃, 143 ℃, 145 ℃, 147 ℃, 149 ℃, 150 ℃, 152 ℃, 154 ℃, 155 ℃, 157 ℃ or 159 ℃.
Preferably, the hot pressing time in the step (2) is 6-10 h, such as 6.2h, 6.5h, 6.7h, 7h, 7.3h, 7.5h, 7.8h, 8h, 8.2h, 8.5h, 8.8h, 9h, 9.2h, 9.5h, 9.7h or 9.9h, etc.
Preferably, the pressure of the hot pressing in step (2) is 3 to 7MPa, such as 3.3MPa, 3.5MPa, 3.8MPa, 4MPa, 4.2MPa, 4.5MPa, 4.8MPa, 5MPa, 5.2MPa, 5.5MPa, 5.8MPa, 6MPa, 6.3MPa, 6.5MPa, 6.7MPa or 6.9MPa, etc.
Preferably, the temperature for opening the mold in the step (2) is 40-60 ℃, such as 41 ℃, 43 ℃, 45 ℃, 47 ℃, 49 ℃, 50 ℃, 52 ℃, 54 ℃, 55 ℃, 57 ℃ or 59 ℃.
Preferably, the first fiber layer in step (2) is obtained by hot-pressing aramid prepreg and fiber prepreg or hot-pressing fiber prepreg, and the hot-pressing has the same selection range of temperature and time as those of the hot-pressing in step (1).
The preparation method of the honeycomb composite board is simple, the honeycomb composite board can be prepared by stacking and hot-pressing and attaching layers, and the honeycomb composite board is taken out after being cooled to 40-60 ℃ after hot pressing is finished, so that the honeycomb composite board is prevented from warping caused by different expansion coefficients when being overheated.
Preferably, the preparation method of the fiber prepreg in the step (1) is as follows: and coating the resin composition on the fiber fabric, and drying to obtain the fiber prepreg.
Preferably, the method of coating is dip coating.
Preferably, the drying temperature is 140 to 160 ℃, such as 141 ℃, 143 ℃, 145 ℃, 147 ℃, 149 ℃, 150 ℃, 152 ℃, 154 ℃, 155 ℃, 157 ℃ or 159 ℃.
In another aspect, the present invention provides a use of the honeycomb composite panel as described above in automotive materials, building materials, packaging materials or transportation materials.
Compared with the prior art, the invention has the following beneficial effects:
the honeycomb composite board provided by the invention comprises a first fiber layer, a first adhesive film layer, a honeycomb core material, a second adhesive film layer and a second fiber layer, wherein the second fiber layer comprises aramid prepreg and fiber prepreg. The honeycomb composite board has the effects of sound insulation, heat insulation and compression resistance, and high-strength stable bonding is formed among layers, so that the honeycomb composite board has good stability and mechanical strength, and the interlayer peeling strength of the honeycomb composite board reaches 80-125N/mm; the first fiber layer and the second fiber layer are used as surface layer materials, so that the honeycomb composite board has the characteristics of good fireproof and flame-retardant performance, oxidation resistance and light weight, and due to the introduction of the aramid prepreg in the second fiber layer, the honeycomb composite board has excellent corrosion resistance, impact resistance and compressive and tensile strength; the density of the honeycomb composite board is lower than 5.4kg/m3The oxygen index is higher than 60%, the strength retention rate in 30% sulfuric acid can reach 93-96%, the bending strength can reach 165MPa, the flat compression strength can reach 2.82MPa, the flat tensile strength is 3.06-3.14 MPa, the impact resistance is 2-10 mm, and the honeycomb composite plate has the characteristics of light weight, corrosion resistance, fire resistance, flame retardance and excellent mechanical strength, is simple in preparation method, and can fully meet the application requirements of the honeycomb composite plate in transportation materials.
Drawings
Fig. 1 is a schematic structural diagram of the honeycomb composite board provided by the present invention, wherein 1 is a first fiber layer, 2 is a first adhesive film layer, 3 is a honeycomb core material, 4 is a second adhesive film layer, and 5 is a second fiber layer.
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.
The experimental materials used in the examples and comparative examples of the present invention were as follows:
(1) aramid prepreg: dupont aramid fabric, 400g/m2The epoxy aramid prepreg is prepared by a dry method, wherein the average mass percentage of the epoxy resin is 35%.
(2) An aluminum honeycomb core: purchased from Jiashan Xiangzhou.
(3) Epoxy adhesive film: purchased from Shandong Ding Cheng composite Co., Ltd.
(4) Fiber fabric: glass fiber, 300g/m2From glass fiber, taishan; carbon fibers, available from taishan glass fibers ltd.
(5) Resin composition: phenolic resin (number average molecular weight of 321g/mol, weight average molecular weight of 679g/mol, brand No. PF5320), polyvinyl alcohol resin (PVA, average relative molecular weight of 17110g/mol, brand No. 1788), polyvinyl butyral resin (PVB, number average molecular weight of 40000g/mol, brand No. B-06HX), and filler aluminum hydroxide (brand No. AH-1).
Example 1
The embodiment provides a honeycomb composite board, and the preparation method comprises the following steps:
(1) preparation of resin composition: mixing 40 parts by weight of phenolic resin, 30 parts by weight of PVA, 5 parts by weight of PVB and 15 parts by weight of filler, adding 30 parts by weight of acetone serving as a diluent, and uniformly stirring and mixing to obtain the resin composition;
(2) preparation of the first fibrous layer: respectively coating the resin composition obtained in the step (1) on 2 layers of glass fibers by a dip coating method, and drying at 150 ℃ to obtain 2 layers of fiber prepregs with gum dipping amount (namely the mass percentage of the resin composition) of 55%; stacking 2 layers of fiber prepregs, and carrying out hot pressing at 150 ℃ for 2 hours to obtain a first fiber layer;
(3) preparation of the second fiber layer: respectively coating the resin composition obtained in the step (1) on 2 layers of glass fibers by a dip coating method, and drying at 150 ℃ to obtain 2 layers of fiber prepregs with gum dipping amounts of 55%; sequentially stacking 2 layers of fiber prepregs and 1 layer of aramid prepreg, and carrying out hot pressing at 150 ℃ for 3 hours to obtain a second fiber layer;
(4) preparing the honeycomb composite board: and (3) sequentially stacking the layers in a mould according to the sequence of the first fiber layer, the first adhesive film layer, the aluminum honeycomb core, the second adhesive film layer and the second fiber layer (the fiber prepreg in the second fiber layer is attached to the second adhesive film layer), carrying out hot pressing at 150 ℃ for 8h, then cooling to 50 ℃, and then opening the mould to obtain the honeycomb composite board.
Example 2
The embodiment provides a honeycomb composite board, and the preparation method comprises the following steps:
(1) the resin composition was prepared in the same manner as in step (1) of example 1;
(2) preparation of the first fibrous layer: respectively coating the resin composition obtained in the step (1) on 2 layers of glass fibers by a dip coating method, and drying at 140 ℃ to obtain 2 layers of fiber prepregs with 50% of gum dipping amount; sequentially stacking 2 layers of fiber prepregs and 1 layer of aramid prepreg in sequence, and carrying out hot pressing at 140 ℃ for 3 hours to obtain a first fiber layer;
(3) preparation of the second fiber layer: same as step (2);
(4) preparing the honeycomb composite board: and (2) sequentially stacking the layers in a mould according to the sequence of the first fiber layer, the first adhesive film layer, the aluminum honeycomb core, the second adhesive film layer and the second fiber layer (the fiber prepreg in the first fiber layer is attached to the first adhesive film layer, and the fiber prepreg in the second fiber layer is attached to the second adhesive film layer), hot-pressing at 140 ℃ for 10 hours, cooling to 60 ℃, and then opening the mould to obtain the honeycomb composite board.
Example 3
The embodiment provides a honeycomb composite board, and the preparation method comprises the following steps:
(1) the resin composition was prepared in the same manner as in step (1) of example 1;
(2) preparation of the first fibrous layer: respectively coating the resin composition obtained in the step (1) on glass fibers by a dip coating method, and drying at 160 ℃ to obtain fiber prepregs with 60% of gum dipping amount; hot-pressing the fiber prepreg at 160 ℃ for 1h to obtain a first fiber layer;
(3) preparation of the second fiber layer: coating the resin composition obtained in the step (1) on glass fibers by a dip coating method, and drying at 160 ℃ to obtain a fiber prepreg with the gum dipping amount of 60%; stacking the fiber prepreg and the aramid prepreg, and carrying out hot pressing at 160 ℃ for 1h to obtain a second fiber layer;
(4) preparing the honeycomb composite board: and (2) sequentially stacking the layers in a mould according to the sequence of the first fiber layer, the first adhesive film layer, the aluminum honeycomb core, the second adhesive film layer and the second fiber layer (the fiber prepreg in the first fiber layer is attached to the first adhesive film layer, and the fiber prepreg in the second fiber layer is attached to the second adhesive film layer), hot-pressing at 160 ℃ for 6h, cooling to 40 ℃, and then opening the mould to obtain the honeycomb composite board.
Example 4
The embodiment provides a honeycomb composite board, and the preparation method comprises the following steps:
(1) preparation of resin composition: mixing 70 parts by weight of phenolic resin, 40 parts by weight of PVA, 10 parts by weight of PVB and 10 parts by weight of filler, adding 15 parts by weight of acetone serving as a diluent, and uniformly stirring and mixing to obtain the resin composition;
(2) preparation of the first fibrous layer: respectively coating the resin composition obtained in the step (1) on glass fibers and carbon fibers by a dip coating method, and drying at 150 ℃ to obtain glass fiber prepregs and carbon fiber prepregs with gum dipping amounts of 55%; stacking glass fiber prepregs and carbon fiber prepregs, and carrying out hot pressing at 150 ℃ for 2h to obtain a first fiber layer;
(3) preparation of the second fiber layer: respectively coating the resin composition obtained in the step (1) on glass fibers and carbon fibers by a dip coating method, and drying at 150 ℃ to obtain glass fiber prepregs and carbon fiber prepregs with gum dipping amounts of 55%; sequentially stacking the carbon fiber prepreg, the glass fiber prepreg and the aramid fiber prepreg in sequence, and carrying out hot pressing at 150 ℃ for 3 hours to obtain a second fiber layer;
(4) preparing the honeycomb composite board: and (3) sequentially stacking the layers in a mould according to the sequence of the first fiber layer, the first adhesive film layer, the aluminum honeycomb core, the second adhesive film layer and the second fiber layer (the carbon fiber prepreg in the second fiber layer is attached to the second adhesive film layer), carrying out hot pressing at 150 ℃ for 8h, then cooling to 50 ℃, and then opening the mould to obtain the honeycomb composite board.
Example 5
This example is different from example 1 in that PVA and PVB were not added to the resin composition in step (1) and the amounts of other components added were not changed.
Example 6
This example differs from example 1 in that the PVA and PVB in step (1) are replaced with equal parts by weight of phenolic resin.
Example 7
This example differs from example 1 in that the PVB in step (1) was replaced with an equal part by weight of PVA.
Example 8
This example differs from example 1 in that the filler in step (1) is replaced with an equal part by weight of phenolic resin.
Comparative example 1
The comparative example provides a honeycomb composite board, and the preparation method comprises the following steps:
(1) the resin composition was prepared in the same manner as in step (1) of example 1;
(2) preparation of the first fibrous layer: respectively coating the resin composition obtained in the step (1) on 2 layers of glass fibers by a dip coating method, and drying at 150 ℃ to obtain 2 layers of fiber prepregs with gum dipping amounts of 55%; stacking 2 layers of fiber prepregs, and carrying out hot pressing at 150 ℃ for 2 hours to obtain a first fiber layer;
(3) preparation of the second fiber layer: same as step (2);
(4) preparing the honeycomb composite board: and sequentially stacking the first fiber layer, the first adhesive film layer, the aluminum honeycomb core, the second adhesive film layer and the second fiber layer in a mould, carrying out hot pressing at 150 ℃ for 8 hours, cooling to 50 ℃, and then opening the mould to obtain the honeycomb composite board.
Comparative example 2
The comparative example provides a honeycomb composite board, and the preparation method comprises the following steps:
(1) the resin composition was prepared in the same manner as in step (1) of example 1;
(2) preparation of the first fibrous layer: respectively coating the resin composition obtained in the step (1) on 2 layers of glass fibers by a dip coating method, and drying at 150 ℃ to obtain 2 layers of fiber prepregs with gum dipping amounts of 55%; stacking 2 layers of fiber prepregs, and carrying out hot pressing at 150 ℃ for 2 hours to obtain a first fiber layer;
(3) preparation of the second fiber layer: respectively coating the resin composition obtained in the step (1) on 3 layers of glass fibers by a dip coating method, and drying at 150 ℃ to obtain 3 layers of fiber prepregs with gum dipping amounts of 55%; stacking 3 layers of fiber prepregs, and carrying out hot pressing at 150 ℃ for 2 hours to obtain a second fiber layer;
(4) preparing the honeycomb composite board: and sequentially stacking the first fiber layer, the first adhesive film layer, the aluminum honeycomb core, the second adhesive film layer and the second fiber layer in a mould, carrying out hot pressing at 150 ℃ for 8 hours, cooling to 50 ℃, and then opening the mould to obtain the honeycomb composite board.
Comparative example 3
The comparative example provides a honeycomb composite board, and the preparation method comprises the following steps:
(1) preparing a first metal layer: wiping the surface of the aluminum plate clean by using acetone;
(2) preparing a second metal layer: the same as the step (1);
(3) preparing the honeycomb composite board: and sequentially stacking the first metal layer, the first adhesive film layer, the aluminum honeycomb core, the second metal layer and the second fiber layer in a mould, carrying out hot pressing at 150 ℃ for 8 hours, cooling to 50 ℃, and then opening the mould to obtain the honeycomb composite board.
And (3) performance testing:
(1) and (3) testing the density: weighing the mass of the honeycomb composite board provided by the embodiments 1-8 and the comparative examples 1-3, and dividing the mass by the volume to obtain the density of the honeycomb composite board;
(2) and (3) testing the fireproof performance: measuring an oxygen index according to the second part of GB/T-2406.1-2008 standard, wherein the higher the oxygen index is, the better the fireproof performance is;
(3) and (3) corrosion resistance testing: taking a sample with the plane size of 20mm multiplied by 20mm, placing the sample in 30% sulfuric acid at 80 ℃, detecting the weight and the strength after 24 hours, and comparing the weight and the strength with the weight and the strength before sulfuric acid treatment, the lower the retention rate is, the better the corrosion resistance is represented;
(4) flat pressing strength: the flat crushing strength is measured according to the method specified in GB/T-1453-;
(5) bending strength: the bending strength is measured according to the method specified by the GB/T-1466 standard;
(6) flat tensile strength: the flat pull strength is measured according to the method specified in the GB/T-1452 standard;
(7) peel strength: the peel strength was measured according to the method prescribed in GB/T-1457-;
(8) impact resistance: falling ball impact test, equipment: a falling ball impact tester and a digital display caliper; the detection method comprises the following steps: measuring the diameter of a pit by using a caliper in a free falling body at a position of 0.8m of a 324 +/-5 g steel ball; the standard requires that: less than 10 mm.
The performance, density, oxygen index and corrosion resistance test data of the honeycomb composite panels provided in examples 1 to 8 and comparative examples 1 to 3 are shown in table 1, and the test data of each mechanical performance is shown in table 2.
TABLE 1
Figure BDA0002316698050000141
Figure BDA0002316698050000151
As can be seen from the data in Table 1, the density of the honeycomb composite panels provided in examples 1 to 8 of the present invention is 4.4 to 5.4kg/m, compared to the conventional aluminum honeycomb composite panel with metal skin (comparative example 3)3Lower density and lighter mass; the flame retardance is better, and the oxygen index can reach more than 60 percent; the corrosion-resistant steel has excellent corrosion resistance, the weight of the steel is basically unchanged after the steel is soaked in 30% sulfuric acid at 80 ℃ for 24 hours, and the strength retention rate reaches 93-96%.
TABLE 2
Figure BDA0002316698050000152
Figure BDA0002316698050000161
As can be seen from the data in table 2, the honeycomb composite panels provided in embodiments 1 to 4 of the present invention have high-strength interlayer bonding performance, and the interlayer peel strength thereof reaches 110N/mm or more; if the resin composition on the fiber prepreg is not the combination of the phenolic resin, the toughening resin (compounded by PVA and PVB) and the filler (examples 5-8), the interlayer bonding performance and the comprehensive mechanical performance of the honeycomb composite board are reduced, and the interlayer peeling strength and the flat tensile strength are obviously reduced.
The honeycomb composite board provided by the embodiments 1 to 4 of the invention has high mechanical strength, the bending strength of the honeycomb composite board can reach 110 to 165MPa, the flat compression strength of the honeycomb composite board is 2.71 to 2.82MPa, and the flat tensile strength of the honeycomb composite board can reach 3.06 to 3.14 MPa. The first fiber layer and the second fiber layer of the honeycomb composite board provided by the embodiment 2 both contain aramid prepregs, and only the second fiber layer in the embodiment 1 contains the aramid prepregs, so that the flat crushing strength, the flat tensile strength, the bending strength and the impact resistance of the embodiment 2 are better than those of the embodiment 1; example 3 provides a honeycomb composite panel in which the first fiber layer and the second fiber layer each contain only 1 glass fiber, and thus the impact resistance and bending strength are lower than those of example 1; example 4 provides a honeycomb composite panel in which the first and second fibrous layers are both a combination of glass fibers and carbon fibers, resulting in a higher flat tensile strength, but lower impact and flexural strength than example 1.
The honeycomb composite boards provided by the comparative examples 1 and 2 do not contain the aramid prepreg, so that the honeycomb composite boards are extremely poor in impact resistance, low in horizontal tensile strength and low in pressure intensity, and cannot meet the requirements of resisting external strong wind and sundry impact when the honeycomb composite boards are applied to transportation materials.
The applicant states that the present invention is illustrated by the above examples of the honeycomb composite panel of the present invention, the preparation method and the application thereof, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims (10)

1. The honeycomb composite board is characterized by comprising a honeycomb core material, a first adhesive film layer and a second adhesive film layer, wherein the first adhesive film layer and the second adhesive film layer are bonded on the upper surface and the lower surface of the honeycomb core material;
the second fiber layer includes aramid prepreg and fiber prepreg.
2. The honeycomb composite panel according to claim 1, wherein said first fiber layer is a fiber prepreg or is the same as said second fiber layer;
preferably, the second fiber layer is a composite layer formed by laminating aramid fiber prepreg and fiber prepreg, and the fiber prepreg is bonded with the second adhesive film layer.
3. The honeycomb composite panel according to claim 1 or 2, wherein the aramid prepreg comprises aramid fabric and epoxy resin;
preferably, the mass percentage content of the epoxy resin in the aramid prepreg is 20-50%.
4. The honeycomb composite panel according to any one of claims 1 to 3, wherein the honeycomb core material is selected from a metal honeycomb core or a non-metal honeycomb core, preferably a metal honeycomb core;
preferably, the metal honeycomb core is an aluminum honeycomb core;
preferably, the first adhesive film layer and the second adhesive film layer are each independently selected from an epoxy adhesive film layer or a polyurethane adhesive film layer, and more preferably an epoxy adhesive film layer.
5. The honeycomb composite panel according to any one of claims 1 to 4, wherein the fiber prepreg comprises a fiber fabric and a resin composition attached thereto by coating and drying;
preferably, the mass percentage content of the resin composition in the fiber prepreg is 50-60%;
preferably, the fiber fabric is glass fiber or carbon fiber, and further preferably glass fiber;
preferably, the resin composition comprises the following components in parts by weight: 30-90 parts of phenolic resin, 5-60 parts of toughening resin and 1-20 parts of filler;
preferably, the toughening resin comprises the following components in percentage by mass: 50-90% of polyvinyl alcohol resin and 10-50% of polyvinyl butyral resin;
preferably, the filler is selected from any one of or a combination of at least two of aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, melamine salt, red phosphorus or triaryl phosphate ester.
6. The honeycomb composite panel according to any one of claims 1 to 5, wherein the first fiber layer has a thickness of 0.4 to 1.2 mm;
preferably, the thickness of the second fiber layer is 0.8-1.2 mm.
7. A method of making a honeycomb composite panel according to any one of claims 1 to 6, comprising the steps of:
(1) carrying out hot pressing on the aramid fiber prepreg and the fiber prepreg to obtain a second fiber layer;
(2) and sequentially stacking the first fiber layer, the first adhesive film layer, the honeycomb core material, the second adhesive film layer and the second fiber layer in a mould, carrying out hot pressing, and opening the mould to obtain the honeycomb composite board.
8. The preparation method according to claim 7, wherein the temperature of the hot pressing in the step (1) is 140-160 ℃;
preferably, the hot pressing time in the step (1) is 1-3 h;
preferably, the pressure of the hot pressing in the step (1) is 3-7 MPa;
preferably, the temperature of the hot pressing in the step (2) is 140-160 ℃;
preferably, the hot pressing time in the step (2) is 6-10 h;
preferably, the pressure of the hot pressing in the step (2) is 3-7 MPa;
preferably, the temperature of the die opening in the step (2) is 40-60 ℃;
preferably, the first fiber layer in step (2) is obtained by hot-pressing aramid prepreg and fiber prepreg or hot-pressing fiber prepreg.
9. The production method according to claim 7 or 8, wherein the fiber prepreg of step (1) is produced by: coating a resin composition on a fiber fabric, and drying to obtain the fiber prepreg;
preferably, the method of coating is dip coating;
preferably, the drying temperature is 140-160 ℃.
10. Use of the honeycomb composite panel according to any one of claims 1 to 6 in automotive materials, construction materials, packaging materials or transportation materials.
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