CN117021711A - Fiber reinforced resin matrix composite material and preparation method and application thereof - Google Patents

Fiber reinforced resin matrix composite material and preparation method and application thereof Download PDF

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Publication number
CN117021711A
CN117021711A CN202311016812.0A CN202311016812A CN117021711A CN 117021711 A CN117021711 A CN 117021711A CN 202311016812 A CN202311016812 A CN 202311016812A CN 117021711 A CN117021711 A CN 117021711A
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China
Prior art keywords
fiber
composite material
polyimide
phenolic resin
reinforced resin
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CN202311016812.0A
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Chinese (zh)
Inventor
徐俊波
胡竹峰
杨超
王敏
孙兵
权维利
赵永忠
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Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
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Priority to CN202311016812.0A priority Critical patent/CN117021711A/en
Publication of CN117021711A publication Critical patent/CN117021711A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
    • 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
    • B32B2260/023—Two or more 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
    • B32B2260/04—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08J2361/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with monohydric phenols
    • C08J2361/10—Phenol-formaldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/40—Weight reduction

Abstract

The invention provides a fiber reinforced resin matrix composite material, a preparation method and application thereof, wherein the fiber reinforced resin matrix composite material comprises a phenolic resin composite material layer and a polyimide composite material layer; the phenolic resin composite material layer comprises one or at least two phenolic resin/fiber composite material layers; the polyimide composite material layer comprises one or at least two polyimide/fiber composite material layers; the preparation raw materials of the polyimide comprise diamine compounds, dianhydride compounds and catalysts, the molding temperature of polyimide resin is regulated and controlled by a catalyst doping method, and the fiber reinforced resin matrix composite material is integrally molded by hot pressing and curing through a layering arrangement procedure, and the prepared fiber reinforced resin matrix composite material has the characteristics of ablation resistance, good mechanical property and quick, batch and low-cost preparation.

Description

Fiber reinforced resin matrix composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a fiber reinforced resin matrix composite material, and a preparation method and application thereof.
Background
Phenolic resin is a high molecular polymer produced by the polycondensation reaction of phenolic compounds and aldehyde compounds. After being infiltrated and compounded with carbon fiber, the phenolic resin based composite material is prepared, and has relatively high carbon residue and relatively stable carbon residue layer, so that the phenolic resin based composite material is widely used as ablation material for spacecraft and provides heat protection for many aerospace tasks. However, amorphous carbon produced by carbonization of phenolic substrates can lead to greater oxidation, corrosion and thermo-mechanical sensitivity than other advanced carbon materials, which make it difficult to meet the higher thermal protection requirements of aerospace materials.
Current methods of improving the ablative resistance of phenolic resins include the addition of inorganic fillers such as ceramic particles (e.g., zirconium carbide, zirconium disilicide, zirconium diboride, etc.). CN115636967a discloses an environment-friendly ablation-resistant phenolic resin prepreg, a composite material and a preparation method, wherein the preparation method comprises the following steps: s1, heating a hot-melt phenolic resin to melt the hot-melt phenolic resin; s2, mixing the melted hot-melt phenolic resin with an anti-ablation auxiliary agent, wherein the anti-ablation auxiliary agent is one or a combination of more of zirconium diboride, silicon carbide, hafnium carbide, boron nitride, glass powder and kaolin; s3, preparing a mixture of the hot-melt phenolic resin and the ablation-resistant auxiliary agent into a glue film; s4, laminating the adhesive film and the reinforcing material, and then heating and compounding to obtain the environment-friendly anti-ablation phenolic resin prepreg. According to the technical scheme, an anti-ablation auxiliary agent is added into a hot-melt phenolic resin matrix, chemical reaction occurs in the heating process of the anti-ablation auxiliary agent, and ablation can be resisted, but because a large temperature difference exists between the ceramsite temperature (about 1000 ℃) of ceramic particles and the thermal degradation temperature (300-800 ℃) of phenolic resin, the phenolic resin can be completely decomposed before the ceramic particles participate in the reaction, so that the coke layer structure is invalid. In addition, the brittleness of the phenolic resin is improved due to the fact that the inorganic filler is too high, and meanwhile, the improvement effect of heat resistance and ablation resistance is limited.
CN115746496a discloses a high heat-resistant high-toughness thermoplastic polyimide modified phenolic moulding compound and a preparation method, wherein the high heat-resistant high-toughness thermoplastic polyimide modified phenolic moulding compound comprises the following components in parts by weight: 50 parts of linear phenolic resin, 10-20 parts of thermoplastic polyimide, 20 parts of reinforcing fiber, 10-15 parts of inorganic filler, 5 parts of curing agent, 1 part of curing accelerator, 0.5-1 part of plasticizer and 0.5-1 part of lubricant. According to the technical scheme, the heat resistance and toughness of the molding compound can be obviously improved by adding a small amount of thermoplastic polyimide, but the mechanical property, heat resistance and ablation resistance of the molding compound are still to be further improved.
Therefore, it is necessary to develop a fiber reinforced resin matrix composite material with good ablation resistance and mechanical properties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a fiber reinforced resin matrix composite material, and a preparation method and application thereof. The fiber reinforced resin matrix composite has the characteristics of ablation resistance, good mechanical property and capability of being prepared rapidly in batches and at low cost.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a fiber reinforced resin-based composite comprising a phenolic resin composite layer and a polyimide composite layer;
the phenolic resin composite material layer comprises one or at least two phenolic resin/fiber composite material layers;
the polyimide composite material layer comprises one or at least two polyimide/fiber composite material layers;
the fiber reinforced resin matrix composite comprises phenolic resin, polyimide and fibers;
the polyimide is prepared from diamine compounds, dianhydride compounds and catalysts.
In the invention, polyimide is a polymer with an imide ring structure in a main chain, and has excellent properties such as heat resistance, thermal oxidation resistance and good mechanical properties due to the conjugation effect between aromatic heterocycle and C-N on the chain. Compared with thermoplastic polyimide, thermosetting polyimide has better heat resistance and high tensile strength, but has high curing temperature and poorer processability, which severely limits the application of the thermosetting polyimide. The forming temperature difference of the phenolic resin and the polyimide resin is large, and how to realize the controllable compounding of the phenolic resin, the polyimide and the fiber is also a difficult problem to be solved. According to the fiber reinforced resin matrix composite, the forming temperature of polyimide resin is regulated and controlled by a method of doping a catalyst, then the phenolic resin composite layer and the polyimide composite layer are compounded, and after compression molding, curing and forming, phenolic resin and polyimide are further reacted in the forming process, so that the crosslinking density is improved, the heat resistance is obviously improved, and the prepared fiber reinforced resin matrix composite has the high carbon residue rate of the phenolic resin and the high-temperature oxidation resistance of the polyimide at the same time, so that the phenolic resin and polyimide domain-separated composite is formed, and is resistant to ablation and good in mechanical property.
Preferably, the raw materials for preparing the phenolic resin comprise phenolic compounds and aldehyde compounds.
Preferably, the phenolic compound comprises any one or a combination of at least two of phenol, cresol or xylenol.
Preferably, the aldehyde compound comprises formaldehyde.
Preferably, the diamine compound comprises 4, 4-diaminodiphenyl ether.
Preferably, the dianhydride compound comprises pyromellitic dianhydride and/or 3,3', 4' -biphenyl tetracarboxylic dianhydride.
Preferably, the catalyst comprises any one or a combination of at least two of benzimidazole, quinoline or parahydroxybenzoic acid.
Preferably, the fibers comprise a fiber cloth.
Preferably, the fiber cloth comprises any one or a combination of at least two of basalt fiber cloth, carbon fiber cloth, quartz fiber cloth or polyimide fiber cloth.
Preferably, the fiber reinforced resin matrix composite comprises the following components in parts by weight: 20 to 35 parts (for example, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, etc.), and 30 to 60 parts (for example, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 55 parts, 58 parts, etc.) of a phenolic resin.
In the invention, the weight part of the fiber in the fiber reinforced resin matrix composite is 30-60 parts, if the weight part of the fiber is too large, the fiber cannot be completely coated by the resin, and the prepared fiber reinforced resin matrix composite has poor ablative performance; if the weight portion of the fiber is too small, the fiber content in the fiber reinforced resin matrix composite is low, so that the mechanical property is reduced.
Preferably, the number of phenolic resin/fiber composite layers in the phenolic resin composite layer is 7-14, for example 8, 9, 10, 11, 12, 13 or 14 layers.
Preferably, the number of polyimide/fiber composite layers in the polyimide composite layer is 7 to 14, for example 8, 9, 10, 11, 12, 13 or 14 layers, etc.
Preferably, the layering mode of the fiber reinforced resin matrix composite material comprises unidirectional layering and multidirectional layering.
Preferably, the layering mode of the fiber reinforced resin matrix composite material comprises multi-directional layering along the direction of 45 degrees of fiber inclination and/or multi-directional layering along the direction perpendicular to the fiber direction.
In the present invention, the unidirectional ply means a unidirectional ply in a 0 ° direction, and the ply in a direction perpendicular to the fiber means a multi-directional ply crossing at 90 °.
According to the invention, the layering mode of the fiber reinforced resin matrix composite has an influence on mechanical properties and ablative properties, the mechanical properties of the fiber reinforced resin matrix composite can be adjusted by adjusting layering orientation of fibers, layering along the fiber direction or layering along the direction perpendicular to the fiber direction is beneficial to improving the mechanical properties and ablative resistance, wherein layering along the direction perpendicular to the fiber direction has an obvious improvement on the mechanical properties, and therefore, fiber reinforced resin matrix composite with different functions can be obtained by adjusting layering arrangement.
In a second aspect, the present invention provides a method for preparing a fiber reinforced resin matrix composite according to the first aspect, the method comprising the steps of: and sequentially layering the prepreg of the phenolic resin/fiber composite material layer and the prepreg of the polyimide/fiber composite material layer, and performing hot pressing to obtain the fiber reinforced resin matrix composite material.
Preferably, the preparation method of the prepreg of the phenolic resin/fiber composite material layer comprises the following steps: mixing the fiber and the impregnation liquid of the phenolic resin, vacuumizing for 1-4h (such as 1.2h, 1.5h, 1.8h, 2h, 2.5h, 3h, 3.5h, 3.6h or 3.8h, and the like), then spreading the fiber loaded with the impregnation liquid on a glass plate adhered with release paper, coating the prepreg on the surface of the fiber with a coater, and drying for 1-5h (such as 1.2h, 1.5h, 1.8h, 2h, 2.5h, 3h, 3.5h, 4h or 4.5h, and the like) at 45-65 ℃ (such as 46 ℃, 48 ℃, 50 ℃, 52 ℃,55 ℃, 58 ℃, 60 ℃, 62 ℃ or 64 ℃ and the like) to obtain the prepreg of the phenolic resin/fiber composite material layer.
Preferably, the preparation method of the prepreg of the polyimide/fiber composite material layer is as follows: mixing the fiber and the impregnating solution of polyimide, vacuumizing for 1-4h (such as 1.2h, 1.5h, 1.8h, 2h, 2.5h, 3h, 3.5h, 3.6h or 3.8h, etc.), then spreading the fiber loaded with the impregnating solution on a glass plate adhered with release paper, coating the impregnating solution on the surface of the fiber with a coater, and drying for 1-5h (such as 1.2h, 1.5h, 1.8h, 2h, 2.5h, 3h, 3.5h, 4h or 4.5h, etc.), thereby obtaining the prepreg of the polyimide/fiber composite material layer.
In the invention, based on a prepreg technology, fibers are firstly immersed in a resin impregnating solution, then the prepreg of a phenolic resin/fiber composite material layer and the prepreg of a polyimide/fiber composite material layer are prepared after drying, and finally the prepreg is cured and formed under the hot pressing of a die, so that the integrated forming of the phenolic aldehyde and polyimide domain-separated functional composite material is realized, the fiber reinforced resin matrix composite material is obtained, the preparation flow of the fiber reinforced resin matrix composite material is shown in a figure 1, the preparation method solves the problems of low efficiency, interface layering, debonding and the like in the integrated forming process of the functional material, and the preparation with high speed, batch and low cost is realized.
In the present invention, the drying function is to partially evaporate the solvent during the preparation of the prepreg of the polyimide/fiber composite material layer and the prepreg of the polyimide/fiber composite material layer, but to maintain the flexibility of the fiber.
Preferably, the impregnating solution of the phenolic resin comprises phenolic compounds and aldehyde compounds.
Preferably, the phenolic resin impregnation liquor has a solids content of 50% -80%, for example 52%, 55%, 60%, 62%, 65%, 68%, 70%, 72%, 75% or 78% etc.
Preferably, the impregnation liquid of the polyimide comprises a diamine compound, a dianhydride compound and a catalyst.
Preferably, the polyimide impregnation fluid has a solids content of 10% to 30%, for example 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26% or 28%, etc.
Preferably, the hot pressing includes heat-pressing at a pressure of 1-5Mpa (e.g., 1.2Mpa, 1.5Mpa, 1.8Mpa, 2Mpa, 2.2Mpa, 2.5Mpa, 3.0Mpa, 3.2Mpa, 3.5Mpa, 4Mpa, or 4.5Mpa, etc.), at 150 ℃ -170 ℃ (e.g., 152 ℃, 154 ℃, 156 ℃, 158 ℃, 160 ℃, 162 ℃, 164 ℃, 166 ℃, or 168 ℃, etc.), for 1-3 hours (e.g., 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, or 2.8 hours, etc.), for 1-3 hours (e.g., 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2.4 hours, 2.6 hours, or 2.8 hours, etc.), at 250 ℃ -270 ℃ (e.252 ℃, 254 ℃, 258 ℃, 260 ℃, 262 ℃, 264 ℃, 266 ℃, or 268 ℃, etc.).
In a third aspect, the present invention provides the use of a fibre reinforced resin-based composite material as described in the first aspect in an aerospace structural material.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the fiber reinforced resin matrix composite material regulates and controls the molding temperature of polyimide resin by a catalyst doping method, and then is compounded by a phenolic resin composite material layer and a polyimide composite material layer, and is molded and cured, so that the phenolic resin and polyimide are further reacted, the crosslinking density is improved, the heat resistance is obviously improved, and the prepared fiber reinforced resin matrix composite material has the characteristics of ablation resistance and good mechanical property. The preparation method of the fiber reinforced resin matrix composite material solves the problems of low efficiency, interface layering, debonding and the like in the integrated forming process of the functional material, and realizes quick, batch and low-cost preparation. The tensile strength of the fiber reinforced resin matrix composite is 359-422MPa, and the mass ablation rate is 0.82-0.99mg s -1 。
Drawings
Fig. 1 is a flowchart of the preparation of the fiber reinforced resin matrix composite.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a fiber reinforced resin matrix composite and a preparation method thereof, wherein the fiber reinforced resin matrix composite comprises a phenolic resin composite layer and a polyimide composite layer;
the phenolic resin composite material layer comprises 7 phenolic resin/fiber composite material layers;
the polyimide composite layer comprises 7 polyimide/fiber composite layers.
The fiber reinforced resin matrix composite comprises the following components in parts by weight: 30 parts of phenolic resin, 30 parts of polyimide and 40 parts of fiber (carbon fiber cloth).
The preparation method of the fiber reinforced resin matrix composite material is as follows.
Preparation of a prepreg for a phenolic resin/fiber composite layer:
mixing carbon fiber cloth and impregnating solution of phenolic resin (comprising phenol, formaldehyde and absolute ethyl alcohol solvent in a mass ratio of 2:2:1.7, wherein the solid content is 70%), vacuumizing for 2 hours, spreading the carbon fiber cloth loaded with the impregnating solution on a glass plate adhered with release paper, coating the impregnating solution on the surface of the carbon fiber cloth with a coater, leveling, and drying at 65 ℃ for 1 hour to obtain the prepreg of the phenolic resin/fiber composite material layer.
Preparation of a prepreg for a polyimide/fiber composite layer:
mixing carbon fiber cloth and impregnating solution of polyimide (comprising 4, 4-diaminodiphenyl ether, pyromellitic dianhydride, benzimidazole and N, N-dimethylacetamide solvent in a mass ratio of 100:100:1:600), vacuumizing for 2 hours, spreading the carbon fiber cloth loaded with the impregnating solution on a glass plate adhered with release paper, coating the impregnating solution on the surface of the carbon fiber cloth with a coating device, leveling, and drying at 65 ℃ for 1 hour to obtain the prepreg of the polyimide/fiber composite material layer.
Preparing a fiber reinforced resin matrix composite:
laminating 7 layers of the prepreg of the phenolic resin/fiber composite material and 7 layers of the prepreg of the polyimide/fiber composite material in a one-way layering mode in sequence, placing the laminated materials into a die, fastening the laminated materials, placing the fastened materials on a high-temperature flat vulcanizing machine, and setting the temperature-raising program to be 25-150 DEG CThe temperature is 50min, the heat preservation time is 50h, then the temperature is raised from 150 ℃ to 250 ℃, the temperature raising time is 100min, the heat preservation time is 3h, and the whole process keeps the pressure of 2 MPa. Naturally cooling to room temperature after heat curing, demolding and taking out a sample to obtain the fiber reinforced resin matrix composite, wherein the size of a sample piece after heat pressing and curing is 100 multiplied by 10 multiplied by 5mm 3 。
Example 2
The embodiment provides a fiber reinforced resin matrix composite and a preparation method thereof, wherein the fiber reinforced resin matrix composite comprises a phenolic resin composite layer and a polyimide composite layer;
the phenolic resin composite material layer comprises 7 phenolic resin/fiber composite material layers;
the polyimide composite layer comprises 7 polyimide/fiber composite layers.
The fiber reinforced resin matrix composite comprises the following components in parts by weight: 35 parts of phenolic resin, 35 parts of polyimide and 30 parts of fiber (basalt fiber cloth).
The preparation method of the fiber reinforced resin matrix composite material is as follows.
Preparation of a prepreg for a phenolic resin/fiber composite layer:
mixing basalt fiber cloth and impregnating solution of phenolic resin (comprising phenol, formaldehyde and absolute ethyl alcohol solvent in a mass ratio of 2:2:1, wherein the solid content is 80%), vacuumizing for 1h, then spreading the carbon fiber cloth loaded with the impregnating solution on a glass plate adhered with release paper, coating the impregnating solution on the surface of the carbon fiber cloth with a coater to be flat, and drying at 55 ℃ for 3h to obtain the prepreg of the phenolic resin/fiber composite material layer.
Preparation of a prepreg for a polyimide/fiber composite layer:
mixing basalt fiber cloth and impregnating solution of polyimide (comprising 4, 4-diaminodiphenyl ether, pyromellitic dianhydride, quinoline and N, N-dimethylacetamide solvent in a mass ratio of 100:100:1:500, wherein the solid content is 28.5%), vacuumizing for 1h, spreading the carbon fiber cloth loaded with the impregnating solution on a glass plate adhered with release paper, coating the impregnating solution on the surface of the carbon fiber cloth with a coater to be flat, and drying at 55 ℃ for 3h to obtain the prepreg of the polyimide/fiber composite material layer.
Preparing a fiber reinforced resin matrix composite:
and (3) sequentially laminating 7 layers of the prepreg of the phenolic resin/fiber composite material and 7 layers of the prepreg of the polyimide/fiber composite material in a one-way layering mode, placing the laminated materials in a die, fastening the laminated materials on a high-temperature flat vulcanizing machine, setting a heating program at 25-150 ℃, setting the heating time at 80min, setting the heat-preserving time at 2h, then heating the laminated materials from 150-250 ℃ for 50min, and preserving the heat for 1h, wherein the whole process maintains the pressure of 5 MPa. Naturally cooling to room temperature after heat curing, demolding and taking out a sample to obtain the fiber reinforced resin matrix composite, wherein the size of the sample after heat pressing and curing is 200 multiplied by 50 multiplied by 10mm 3 。
Example 3
The embodiment provides a fiber reinforced resin matrix composite and a preparation method thereof, wherein the fiber reinforced resin matrix composite comprises a phenolic resin composite layer and a polyimide composite layer;
the phenolic resin composite material layer comprises 7 phenolic resin/fiber composite material layers;
the polyimide composite layer comprises 7 polyimide/fiber composite layers.
The fiber reinforced resin matrix composite comprises the following components in parts by weight: 20 parts of phenolic resin, 20 parts of polyimide and 60 parts of fiber (quartz fiber cloth).
The preparation method of the fiber reinforced resin matrix composite material is as follows.
Preparation of a prepreg for a phenolic resin/fiber composite layer:
mixing quartz fiber cloth and impregnating solution of phenolic resin (comprising phenol, formaldehyde and absolute ethyl alcohol solvent in a mass ratio of 2:2:4, wherein the solid content is 50%), vacuumizing for 4 hours, then spreading the carbon fiber cloth loaded with the impregnating solution on a glass plate adhered with release paper, coating the impregnating solution on the surface of the carbon fiber cloth with a coater to be flat, and drying at 45 ℃ for 5 hours to obtain the prepreg of the phenolic resin/fiber composite material layer.
Preparation of a prepreg for a polyimide/fiber composite layer:
mixing quartz fiber cloth and polyimide impregnating solution (comprising 4, 4-diaminodiphenyl ether, pyromellitic dianhydride, benzimidazole and N, N-dimethylacetamide solvent in a mass ratio of 100:100:1:1000, wherein the solid content is 16.7%), vacuumizing for 4 hours, spreading the carbon fiber cloth loaded with the impregnating solution on a glass plate adhered with release paper, coating the impregnating solution on the surface of the carbon fiber cloth with a coater to be flat, and drying at 45 ℃ for 5 hours to obtain the prepreg of the polyimide/fiber composite material layer.
Preparing a fiber reinforced resin matrix composite:
and (3) sequentially laminating 7 layers of the prepreg of the phenolic resin/fiber composite material and 7 layers of the prepreg of the polyimide/fiber composite material in a one-way layering mode, placing the laminated layers in a die, fastening the laminated layers on a high-temperature flat vulcanizing machine, setting a heating program at 25-150 ℃, setting the heating time at 100min, setting the heat preservation time at 1h, then heating the laminated layers from 150-250 ℃ for 40min, and keeping the heat preservation for 3h, wherein the whole process keeps the pressure of 1 MPa. Naturally cooling to room temperature after heat curing, demolding and taking out a sample to obtain the fiber reinforced resin matrix composite, wherein the size of a sample piece after heat pressing and curing is 150 multiplied by 25 multiplied by 8mm 3 。
Example 4
The present embodiment provides a fiber-reinforced resin-based composite material and a method for preparing the same, which differ from embodiment 1 only in that the phenolic resin composite material layer includes 9 phenolic resin/fiber composite material layers; the polyimide composite layer comprises 9 polyimide/fiber composite layers.
In the preparation of the fiber reinforced resin matrix composite, 9 layers of the prepreg of the phenolic resin/fiber composite and 9 layers of the prepreg of the polyimide/fiber composite are sequentially stacked in a mold according to a unidirectional layering manner, and the other steps are the same as in example 1.
Example 5
The present embodiment provides a fiber-reinforced resin-based composite material and a method for preparing the same, which differ from embodiment 1 only in that the phenolic resin composite material layer includes 11 phenolic resin/fiber composite material layers; the polyimide composite layer includes 11 polyimide/fiber composite layers.
In the preparation of the fiber reinforced resin matrix composite, 11 layers of the prepreg of the phenolic resin/fiber composite and 11 layers of the prepreg of the polyimide/fiber composite are sequentially stacked in a mold according to a unidirectional layering manner, and the other steps are the same as in example 1.
Example 6
The present embodiment provides a fiber-reinforced resin-based composite material and a method for preparing the same, which differ from embodiment 1 only in that the phenolic resin composite material layer includes 14 phenolic resin/fiber composite material layers; the polyimide composite layer comprised 14 polyimide/fiber composite layers.
In the preparation of the fiber reinforced resin matrix composite, 14 layers of the prepreg of the phenolic resin/fiber composite and 14 layers of the prepreg of the polyimide/fiber composite are sequentially stacked in a mold according to a unidirectional layering manner, and the other steps are the same as in example 1.
Example 7
The present embodiment provides a fiber-reinforced resin-based composite material and a method for preparing the same, which differ from embodiment 1 only in that the phenolic resin composite material layer includes 5 phenolic resin/fiber composite material layers; the polyimide composite layer comprises 5 polyimide/fiber composite layers.
In the preparation of the fiber reinforced resin matrix composite, 5 layers of the prepreg of the phenolic resin/fiber composite and 5 layers of the prepreg of the polyimide/fiber composite are sequentially stacked in a mold according to a unidirectional layering manner, and the other steps are the same as in example 1.
Example 8
This example provides a fiber-reinforced resin-based composite material and a method for producing the same, which differ from example 1 only in that 7 layers of the prepreg of the above phenolic resin/fiber composite material and 7 layers of the prepreg of the above polyimide/fiber composite material are sequentially stacked in a mold in such a manner that the prepreg is laid up in a multi-directional manner in a direction 45 ° to the fiber, and the other is the same as example 1.
Example 9
This example provides a fiber-reinforced resin-based composite material and a method for producing the same, which differ from example 1 only in that 7 layers of the above-mentioned prepreg of the phenolic resin/fiber composite material and 7 layers of the above-mentioned prepreg of the polyimide/fiber composite material are sequentially stacked in a mold in a multi-directional lay-up manner in a direction perpendicular to the fibers in the production of the fiber-reinforced resin-based composite material, and the other are the same as in example 1.
Example 10
The embodiment provides a fiber reinforced resin matrix composite and a preparation method thereof, which are different from embodiment 1 only in that the fiber reinforced resin matrix composite comprises the following components in parts by weight: 30 parts of phenolic resin, 30 parts of polyimide and 20 parts of fiber (carbon fiber cloth).
In the preparation method of the fiber reinforced resin matrix composite, the components of the impregnating solution of the phenolic resin are adjusted to phenol, formaldehyde and absolute ethyl alcohol solvent with the mass ratio of 2:2:0.98, and the solid content of the impregnating solution of the phenolic resin is 90%; the components of the impregnating solution of the polyimide are adjusted to be 4, 4-diaminodiphenyl ether, pyromellitic dianhydride, benzimidazole and N, N-dimethylacetamide solvent with the mass ratio of 100:100:1:370, and the solid content of the impregnating solution of the polyimide is 35%.
Otherwise, the same as in example 1 was used.
Example 11
The embodiment provides a fiber reinforced resin matrix composite and a preparation method thereof, which are different from embodiment 1 only in that the fiber reinforced resin matrix composite comprises the following components in parts by weight: 30 parts of phenolic resin, 30 parts of polyimide and 70 parts of fiber (carbon fiber cloth).
In the preparation method of the fiber reinforced resin matrix composite, the components of the impregnating solution of the phenolic resin are adjusted to phenol, formaldehyde and absolute ethyl alcohol solvents with the mass ratio of 2:2:5, and the solid content of the impregnating solution of the phenolic resin is 44%; the components of the impregnating solution of the polyimide are adjusted to be 4, 4-diaminodiphenyl ether, pyromellitic dianhydride, benzimidazole and N, N-dimethylacetamide solvent with the mass ratio of 100:100:1:1200, and the solid content of the impregnating solution of the polyimide is 14%.
Otherwise, the same as in example 1 was used.
Comparative example 1
This comparative example provides a fiber reinforced resin-based composite material and a method of preparing the same, which differs from example 1 only in that the fiber reinforced resin-based composite material does not include a polyimide composite material layer, and the phenolic resin composite material layer includes 14 phenolic resin/fiber composite material layers;
the fiber reinforced resin matrix composite comprises the following components in parts by weight: 60 parts of phenolic resin and 40 parts of fiber (carbon fiber cloth).
14 layers of the prepreg of the phenolic resin/fiber composite material are sequentially stacked in a unidirectional layering manner in a mold, and the layers are stacked in the mold, otherwise, the prepreg is the same as in example 1.
Comparative example 2
This comparative example provides a fiber reinforced resin-based composite material and a method of preparing the same, which is different from example 1 only in that the fiber reinforced resin-based composite material does not include a phenolic resin composite material layer including 14 polyimide/fiber composite material layers;
the fiber reinforced resin matrix composite comprises the following components in parts by weight: 60 parts of polyimide and 40 parts of fiber (carbon fiber cloth).
Preparation of fiber-reinforced resin matrix composite the 14 layers of the polyimide/fiber composite prepreg were sequentially stacked in a unidirectional lay-up manner in a mold and stacked in the mold, the other being the same as in example 1.
The following performance tests were performed on the fiber reinforced resin matrix composites provided in examples and comparative examples:
(1) Tensile strength: according to the GB/T1040.1-2018 test, the test conditions refer to GB/T1040.2-2006, and the test direction of the tensile strength is perpendicular to the direction of the fibers in the outermost phenolic resin/fiber composite material layer.
(2) Ablation resistance: the mass ablation rate was tested using a self-heating protective material ablation test platform whose parameters are shown in table 1.
TABLE 1
Device information Related parameters Device information Related parameters
Ablation gas Butane Center flame temperature >1500℃
Nozzle diameter 2.0mm Gas working pressure 0.4MPa
Ablation distance 60mm Gas flow rate 558L/h
Ablation angle 90° Heat flux density 1038±103.8KW/m 2
Temperature measurement optris CT 3M Ablation time 120s
The test results are shown in Table 2.
TABLE 2
As can be seen from the test results in Table 2, the fiber-reinforced resin-based composite materials provided in examples 1 to 11 had tensile strengths of 359 to 422MPa and mass ablation rates of 0.82 to 0.99mg s -1 。
As can be seen from comparison of examples 1 and examples 4-6, the tensile properties of the composite materials are gradually improved with increasing ply thickness, up to 422MPa, and the ablation properties are not significantly changed.
As compared with example 1, if the number of phenolic resin/fiber composite layers in the phenolic resin composite layer and the number of polyimide/fiber composite layers in the polyimide composite layer are too low (example 7), the tensile properties of the fiber reinforced resin matrix composite are reduced, which proves that the number of phenolic resin/fiber composite layers in the phenolic resin composite layer and the number of polyimide/fiber composite layers in the polyimide composite layer are both within specific ranges, and the prepared fiber reinforced resin matrix composite has better properties.
As compared with example 1, when the fibers are laminated in a multi-directional ply manner in a direction inclined by 45 ° (example 8), the tensile strength is improved and the mass ablation rate is lowered; when the layers are stacked in a multi-directional layering manner perpendicular to the fiber direction (example 9), the tensile strength increases and the mass ablation rate decreases. Different mechanical properties can be obtained by adjusting the layering orientation of the fibers, and the mechanical properties are improved along the direction of 45 degrees inclined to the fibers and along the direction perpendicular to the fibers, wherein the ablation properties are slightly improved along the direction perpendicular to the fibers. The fiber reinforced resin matrix composite material prepared by multi-directional layering along the direction of 45 degrees of fiber inclination and/or multi-directional layering along the direction perpendicular to the fiber direction has better effect.
As is clear from comparison with example 1, if the weight fraction of the fibers is too low (example 10), the tensile strength of the fiber-reinforced resin-based composite material decreases, and the mechanical properties decrease; if the weight fraction of the fibers is too high (example 11), the ablation resistance of the fiber reinforced resin matrix composite is reduced; the fiber reinforced resin matrix composite prepared by adopting the fiber with specific weight parts has better effect.
As can be seen from comparison with example 1, if the fiber reinforced resin matrix composite material does not include a polyimide composite material layer (comparative example 1), the tensile strength is lowered, the mass ablation rate is improved, and the ablation performance is lowered; if the fiber reinforced resin matrix composite material does not include the phenolic resin composite material layer (comparative example 2), the tensile strength is reduced, and the fiber reinforced resin matrix composite material prepared by using the polyimide composite material layer and the phenolic resin composite material layer has better effect.
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to, i.e. does not mean that the invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.

Claims (10)

1. The fiber reinforced resin matrix composite is characterized by comprising a phenolic resin composite layer and a polyimide composite layer;
the phenolic resin composite material layer comprises one or at least two phenolic resin/fiber composite material layers;
the polyimide composite material layer comprises one or at least two polyimide/fiber composite material layers;
the fiber reinforced resin matrix composite comprises phenolic resin, polyimide and fibers;
the polyimide is prepared from diamine compounds, dianhydride compounds and catalysts.
2. The fiber reinforced resin matrix composite according to claim 1, wherein the raw materials for preparing the phenolic resin comprise phenolic compounds and aldehyde compounds;
preferably, the phenolic compound comprises any one or a combination of at least two of phenol, cresol or xylenol;
preferably, the aldehyde compound comprises formaldehyde.
3. The fiber reinforced resin matrix composite of claim 1 or 2, wherein the diamine compound comprises 4, 4-diaminodiphenyl ether;
preferably, the dianhydride compound comprises pyromellitic dianhydride and/or 3,3', 4' -biphenyl tetracarboxylic dianhydride;
preferably, the catalyst comprises any one or a combination of at least two of benzimidazole, quinoline or parahydroxybenzoic acid.
4. A fibre reinforced resin matrix composite according to any one of claims 1 to 3, wherein the fibres comprise a fibre cloth;
preferably, the fiber cloth comprises any one or a combination of at least two of basalt fiber cloth, carbon fiber cloth, quartz fiber cloth or polyimide fiber cloth.
5. The fiber reinforced resin matrix composite of any of claims 1-4, wherein the fiber reinforced resin matrix composite comprises the following components in parts by weight: 20-35 parts of phenolic resin, 20-35 parts of polyimide and 30-60 parts of fiber.
6. The fiber reinforced resin matrix composite according to any one of claims 1 to 5, wherein the number of phenolic resin/fiber composite layers in the phenolic resin composite layer is 7 to 14;
preferably, the number of polyimide/fiber composite material layers in the polyimide composite material layer is 7-14;
preferably, the layering mode of the fiber reinforced resin matrix composite material comprises unidirectional layering and multidirectional layering;
preferably, the layering mode of the fiber reinforced resin matrix composite material comprises multi-directional layering along the direction of 45 degrees of fiber inclination and/or multi-directional layering along the direction perpendicular to the fiber direction.
7. A method of preparing a fiber reinforced resin based composite according to any one of claims 1 to 6, comprising the steps of: and sequentially layering the prepreg of the phenolic resin/fiber composite material layer and the prepreg of the polyimide/fiber composite material layer, and performing hot pressing to obtain the fiber reinforced resin matrix composite material.
8. The method of preparing a prepreg of the phenolic resin/fiber composite layer according to claim 7, wherein the method of preparing a prepreg of the phenolic resin/fiber composite layer comprises the steps of: mixing the fiber with the impregnating solution of the phenolic resin, vacuumizing for 1-4 hours, then spreading the fiber loaded with the impregnating solution on a glass plate stuck with release paper, coating the prepreg on the surface of the fiber with a coater, and drying at 45-65 ℃ for 1-5 hours to obtain the prepreg of the phenolic resin/fiber composite material layer;
preferably, the preparation method of the prepreg of the polyimide/fiber composite material layer is as follows: mixing the fiber with the impregnating solution of polyimide, vacuumizing for 1-4 hours, spreading the fiber loaded with the impregnating solution on a glass plate stuck with release paper, coating the impregnating solution on the surface of the fiber to be smooth by using a coater, and drying at 45-65 ℃ for 1-5 hours to obtain the prepreg of the polyimide/fiber composite material layer;
preferably, the impregnating solution of the phenolic resin comprises phenolic compounds and aldehyde compounds;
preferably, the solid content of the impregnating solution of the phenolic resin is 50% -80%;
preferably, the impregnating solution of the polyimide comprises diamine compounds, dianhydride compounds and catalysts;
preferably, the solid content of the impregnation liquid of the polyimide is 10-30%.
9. The method of claim 7 or 8, wherein the hot pressing comprises heat-pressing at a pressure of 1-5Mpa, heat-pressing at 150-170 ℃ for 1-3h, and heat-pressing at 250-270 ℃ for 1-3h.
10. Use of a fiber reinforced resin based composite material according to any one of claims 1-6 in aerospace structural materials.
CN202311016812.0A 2023-08-14 2023-08-14 Fiber reinforced resin matrix composite material and preparation method and application thereof Pending CN117021711A (en)

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