CN118061604B - High-toughness aramid paper honeycomb sandwich plate - Google Patents

High-toughness aramid paper honeycomb sandwich plate Download PDF

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Publication number
CN118061604B
CN118061604B CN202410494980.9A CN202410494980A CN118061604B CN 118061604 B CN118061604 B CN 118061604B CN 202410494980 A CN202410494980 A CN 202410494980A CN 118061604 B CN118061604 B CN 118061604B
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resin
aramid paper
paper honeycomb
layer
drying
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CN118061604A (en
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吴雪岑
崔阳
陈林
钱鑫
方国美
汪荣华
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Jiaxing Cmag Composite Material Co ltd
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Jiaxing Cmag Composite Material 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
    • 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
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/02—Layered products comprising a layer of paper or cardboard 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
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • 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
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/028—Paper 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
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability

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Abstract

The invention provides a high-toughness aramid paper honeycomb sandwich plate, and relates to the technical field of composite materials. The honeycomb sandwich plate comprises a first panel layer, a second panel layer and a honeycomb layer arranged between the first panel and the second panel, wherein the honeycomb layer comprises an aramid paper honeycomb core body and a resin layer formed on the surface of the aramid paper honeycomb core body, the aramid paper honeycomb core body is formed by mutually bonding multiple layers of aramid paper, a plurality of through holes with regular hexagons in cross section are formed after bonding two adjacent layers of aramid paper, raw materials of the resin layer comprise phenolic resin, epoxy resin, a toughening agent and reinforcing filler, and the toughening agent comprises nano core-shell rubber and modified polysulfonamide pulp. The resin layer of the aramid paper honeycomb core body is crosslinked and solidified with resin through the toughening agent to form a semi-interpenetrating network structure, the aramid paper honeycomb core body has good dimensional stability and heat resistance, and the toughness and strength of the Gao Renfang aramid paper honeycomb sandwich plate are effectively improved.

Description

High-toughness aramid paper honeycomb sandwich plate
Technical Field
The invention relates to the technical field of composite materials, in particular to a high-toughness aramid paper honeycomb sandwich plate.
Background
The aramid paper honeycomb material is a bionic honeycomb core material with excellent performance, and is widely applied to the fields of aerospace, ships and the like due to the outstanding characteristics of flame retardance, corrosion resistance, wave permeability, good mechanical properties and the like.
At present, the impregnating resin adopted in the preparation process of the aramid paper honeycomb mainly comprises the following components: epoxy resin, phenolic resin, urea resin, polyurethane and the like, wherein the phenolic resin has the characteristics of high strength, good heat resistance and the like, has lower production cost, and is widely applied to the preparation of honeycomb core materials by impregnating aramid paper honeycomb. However, aramid paper honeycomb suffers from a number of problems after phenolic resin impregnation. One of the important problems is: after the phenolic resin is solidified, molecules are highly crosslinked, aromatic rings in a molecular structure are connected by methylene only, rigid groups are too dense, and flexible groups are absent, so that the material taking the phenolic resin as matrix resin is too brittle, poor in toughness and extremely easy to generate stress cracks in products, and the product performance is seriously affected.
Disclosure of Invention
The invention aims to provide a high-toughness aramid paper honeycomb sandwich plate which is excellent in strength and toughness.
The invention solves the technical problems by adopting the following technical scheme.
The invention provides a high-toughness aramid paper honeycomb sandwich plate, which comprises: the honeycomb layer comprises an aramid paper honeycomb core body and a resin layer formed on the surface of the aramid paper honeycomb core body, wherein the aramid paper honeycomb core body is formed by mutually bonding multiple layers of aramid paper, a plurality of through holes with regular hexagons in cross section are formed after bonding two adjacent layers of aramid paper, raw materials of the resin layer comprise phenolic resin, epoxy resin, a toughening agent and reinforcing filler, and the toughening agent comprises nano core-shell rubber and modified polysulfonamide pulp.
Further, in a preferred embodiment of the present invention, the first panel layer and the second panel layer are made of carbon fiber prepregs through hot press molding, and the resin matrix in the carbon fiber prepregs is cyanate resin or PET resin.
Further, in a preferred embodiment of the present invention, the preparation process of the honeycomb layer includes:
S1, preparing resin raw materials, wherein the resin raw materials comprise the following components in parts by weight: 50-100 parts of phenolic resin, 1-30 parts of epoxy resin, 1-10 parts of toughening agent, 0.1-3 parts of reinforcing filler, 1-15 parts of organic solvent and 50-100 parts of diluent; wherein the toughening agent comprises nano core-shell rubber and modified polysulfonamide pulp;
s2, dispersing the toughening agent in the organic solvent, adding the epoxy resin for heating and stirring, then adding the reinforcing filler for heating and stirring, and cooling to obtain a pre-dispersion;
s3, mixing and grinding the pre-dispersion and the phenolic resin, and then adding the diluent for dilution to obtain impregnated resin;
S4, carrying out gum dipping treatment on the aramid paper honeycomb core body for a plurality of times in a gum dipping groove containing the dipping resin, and then curing to form a resin layer on the surface of the aramid paper honeycomb core body, thereby obtaining the honeycomb layer.
Further, in a preferred embodiment of the present invention, in step S1, the preparation step of the modified polysulfonamide pulp includes: dispersing polysulfonamide pulp in a solvent, and adding methyltrimethoxysilane to obtain a pretreatment product; dissolving divalent metal salt, trivalent metal salt and urea in water, mixing, performing hydrothermal reaction, and filtering after the reaction is finished to obtain layered double metal oxide; and stirring and mixing the pretreatment product and the layered bimetallic oxide, adding isophorone diisocyanate and triethylamine, reacting for 30-50 hours, washing, and drying to obtain the modified polysulfonamide pulp.
Further, in a preferred embodiment of the present invention, the core rubber portion of the nano core-shell rubber is selected from one or both of polybutadiene rubber and nitrile rubber; the shell part of the nano core-shell rubber is selected from a mixture of styrene and methyl methacrylate or alicyclic epoxy resin; the weight average molecular weight of the nano core-shell rubber is 2000-3000.
Further, in a preferred embodiment of the present invention, the organic solvent is ethyl acetate and the diluent is ethanol.
Further, in the preferred embodiment of the present invention, in the step S2, the epoxy resin is added to perform heating and stirring, the heating temperature is 60-90 ℃, the stirring time is 1-2 hours, and the stirring speed is 1200-1500 r/min.
Further, in the preferred embodiment of the present invention, in step S2, the reinforcing filler is added for heating and stirring, the heating temperature is 40-70 ℃, the stirring time is 0.5-1 h, and the stirring speed is 800-1000 r/min.
Further, in a preferred embodiment of the present invention, in step S4, the step of curing includes: curing for 30-40 min at 40-70 ℃, then curing for 30-40 min at 100-140 ℃, and finally curing for 80-100 min at 150-190 ℃.
Further, in the preferred embodiment of the present invention, in step S4, in the multiple impregnation process, the axial direction of the aramid paper honeycomb core is controlled to be kept perpendicular to the horizontal plane, and the drying process is performed at the interval of every two impregnation processes, where the drying process includes: drying at 40-70 ℃ for 15-25 min, then drying at 100-140 ℃ for 15-25 min, and finally drying at 130-145 ℃ for 30-50 min.
Further, in a preferred embodiment of the present invention, the reinforcing filler is prepared as follows: heating and refluxing fluorinated fullerene in sodium hydroxide aqueous solution for 1-2 hours, and then cleaning and drying to obtain reinforced particles; and mixing the reinforcing particles, amino-terminated silicone oil and epoxy resin, carrying out melt blending for 2-5 hours at the temperature of 70-120 ℃, washing and drying to obtain the reinforcing filler.
The high-toughness aramid paper honeycomb sandwich plate provided by the embodiment of the invention has the beneficial effects that:
By adding the nano core-shell rubber and the modified polysulfonamide pulp into the impregnating resin as toughening agents, the nano core-shell rubber and the modified polysulfonamide pulp can be crosslinked and solidified with the phenolic resin to form a semi-interpenetrating network structure, and the semi-interpenetrating network structure has thermoplastic resin and thermosetting resin networks, so that good toughness of the thermoplastic resin and good dimensional stability and heat resistance of the thermosetting resin are simultaneously maintained. And further, by adding the reinforcing filler into the semi-interpenetrating network structure, the three components exert different mechanical reinforcing effects and synergistically increase the mechanical properties of the aramid fiber paper honeycomb sandwich structure.
Further, in the curing process, the epoxy groups of the epoxy resin undergo a ring-opening reaction and undergo a chemical reaction with phenolic hydroxyl groups or hydroxymethyl groups in the phenolic resin to obtain a co-cured epoxy/phenolic resin cured product, and the epoxy/phenolic resin cured product has good mechanical properties while retaining the excellent flame retardant property of the phenolic resin. The impregnating resin has proper viscosity and good wettability, can be effectively compounded with the aramid paper honeycomb core body, and can effectively improve the toughness, strength and durability of the material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some examples of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of a high-toughness aramid paper honeycomb sandwich plate according to an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The high-toughness aramid paper honeycomb sandwich plate of the embodiment of the invention is specifically described below.
The embodiment of the invention provides a high-toughness aramid paper honeycomb sandwich plate, which comprises the following components: a first panel layer 10, a second panel layer 30, and a honeycomb layer 20 disposed between the first panel 10 and the second panel 30. The honeycomb layer 20 includes an aramid paper honeycomb core and a resin layer formed on the surface of the aramid paper honeycomb core. The aramid paper honeycomb core is formed by mutually bonding multiple layers of aramid paper, a plurality of through holes with regular hexagons in cross section are formed after bonding two adjacent layers of aramid paper, and raw materials of the resin layer comprise phenolic resin, epoxy resin, a toughening agent and reinforcing filler.
In one embodiment, the first panel layer and the second panel layer are made of carbon fiber prepregs through hot press molding, and the resin matrix in the carbon fiber prepregs is cyanate resin or PET resin. The carbon fiber prepreg may be obtained by a commercially available product. The carbon fiber prepreg is used as the first panel layer and the second panel layer, has the excellent characteristics of light weight, high strength, good rigidity and the like, and can effectively improve the mechanical properties of the honeycomb sandwich panel.
In one embodiment, the preparation process of the honeycomb layer 20 includes the following steps S1 to S4.
Specifically, in the present embodiment, step S1 includes: preparing resin raw materials, wherein the resin raw materials comprise the following components in parts by weight: 50-100 parts of phenolic resin, 1-30 parts of epoxy resin, 1-10 parts of toughening agent, 0.1-3 parts of reinforcing filler, 1-15 parts of organic solvent and 50-100 parts of diluent; wherein the toughening agent comprises nano core-shell rubber and modified polysulfonamide pulp.
Further, in the step S1, in the toughening agent, the mass ratio of the nano core-shell rubber to the modified polysulfonamide pulp is 10: 2-5. The synergistic effect of the nano core-shell rubber and the modified polysulfonamide pulp can be better improved by regulating and controlling the proportion of the nano core-shell rubber and the modified polysulfonamide pulp, and the mechanical property of the product is further improved.
Further, in the step S1, the mass of the nano core-shell rubber is 10% -30% of that of the epoxy resin; the dispersion effect of the nano core-shell rubber is ensured by adjusting the addition amount of the nano core-shell rubber, and the strength and the toughness of the interpenetrating network structure are effectively regulated and controlled.
Further, in the step S1, the dosage ratio of the nano core-shell rubber to the organic solvent is 1:1.2-2, and the dosage of the organic solvent is higher than that of the nano core-shell rubber so as to ensure the full dispersion of the nano core-shell rubber.
In the step S1, the mass ratio of the phenolic resin to the diluent is 1:1-1.5.
Further, in the step S1, the mass of the epoxy resin is 5% -15% of that of the phenolic resin. Further preferably, the mass of the epoxy resin is 5% -10% of that of the phenolic resin. At this ratio, the effect of modifying the impregnating resin is most excellent.
Further, in step S1, the core rubber portion of the nano core-shell rubber is selected from one or both of polybutadiene rubber and nitrile rubber. The shell portion of the nano core-shell rubber is selected from a mixture of styrene and methyl methacrylate or a cycloaliphatic epoxy resin. Preferably, the core rubber portion of the nano core-shell rubber is selected from polybutadiene rubber and the shell portion of the nano core-shell rubber is selected from cycloaliphatic epoxy resin. The nanometer core-shell rubber can effectively improve the plastic deformation capability of the hard resin and reduce the occurrence of adverse conditions such as cracking and the like.
The nano core-shell rubber can be obtained by commercial products. For example, MX-553 nanometer core-shell rubber is selected.
In the step S1, the weight average molecular weight of the nano core-shell rubber is 2000-3000. The nanometer core-shell rubber with the weight average molecular weight can better improve the toughness of products.
Further, in the step S1, the preparation steps of the modified polysulfonamide pulp include: dispersing polysulfonamide pulp in a solvent, and adding methyltrimethoxysilane to obtain a pretreatment product; dissolving divalent metal salt, trivalent metal salt and urea in water, mixing, performing hydrothermal reaction, and filtering after the reaction is finished to obtain layered double metal oxide; and stirring and mixing the pretreatment product and the layered bimetallic oxide, adding isophorone diisocyanate and triethylamine, reacting for 30-50 hours, washing, and drying to obtain the modified polysulfonamide pulp.
Further, in the preparation process of the modified polysulfonamide pulp, the solvent can be selected from organic solvents such as acetone and the like. In the pretreatment product, the mass of the methyltrimethoxysilane is 2-5% of that of polysulfonamide pulp. And (3) carrying out surface silanization pretreatment on polysulfonamide pulp by methyltrimethoxysilane. Further, the mass of the layered bimetal oxide is 60-80% of that of polysulfonamide pulp.
In the process, the surface-pretreated polysulfonamide pulp is mixed with the layered bimetallic oxide, and the mixture is subjected to crosslinking polymerization under the action of isophorone diisocyanate and triethylamine to obtain the modified polysulfonamide pulp. The modified polysulfonamide pulp is added into a resin matrix, and the toughening effect on the resin matrix can be greatly enhanced by utilizing the fiber characteristics of the layered bimetallic oxide with high aspect ratio and the polysulfonamide pulp. And the introduction of the layered double metal oxide can also effectively improve the heat resistance and flame retardance of the resin matrix.
Further, in step S1, the preparation steps of the reinforcing filler are as follows: heating and refluxing fluorinated fullerene in sodium hydroxide aqueous solution for 1-2 hours, and then cleaning and drying to obtain reinforced particles; and mixing the reinforcing particles, amino-terminated silicone oil and epoxy resin, carrying out melt blending for 2-5 hours at the temperature of 70-120 ℃, washing and drying to obtain the reinforcing filler.
Further, the mass ratio of the fluorinated fullerene, the amino-terminated silicone oil and the epoxy resin is 0.05-0.1: 0.2-0.8:1. In the preparation process, hydroxyl groups are introduced on the surface of the fluorinated fullerene, and then in-situ polymerization is carried out on the fluorinated fullerene, amino-terminated silicone oil and epoxy resin, and the fluorinated fullerene is introduced into the amino-terminated modified epoxy resin matrix, so that the flexibility modification of the resin is realized while the strength is enhanced. And the fluorinated fullerene is polymerized in situ in the resin matrix, has excellent compatibility with impregnating resin, can be uniformly dispersed, and has synergistic effect with the toughening agent, so that the mechanical property of the product is further improved.
Further, in step S1, the organic solvent is ethyl acetate, and the diluent is ethanol.
Specifically, in the present embodiment, step S2 includes: dispersing the toughening agent in the organic solvent, adding the epoxy resin for heating and stirring, then adding the reinforcing filler for heating and stirring, and cooling to obtain the pre-dispersion.
Further, in the step S2, in the process of adding the epoxy resin for heating and stirring, the heating temperature is 60-90 ℃, the stirring time is 1-2 hours, and the stirring speed is 1200-1500 r/min.
Further, in the step S2, the reinforcing filler is added for heating and stirring, the heating temperature is 40-70 ℃, the stirring time is 0.5-1 h, and the stirring speed is 800-1000 r/min.
In the step, the toughening agent is dispersed, then the toughening agent and the epoxy resin are heated and stirred, then the reinforcing filler is added, and the heating and stirring are performed again, so that the dispersing effect of the toughening agent and the reinforcing filler in the epoxy resin matrix can be effectively improved, agglomeration is avoided, and the reinforcing and toughening effect of the product is effectively ensured.
Specifically, in the present embodiment, step S3 includes: and mixing and grinding the pre-dispersion and the phenolic resin, and then adding the diluent for dilution to obtain the impregnating resin.
Further, in step S3, the process of mixing and grinding the pre-dispersion and the phenolic resin is as follows: stirring at a speed of 500-700 r/min for 1-3 h, and then grinding for 1.5-2.5 h by using a grinder. Stirring and mixing are carried out at a lower speed, and grinding is carried out so that the pre-dispersion is fully mixed with the phenolic resin.
The viscosity of the impregnating resin obtained through the steps is 20-30 cps, the solid content is 40-50%, and the water content is 4-6%. The impregnating resin has proper viscosity and good wettability, and can effectively uniformly infiltrate the aramid paper in the curing process of the impregnating resin and the aramid paper, thereby further improving the mechanical property of the product.
Specifically, in the present embodiment, step S4 includes: and (3) carrying out gum dipping treatment on the aramid paper honeycomb core body for a plurality of times in a gum dipping tank containing the dipping resin, and then curing to form a resin layer on the surface of the aramid paper honeycomb core body, thereby obtaining the honeycomb layer.
It is understood that the aramid paper honeycomb core is formed by gluing, laminating, pressing, solidifying, stretching and shaping a plurality of layers of aramid paper. The specific preparation process can be carried out according to the prior art, and no further description is given here.
Further, in step S4, in the multiple impregnation process, the axial direction of the aramid paper honeycomb core is controlled to be kept perpendicular to the horizontal plane, and the drying treatment is performed at the interval of every two impregnation processes, and the drying process includes: drying at 40-70 ℃ for 15-25 min, then drying at 100-140 ℃ for 15-25 min, and finally drying at 130-145 ℃ for 30-50 min.
Further, in step S4, the number of times of impregnation is determined according to the density of the honeycomb layer, that is, the number of times of impregnation is performed until the density of the honeycomb layer reaches the standard.
Further, in step S4, the step of the curing process includes: curing for 30-40 min at 40-70 ℃, then curing for 30-40 min at 100-140 ℃, and finally curing for 80-100 min at 150-190 ℃.
In the above-mentioned impregnation and curing process, drying is performed between impregnation. The drying process and the curing process are performed at a lower temperature, then the curing and crosslinking are performed at a medium temperature and a high temperature respectively, the co-curing effect of the epoxy resin and the phenolic resin can be effectively ensured in a section-by-section heating curing mode, the strength and the toughness are further improved, the durability of the product can be effectively improved, and the occurrence of adverse phenomena such as stripping and cracking is reduced. In addition, the final curing process takes longer than the drying process, so that the stress in the resin can be further reduced and the strength can be increased.
The honeycomb layer prepared by the preparation method has excellent mechanical properties, the unsteady plane compression strength reaches 1.81-2.90 MPa, the plane shear strength and the plane shear modulus are also effectively improved, and the strength and the toughness of the aramid paper honeycomb sandwich plate can be greatly improved.
Further, in this embodiment, after the honeycomb layer is prepared, the second panel layer, the honeycomb layer and the first panel layer are sequentially laid, and then are placed on a flat hot press device to be hot pressed and cured, so as to obtain the aramid paper honeycomb sandwich panel. The thermocompression curing process may be, for example: pressurizing to 0.3MPa, heating to 75 ℃, preserving heat for 3 hours, then heating to 110 ℃, maintaining for 1.5 hours, continuously heating to 240 ℃, maintaining for 2 hours, further heating to 300 ℃, maintaining for 1.5 hours, cooling, decompressing and taking out to obtain the aramid paper honeycomb sandwich plate.
The honeycomb layer 20 of the aramid paper honeycomb sandwich panel of the present invention is described in further detail below in connection with the examples.
Example 1, this example provides a honeycomb layer obtained according to the following preparation method:
(1) Preparing raw materials: 10000g of phenolic resin, 1000g of epoxy resin, 100g of nano core-shell rubber, 30g of modified polysulfonamide pulp, 15g of reinforcing filler, 150g of ethyl acetate and 10000g of ethanol.
Wherein, the modified polysulfonamide pulp is obtained by the following steps: a. 20 g polysulfonamide pulp is dispersed in a 30wt% acetone solution of 100 g, 0.05g of methyltrimethoxysilane is added, and ultrasonic dispersion is carried out for 30min, so as to obtain a pretreatment liquid. b. 0.2 mol of magnesium chloride, 0.08 of magnesium chloride mol of aluminum chloride 0.1 of aluminum chloride mol and 0.4 of urea mol are dissolved in deionized water, then ultrasonic treatment is carried out for 30min, transferred to a high-pressure reaction kettle, then 16 h is reacted at 200 ℃, and the layered double metal oxide is obtained by filtration and washing. c. Adding 15 g lamellar bimetal oxide into pretreatment liquid, then adding 6g isophorone diisocyanate and 0.6 g triethylamine, introducing N 2, reacting at 60 ℃ for 40 h, washing, and drying to obtain the modified polysulfonamide pulp.
Wherein, the reinforcing filler is obtained according to the following steps: a. and (3) heating and refluxing the 5g fluorinated fullerene in a 10wt% sodium hydroxide aqueous solution for 1.5 hours, and then washing and drying to obtain the reinforced particles. b. Mixing the reinforcing particles with 25 g amino-terminated silicone oil and 100g epoxy resin, melt blending for 3 hours at 90 ℃, washing and drying to obtain the reinforcing filler.
(2) Dispersing the nano core-shell rubber and the modified polysulfonamide pulp in ethyl acetate, heating to 70 ℃, and stirring for 1h at a speed of 1500r/min to obtain a dispersion liquid A.
(3) The epoxy resin was heated and poured into the reaction vessel, and stirring was started. The solution A is added into a reaction vessel and stirred for 1h at a constant temperature of 1200r/min under the condition of 60 ℃ to obtain a solution B. Adding reinforcing filler into the solution B, keeping the temperature at 60 ℃ and stirring at the speed of 800r/min for 1h to obtain the pre-dispersion.
(4) Adding the pre-dispersion obtained in the step (3) and phenolic resin into a stirrer, and stirring at the speed of 600r/min for 1.5 h to obtain a mixed solution. And grinding the mixed solution by using a grinder for 2 hours to obtain a grinding product.
(5) 10000G of ethanol is added into the ground product for dilution treatment, and the prepreg resin is obtained.
(6) And (3) placing the presoaked resin in a glue groove of a glue dipping machine, and carrying out glue dipping treatment on the aramid paper honeycomb core for a plurality of times. The axial direction of the cells of the aramid paper honeycomb core is ensured to be vertical to the horizontal plane during gum dipping. And 2 times of gum dipping, the aramid paper honeycomb core is dried, and the drying procedure is as follows: drying at 60deg.C for 20min, 120 deg.C for 20min, and 140 deg.C for 40min. Repeating gum dipping for a plurality of times until the density reaches the standard (in the embodiment, the side length of a honeycomb cell is 1.83mm, the density is 48kg/m 3), and after the gum dipping for the last time is finished, putting the honeycomb into an oven for curing treatment, wherein the curing procedure is as follows: curing at 60℃for 30min, 120℃for 30min, 175℃for 90min.
Embodiment 2, this embodiment provides a honeycomb layer, which is different from embodiment 1 in that:
In the step (1), raw materials are prepared: 10000g of phenolic resin, 1000g of epoxy resin, 200g of nano core-shell rubber, 50g of modified polysulfonamide pulp, 15g of reinforcing filler, 300g of ethyl acetate and 10000g of ethanol.
Embodiment 3, this embodiment provides a honeycomb layer, which is different from embodiment 1 in that:
In the step (1), raw materials are prepared: 10000g of phenolic resin, 1000g of epoxy resin, 300g of nano core-shell rubber, 60g of modified polysulfonamide pulp, 15g of reinforcing filler, 450g of ethyl acetate and 10000g of ethanol.
Embodiment 4, the honeycomb layer provided in this embodiment is different from embodiment 1 in that:
in the step (1), raw materials are prepared: 10000g of phenolic resin, 500g of epoxy resin, 100g of nano core-shell rubber, 30g of modified polysulfonamide pulp, 15g of reinforcing filler, 150g of ethyl acetate and 10000g of ethanol.
Embodiment 5, the honeycomb layer provided in this embodiment is different from embodiment 1 in that:
In the step (1), raw materials are prepared: 10000g of phenolic resin, 1500g of epoxy resin, 300g of nano core-shell rubber, 60g of modified polysulfonamide pulp, 15g of reinforcing filler, 450g of ethyl acetate and 10000g of ethanol.
Embodiment 6, the honeycomb layer provided in this embodiment is different from embodiment 1 in that:
In the step (6), the drying procedure is as follows: drying at 140℃for 80min. The curing procedure is: 150 min cured at 175 ℃.
Comparative example 1
The honeycomb layer provided in this comparative example was obtained according to the following preparation method:
(1) Preparing raw materials: 10000g of phenolic resin, 1000g of epoxy resin, 150g of ethyl acetate and 10000g of ethanol.
(2) Adding the epoxy resin and the phenolic resin into a stirrer, and stirring at the speed of 600r/min for 1.5 h to obtain a mixed solution. And grinding the mixed solution by using a grinder for 2 hours to obtain a grinding product.
(3) 10000G of ethanol is added into the ground product for dilution treatment, and the prepreg resin is obtained.
(4) And (3) placing the presoaked resin in a glue groove of a glue dipping machine, and carrying out glue dipping treatment on the aramid paper honeycomb core for a plurality of times. The axial direction of the cells of the aramid paper honeycomb core is ensured to be vertical to the horizontal plane during gum dipping. And 2 times of gum dipping, the aramid paper honeycomb core is dried, and the drying procedure is as follows: drying at 60deg.C for 20min, 120 deg.C for 20min, and 140 deg.C for 40min. Repeating the gum dipping for a plurality of times until the density reaches the standard (the density is the same as that of the embodiment 1), and after the gum dipping is completed for the last time, putting the honeycomb into an oven for curing treatment, wherein the curing procedure is as follows: curing at 60℃for 30min, 120℃for 30min, 175℃for 90min.
Comparative example 2
This comparative example provides a honeycomb layer which differs from that of example 1 in that:
In the step (1), raw materials are prepared: 10000g of phenolic resin, 1000g of epoxy resin, 100g of nano core-shell rubber, 15g of reinforcing filler (the preparation method is the same as that of the example 1), 150g of ethyl acetate and 10000g of ethanol.
Comparative example 3
This comparative example provides a honeycomb layer which differs from that of example 1 in that:
in the step (1), raw materials are prepared: 10000g of phenolic resin, 1000g of epoxy resin, 100g of nano core-shell rubber, 30g of modified polysulfonamide pulp (the preparation method is the same as that of the example 1), 150g of ethyl acetate and 10000g of ethanol.
Comparative example 4
This comparative example provides a honeycomb layer which differs from that of example 1 in that:
In the step (1), raw materials are prepared: 10000g of phenolic resin, 1000g of epoxy resin, 100g of nano core-shell rubber, 30g of polysulfonamide pulp, 5g of reinforcing filler (the reinforcing filler is fluorinated fullerene), 150g of ethyl acetate and 10000g of ethanol.
Test examples
The compressive strength and shear strength of the honeycomb layers obtained in examples 1 to 6 and comparative examples 1 to 4 were measured by using a universal tester CMT6104, and the results are shown in table 1:
TABLE 1
As can be seen from table 1, by comparing examples 1 to 6 with comparative example 1, it can be seen that the mechanical properties of the honeycomb layer can be significantly improved by modifying the gum dipping resin with the toughening agent, the reinforcing agent and the epoxy resin, thereby obtaining the aramid paper honeycomb sandwich panel with high toughness and strength.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

Claims (8)

1. A high-toughness aramid paper honeycomb sandwich panel, comprising: the honeycomb layer comprises an aramid paper honeycomb core body and a resin layer formed on the surface of the aramid paper honeycomb core body, wherein the aramid paper honeycomb core body is formed by mutually bonding multiple layers of aramid paper, a plurality of through holes with regular hexagons in cross section are formed after bonding two adjacent layers of aramid paper, raw materials of the resin layer comprise phenolic resin, epoxy resin, a toughening agent and reinforcing filler, and the toughening agent comprises nano core-shell rubber and modified polysulfonamide pulp;
The core rubber part of the nano core-shell rubber is selected from one or two of polybutadiene rubber and nitrile rubber; the shell part of the nano core-shell rubber is selected from a mixture of styrene and methyl methacrylate or alicyclic epoxy resin; the weight average molecular weight of the nano core-shell rubber is 2000-3000;
The preparation method of the modified polysulfonamide pulp comprises the following steps of: dispersing polysulfonamide pulp in a solvent, and adding methyltrimethoxysilane to obtain a pretreatment product; dissolving divalent metal salt, trivalent metal salt and urea in water, mixing, performing hydrothermal reaction, and filtering after the reaction is finished to obtain layered double metal oxide; stirring and mixing the pretreatment product and the layered bimetallic oxide, adding isophorone diisocyanate and triethylamine, reacting for 30-50 hours, washing, and drying to obtain the modified polysulfonamide pulp;
The preparation steps of the reinforcing filler are as follows: heating and refluxing fluorinated fullerene in sodium hydroxide aqueous solution for 1-2 hours, and then cleaning and drying to obtain reinforced particles; and mixing the reinforcing particles, amino-terminated silicone oil and epoxy resin, carrying out melt blending for 2-5 hours at the temperature of 70-120 ℃, washing and drying to obtain the reinforcing filler.
2. The Gao Renfang-fiber paper honeycomb sandwich panel according to claim 1, wherein the first panel layer and the second panel layer are made of carbon fiber prepregs by hot press molding, and the resin matrix in the carbon fiber prepregs is cyanate resin or PET resin.
3. The Gao Renfang-fiber paper honeycomb sandwich panel of claim 1 wherein the honeycomb layer is prepared by a process comprising:
S1, preparing resin raw materials, wherein the resin raw materials comprise the following components in parts by weight: 50-100 parts of phenolic resin, 1-30 parts of epoxy resin, 1-10 parts of toughening agent, 0.1-3 parts of reinforcing filler, 1-15 parts of organic solvent and 50-100 parts of diluent;
s2, dispersing the toughening agent in the organic solvent, adding the epoxy resin for heating and stirring, then adding the reinforcing filler for heating and stirring, and cooling to obtain a pre-dispersion;
s3, mixing and grinding the pre-dispersion and the phenolic resin, and then adding the diluent for dilution to obtain impregnated resin;
S4, carrying out gum dipping treatment on the aramid paper honeycomb core body for a plurality of times in a gum dipping groove containing the dipping resin, and then curing to form a resin layer on the surface of the aramid paper honeycomb core body, thereby obtaining the honeycomb layer.
4. A Gao Renfang-fiber paper honeycomb sandwich panel according to claim 3 wherein the organic solvent is ethyl acetate and the diluent is ethanol.
5. The Gao Renfang-fiber paper honeycomb sandwich panel according to claim 3, wherein in the step S2, in the process of adding the epoxy resin for heating and stirring, the heating temperature is 60-90 ℃, the stirring time is 1-2 h, and the stirring speed is 1200-1500 r/min.
6. The Gao Renfang-fiber paper honeycomb sandwich panel according to claim 3, wherein in the step S2, in the process of adding the reinforcing filler for heating and stirring, the heating temperature is 40-70 ℃, the stirring time is 0.5-1 h, and the stirring speed is 800-1000 r/min.
7. A Gao Renfang-fiber paper honeycomb sandwich panel according to claim 3, wherein in step S4, the step of curing comprises: curing for 30-40 min at 40-70 ℃, then curing for 30-40 min at 100-140 ℃, and finally curing for 80-100 min at 150-190 ℃.
8. A Gao Renfang-fiber paper honeycomb sandwich panel according to claim 3, wherein in step S4, in the multiple impregnation process, the axial direction of the aramid paper honeycomb core is controlled to be vertical to the horizontal plane, and the drying treatment is performed at the interval of every two impregnation processes, and the drying process includes: drying at 40-70 ℃ for 15-25 min, then drying at 100-140 ℃ for 15-25 min, and finally drying at 130-145 ℃ for 30-50 min.
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