CN117325485B - Carbon fiber reinforced polyamide composite material for wind power blade and preparation method thereof - Google Patents

Carbon fiber reinforced polyamide composite material for wind power blade and preparation method thereof Download PDF

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Publication number
CN117325485B
CN117325485B CN202311620806.6A CN202311620806A CN117325485B CN 117325485 B CN117325485 B CN 117325485B CN 202311620806 A CN202311620806 A CN 202311620806A CN 117325485 B CN117325485 B CN 117325485B
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carbon fiber
fiber cloth
composite material
polyamide
wind power
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CN117325485A (en
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王震
蔡瑜
刘辉
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Zhejiang Hangyin New Material Technology Co ltd
Wu Zhenshiyanshi
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Zhejiang Hangyin New Material Technology Co ltd
Wu Zhenshiyanshi
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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/02—Conditioning or physical treatment of the material to be shaped by heating
    • B29B13/023—Half-products, e.g. films, plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • B29B15/10—Coating or impregnating independently of the moulding or shaping step
    • B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • B29B15/10—Coating or impregnating independently of the moulding or shaping step
    • B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
    • B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
    • B29B15/125—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex by dipping
    • 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
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • 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
    • B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0036—Heat treatment
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03D—WIND MOTORS
    • F03D80/00—Details, components or accessories not provided for in groups F03D1/00 - F03D17/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/08—Blades for rotors, stators, fans, turbines or the like, e.g. screw propellers
    • B29L2031/082—Blades, e.g. for helicopters
    • B29L2031/085—Wind turbine blades
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • 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
    • B32B2250/42—Alternating layers, e.g. ABAB(C), AABBAABB(C)
    • 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
    • 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
    • B32B2307/308—Heat stability
    • 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
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • B32B2603/00—Vanes, blades, propellers, rotors with blades
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05B—INDEXING SCHEME RELATING TO WIND, SPRING, WEIGHT, INERTIA OR LIKE MOTORS, TO MACHINES OR ENGINES FOR LIQUIDS COVERED BY SUBCLASSES F03B, F03D AND F03G
    • F05B2280/00—Materials; Properties thereof
    • F05B2280/40—Organic materials
    • F05B2280/4002—Cellulosic materials, e.g. wood
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05B—INDEXING SCHEME RELATING TO WIND, SPRING, WEIGHT, INERTIA OR LIKE MOTORS, TO MACHINES OR ENGINES FOR LIQUIDS COVERED BY SUBCLASSES F03B, F03D AND F03G
    • F05B2280/00—Materials; Properties thereof
    • F05B2280/40—Organic materials
    • F05B2280/4006—Polyamides, e.g. NYLON
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/70—Wind energy
    • Y02E10/72—Wind turbines with rotation axis in wind direction

Abstract

The invention provides a preparation method of a carbon fiber reinforced polyamide composite material for a wind power blade, which comprises the following steps: a) Soaking the carbon fiber cloth in polyamide acid solution, placing the soaked carbon fiber cloth in water for solvent replacement, taking out the carbon fiber cloth after the replacement is finished, and drying to obtain the carbon fiber cloth coated with polyamide acid; b) Heating and solidifying the carbon fiber cloth coated with the polyamide acid, and carbonizing to obtain modified carbon fiber cloth; c) And alternately stacking the modified carbon fiber cloth and the polyamide sheet, and performing hot pressing and cooling to obtain the modified carbon fiber cloth. According to the invention, an interconnection network is constructed in the carbon fiber by a polyimide in-situ carbonization method, and the composite material prepared by the method has better mechanical properties due to the stress dispersion effect of the carbon fiber interconnection network, and has the advantages of easy recovery, good thermal stability, low cost and the like.

Description

Carbon fiber reinforced polyamide composite material for wind power blade and preparation method thereof
Technical Field
The invention relates to the technical field of materials, in particular to a carbon fiber reinforced polyamide composite material for wind power blades and a preparation method thereof.
Background
The basic principle of wind power generation is that a wind wheel is utilized to drive a wind driven generator to rotate, so that the rotating power of the wind driven generator is converted into electric energy through the generator. Wind power generators generally consist of a tower, a wind wheel and a generator. The wind wheel is usually composed of a plurality of blades, and when wind blows over the blades, a pressure difference is generated to drive the wind wheel to rotate. In the whole set of assembly, the wind power blade is a crucial part, and the wind power blade which is widely used at present is made of epoxy resin/glass fiber composite material. However, due to the permanent cross-linking nature of epoxy, as the amount of wind power equipment in the future increases, a large number of retired blades will impose a significant environmental burden.
The carbon fiber reinforced thermoplastic composite is a composite consisting of a thermoplastic polymer matrix and a carbon fiber reinforced material. Carbon fiber is a fiber material with high strength and high modulus, and has excellent mechanical properties and light weight. The carbon fiber is combined with the thermoplastic polymer matrix, and a composite material which has high strength, high rigidity, low weight and easy recovery can be obtained.
The carbon fiber reinforced thermoplastic composite material has wide application in the fields of aerospace, automobile industry, sports goods and the like. In the field of aerospace, the composite material can be used for manufacturing parts such as an airplane body, a wing panel, a control surface and the like so as to realize light structure and improve the performance and fuel efficiency of the airplane. In the automotive industry, they may be used to manufacture body parts, seating structures, etc. to reduce the weight of automobiles and improve safety performance. In the field of sporting goods, they can be used to make high performance golf clubs, tennis rackets, etc.
Document 1: CN115678204a discloses an epoxy fiber composite material for wind power blades and a preparation method thereof, wherein the preparation method comprises the steps of preparing glycidyl ester type epoxy resin, preparing an epoxy resin composition, impregnating inorganic fibers with the epoxy resin composition, and drying to obtain the epoxy composite material for wind power blades. The epoxy resin/glass fiber composite material prepared by the preparation method can be degraded by high-boiling-point alcohol such as ethylene glycol, so that the recycling of the material is realized. The preparation method adopts a method of chain extension of small molecules with low molecular weight into a macromolecular structure, thereby increasing the gel reaction time and providing great convenience for construction. Although document 1 can realize recycling of materials by resin degradation, the process of the method is complex, and part of waste materials still exist and cannot be fully recycled.
It is therefore highly desirable to provide a thermoplastic composite of carbon fiber reinforced polyamide for wind turbine blades that is easy to recycle and has a high mechanical strength.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a carbon fiber reinforced polyamide composite material for wind power blades, which has good mechanical properties and is easy to recycle.
The invention provides a preparation method of a carbon fiber reinforced polyamide composite material for a wind power blade, which comprises the following steps:
a) Soaking the carbon fiber cloth in polyamide acid solution, placing the soaked carbon fiber cloth in water for solvent replacement, taking out the carbon fiber cloth after the replacement is finished, and drying to obtain the carbon fiber cloth coated with polyamide acid;
b) Heating and solidifying the carbon fiber cloth coated with the polyamide acid, and carbonizing to obtain modified carbon fiber cloth;
c) And alternately stacking the modified carbon fiber cloth and the polyamide sheet, and performing hot pressing and cooling to obtain the modified carbon fiber cloth.
Preferably, the concentration of the polyamic acid solution in the step A) is 1 to 30 weight percent; the carbon fiber cloth comprises any one of plain weave, satin weave and twill weave.
Preferably, the soaking in the step A) is specifically soaking for 20-24 hours at 25 ℃.
Preferably, the solvent replacement temperature in the step A) is 25 ℃, and the replacement time is 1-72 h; the drying temperature is 80 ℃ and the drying time is 2 hours.
Preferably, the heat curing in the step B) is specifically: curing for 0-2 h at 280-350 ℃.
Preferably, the carbonization in step B) is specifically: carbonizing for 1-5 h at 800-1800 ℃ in an argon atmosphere.
Preferably, the thickness of the polyamide sheet in the step C) is 0.02-1 mm.
Preferably, the hot pressing in step C) is specifically: hot-pressing for 2-180 min at 200-300 ℃ under the condition of 0.1-2 MPa;
the thickness of the carbon fiber reinforced polyamide composite material for the wind power blade is preferably 2 mm-200 mm.
The invention can determine the number of stacked layers according to the required thickness, and the number of layers required to be alternately stacked with the thickness of 2mm is 10-20.
The invention provides a carbon fiber reinforced polyamide composite material for a wind power blade, which is prepared by the preparation method according to any one of the technical schemes.
The invention provides a wind power blade, which comprises the carbon fiber reinforced polyamide composite material according to the technical scheme.
Compared with the prior art, the invention provides a preparation method of a carbon fiber reinforced polyamide composite material for a wind power blade, which comprises the following steps: a) Soaking the carbon fiber cloth in polyamide acid solution, placing the soaked carbon fiber cloth in water for solvent replacement, taking out the carbon fiber cloth after the replacement is finished, and drying to obtain the carbon fiber cloth coated with polyamide acid; b) Heating and solidifying the carbon fiber cloth coated with the polyamide acid, and carbonizing to obtain modified carbon fiber cloth; c) And alternately stacking the modified carbon fiber cloth and the polyamide sheet, and performing hot pressing and cooling to obtain the modified carbon fiber cloth. Compared with a thermosetting composite material, the thermoplastic composite material has obvious advantages in the aspects of recoverability, high specific strength, high specific stiffness, high corrosion resistance, cost effectiveness, design flexibility and the like, and the resin and the fiber reinforced material can be easily recovered only by heating and melting the composite material. In addition, the method of in-situ carbonization of polyimide constructs an interconnection network in the carbon fiber, and the composite material prepared by the method has better mechanical properties due to the stress dispersion effect of the carbon fiber interconnection network, and has the advantages of easy recovery, good thermal stability, low cost and the like.
Detailed Description
The invention provides a carbon fiber reinforced polyamide composite material for a wind power blade and a preparation method thereof, and a person skilled in the art can refer to the content of the carbon fiber reinforced polyamide composite material and properly improve the technological parameters. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and they are intended to be within the scope of the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the invention can be practiced and practiced with modification and alteration and combination of the methods and applications herein without departing from the spirit and scope of the invention.
In the present application, the term "and/or" describes an association relationship of an association object, which means that three relationships may exist, for example, a and/or B may mean that a exists alone, a and B exist together, and B exists alone. Wherein A, B may be singular or plural.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s).
It should be understood that, in various embodiments of the present application, the sequence number of each process does not mean that the sequence of execution is sequential, and some or all of the steps may be executed in parallel or sequentially, where the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The invention provides a preparation method of a carbon fiber reinforced polyamide composite material for a wind power blade, which comprises the following steps:
a) Soaking the carbon fiber cloth in polyamide acid solution, placing the soaked carbon fiber cloth in water for solvent replacement to remove the solvent, taking out the carbon cloth after the replacement is finished, and drying to obtain the carbon fiber cloth coated with polyamide acid;
b) Heating and solidifying the carbon fiber cloth coated with the polyamide acid, and carbonizing to obtain modified carbon fiber cloth;
c) And alternately stacking the modified carbon fiber cloth and the polyamide sheet, and performing hot pressing and cooling to obtain the modified carbon fiber cloth.
The invention provides a preparation method of a carbon fiber reinforced polyamide composite material for a wind power blade.
The carbon fiber cloth comprises any one of plain weave, satin weave and twill weave.
The specification of the carbon fiber cloth is not limited, and those skilled in the art can know the specification.
In some embodiments, the carbon fiber cloth gauge is 350mm x 350mm;
in some embodiments, the number of carbon fiber cloths is 5-7.
The concentration of the polyamic acid solution is 1-30wt%; more preferably 2-20 wt%; most preferably 5 to 20 wt%.
Wherein the soaking is specifically soaking for 20-24 hours at 25 ℃; preferably, the infiltration is specifically performed at 25 ℃ for 22-24 hours; more preferably, the infiltration is specifically infiltration for 24 hours at 25 ℃.
The polyimide is used as a solid carbon source, and a bridged network is constructed in the carbon fiber cloth, so that the polyimide has a function of dredging concentrated stress, and the enhanced mechanical property is realized. And (3) impregnating the carbon fiber cloth by using the polyamic acid solution to realize uniform netlike carbon bridging. The solvent is removed by using a solvent replacement method, so that the continuity of the bridging structure is ensured, if a solvent evaporation method is used, a large amount of solvent volatilizes in the process to cause pollution, and the solvent volatilizes to cause shrinkage of the structure to cause damage of the bridging structure. Thermoplastic polyamide is used as a matrix material, so that the recycling property is strong and the cost is low.
And (3) placing the carbon cloth in water for solvent replacement after the infiltration is completed, taking out the carbon cloth after the replacement is completed, and drying to obtain the carbon fiber cloth coated with polyamide acid.
After the infiltration is completed, the carbon cloth is taken out, the surface residual polyamic acid solution is slightly wiped,
wherein the solvent replacement temperature is 25 ℃, and the replacement time is 1-72 h;
in some embodiments, the solvent displacement temperature is 25 ℃, and the displacement time is 10-70 hours;
in some embodiments, the solvent displacement temperature is 25 ℃, and the displacement time is 24-50 hours;
in some embodiments, the solvent displacement temperature is 25 ℃ and the displacement time is 48 hours.
Immersing in water for solvent replacement, removing DMAC solvent, and drying to coat a layer of polyamic acid on the surface of the carbon fiber cloth.
The drying temperature is 80 ℃ and the drying time is 2 hours.
Heating and solidifying the carbon fiber cloth coated with the polyamide acid,
the prepared material is put into a carbonization furnace and is converted into polyimide after being heated and cured, and the heating and curing are specifically as follows: curing for 0.5-2 hours at 280-350 ℃; more preferably, it is cured at 350℃for 1 hour.
The structural formula of the polyamic acid is:
the polyamide acid is converted into polyimide after being solidified, and the structural formula is as follows:
and (3) after the heating and curing, carbonizing to obtain the modified carbon fiber cloth.
Polyimide is converted into a carbon structure after high-temperature carbonization. The carbonization specifically comprises the following steps: carbonizing for 1-5 h at 800-1800 ℃ in an argon atmosphere.
In some embodiments, the carbonization is specifically: carbonizing for 1-4 h at 900-1600 ℃ in an argon atmosphere.
In some embodiments, the carbonization is specifically: carbonizing for 1-3 h at 1000-1400 ℃ in an argon atmosphere.
And alternately stacking the modified carbon fiber cloth and the polyamide sheet, and performing hot pressing and cooling to obtain the modified carbon fiber cloth.
The thickness of the polyamide sheet is 0.02-1 mm.
The hot pressing specifically comprises the following steps: hot-pressing for 2-180 min at 200-300 ℃ under the condition of 0.1-2 MPa;
the thickness of the carbon fiber reinforced polyamide composite material for the wind power blade is generally 2 mm-200 mm.
The number of stacked layers is determined according to the required thickness, and the number of layers required to be alternately stacked for the thickness of 2mm is 10-20 layers.
In some preferred embodiments, the hot pressing is specifically: heating to 220 ℃ under the condition of 0.1-2 MPa, preserving heat for 10min, heating to 250 ℃ at the speed of 10 ℃/min, and preserving heat for 10min, wherein the temperature is 25 ℃.
In some preferred embodiments, the hot pressing is performed by placing the stacked materials in a press vulcanizer, setting the pressure to 0.1MPa, heating to 220 ℃, maintaining the temperature for 10min, setting the pressure to 2MPa, heating to 250 ℃ at a speed of 10 ℃/min, maintaining the temperature for 10min, setting the pressure to 0.1MPa, and maintaining the temperature to 25 ℃. Waiting for natural cooling.
According to the invention, the polymer is used as a carbon source, and graphene grows in situ through pyrolyzing the polymer, so that the method is an effective method for preparing the covalent bond connection three-dimensional structure. In the present invention, polyimide is selected as a solid carbon source of graphene because polyimide has high carbon content and has an aromatic heterocyclic skeleton with high carbon yield. The pyrolysis of polyimide is mainly divided into two stages, wherein the first stage is 450-650 ℃, a series of changes of molecular chain structures mainly occur, imide rings are broken to remove carbonyl groups to form benzene ring type compounds, and the compounds containing conjugated cyano groups and isocyano groups are subjected to a series of complex polymerization to finally temporarily form polycyclic aromatic hydrocarbon structures. The second stage is that after 650 ℃, the aromatic heterocyclic structures are gradually combined, redundant nitrogen atoms and oxygen atoms are further removed to obtain a nitrogen-containing aromatic heterocyclic compound, and then the nitrogen-containing aromatic heterocyclic compound is pyrolyzed for a long time to finally generate a netlike carbon layer structure similar to a graphite hexagonal lamellar structure.
In order to realize uniform compounding of polyimide to the carbon fiber cloth, the carbon fiber cloth is soaked by the polyamic acid solution, so that uniform distribution of polyimide is realized. After pyrolysis, the netlike carbon layer connects adjacent carbon fibers in a covalent bond mode, so that the stability of the three-dimensional structure is improved. When being stressed, the adjacent carbon fibers can share the stress together, thereby realizing higher mechanical strength.
The invention provides a carbon fiber reinforced polyamide composite material for a wind power blade, which is prepared by the preparation method according to any one of the technical schemes.
The preparation method of the carbon fiber reinforced polyamide composite material for the wind power blade provided by the invention has been described above clearly, and will not be described in detail herein.
The invention provides a wind power blade, which comprises the carbon fiber reinforced polyamide composite material according to the technical scheme.
The specific materials and the preparation process of the wind power blade are not limited, and the wind power blade is well known to those skilled in the art.
The wind power blade material has good mechanical property, good thermal stability and low production cost, and resin and carbon fibers can be easily separated by heating and melting, so that the wind power blade material can be recycled almost completely and has higher economy.
The polyimide in-situ pyrolysis of the invention forms a lamellar graphite structure and is combined with carbon fibers by covalent bonds, the three-dimensional structure has good stability and strong binding force, the reinforcing effect on the composite material is obvious, and the problem of insufficient mechanical property when the traditional thermoplastic composite material is used as a wind power blade material is solved. The solvent is removed by using a solvent replacement method, and the method has the advantages of simple operation, good structural integrity and high recovery efficiency. The thermoplastic polyamide resin is used for preparing the composite material, the material has good recoverability, the separation of the polymer and the carbon fiber can be easily realized only by heating and melting, and the recovery process is simple, economical and environment-friendly.
In order to further illustrate the invention, the following describes in detail a carbon fiber reinforced polyamide composite material for wind power blades and a preparation method thereof in connection with examples.
Example 1
Adding DMAC to adjust the concentration of the polyamide acid solution with the mass fraction of 20% to 5%, immersing 7 carbon cloths with the mass fraction of 350mm in the polyamide acid solution with the mass fraction of 5%, and soaking for 24 hours at 25 ℃. After the soaking is completed, the carbon cloth is taken out, the polyamide acid solution remained on the surface is slightly wiped, the polyamide acid solution is soaked in water, the soaking is carried out for 48 hours at 25 ℃ for solvent replacement, after the replacement is completed, the carbon cloth is taken out, and the carbon cloth is placed in an oven for drying for 2 hours at 80 ℃. And (3) after drying, placing the carbon cloth into a tube furnace, introducing argon, heating to 350 ℃ at the speed of 10 ℃/min, preserving heat for 1h, and then continuously heating to 1000 ℃ at the speed of 10 ℃/min, preserving heat for 1h to finish carbonization. Taking out the carbon cloth after cooling to room temperature, taking 8 PA6 films with the thickness of 0.3mm and 350mm, putting the films into an oven for drying at 80 ℃ for 12 hours, alternately stacking the PA6 films and the carbonized carbon cloth, putting the films into a flat vulcanizing machine, setting the pressure to be 0.1MPa, heating to 220 ℃, preserving heat for 10min, setting the pressure to be 2MPa, heating to 250 ℃ at the speed of 10 ℃/min, preserving heat for 10min, setting the pressure to be 0.1MPa, setting the temperature to be 25 ℃, and taking out the material after natural cooling.
Example 2
Adding DMAC to adjust the concentration of the polyamide acid solution with the mass fraction of 20% to 10%, immersing 7 carbon cloths with the mass fraction of 350mm in the polyamide acid solution with the mass fraction of 10%, and soaking for 24 hours at 25 ℃. After the soaking is completed, the carbon cloth is taken out, the polyamide acid solution remained on the surface is slightly wiped, the polyamide acid solution is soaked in water, the soaking is carried out for 48 hours at 25 ℃ for solvent replacement, after the replacement is completed, the carbon cloth is taken out, and the carbon cloth is placed in an oven for drying for 2 hours at 80 ℃. And (3) after drying, placing the carbon cloth into a tube furnace, introducing argon, heating to 350 ℃ at the speed of 10 ℃/min, preserving heat for 1h, and then continuously heating to 1000 ℃ at the speed of 10 ℃/min, preserving heat for 1h to finish carbonization. Taking out the carbon cloth after cooling to room temperature, taking 8 PA6 films with the thickness of 0.3mm and 350mm, putting the films into an oven for drying at 80 ℃ for 12 hours, alternately stacking the PA6 films and the carbonized carbon cloth, putting the films into a flat vulcanizing machine, setting the pressure to be 0.1MPa, heating to 220 ℃, preserving heat for 10min, setting the pressure to be 2MPa, heating to 250 ℃ at the speed of 10 ℃/min, preserving heat for 10min, setting the pressure to be 0.1MPa, setting the temperature to be 25 ℃, and taking out the material after natural cooling.
Example 3
Adding DMAC to adjust the concentration of the polyamide acid solution with the mass fraction of 20% to 15%, immersing 7 carbon cloths with the mass fraction of 350mm in the polyamide acid solution with the mass fraction of 15%, and soaking for 24 hours at 25 ℃. After the soaking is completed, the carbon cloth is taken out, the polyamide acid solution remained on the surface is slightly wiped, the polyamide acid solution is soaked in water, the soaking is carried out for 48 hours at 25 ℃ for solvent replacement, after the replacement is completed, the carbon cloth is taken out, and the carbon cloth is placed in an oven for drying for 2 hours at 80 ℃. And (3) after drying, placing the carbon cloth into a tube furnace, introducing argon, heating to 350 ℃ at the speed of 10 ℃/min, preserving heat for 1h, and then continuously heating to 1000 ℃ at the speed of 10 ℃/min, preserving heat for 1h to finish carbonization. Taking out the carbon cloth after cooling to room temperature, taking 8 PA6 films with the thickness of 0.3mm and 350mm, putting the films into an oven for drying at 80 ℃ for 12 hours, alternately stacking the PA6 films and the carbonized carbon cloth, putting the films into a flat vulcanizing machine, setting the pressure to be 0.1MPa, heating to 220 ℃, preserving heat for 10min, setting the pressure to be 2MPa, heating to 250 ℃ at the speed of 10 ℃/min, preserving heat for 10min, setting the pressure to be 0.1MPa, setting the temperature to be 25 ℃, and taking out the material after natural cooling.
Comparative example 1
Taking 7 carbon cloths with 350mm and 8 PA6 films with 0.3mm with 350mm, firstly putting the PA6 films into an oven to be dried for 12 hours at 80 ℃, then alternately stacking the PA6 films and the carbon cloths, putting the carbon cloths into a flat vulcanizing machine, setting the pressure to be 0.1MPa, heating to 220 ℃, preserving heat for 10min, setting the pressure to be 2MPa, heating to 250 ℃ at the speed of 10 ℃/min, preserving heat for 10min, setting the pressure to be 0.1MPa, setting the temperature to be 25 ℃, and taking out the material after natural cooling.
The following table shows the mechanical property data of the carbon fiber reinforced polyamide composite materials for preparing the wind power blade according to the embodiment and the comparative example
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (7)

1. The preparation method of the carbon fiber reinforced polyamide composite material for the wind power blade is characterized by comprising the following steps of:
a) Soaking the carbon fiber cloth in polyamide acid solution, placing the soaked carbon fiber cloth in water for solvent replacement, taking out the carbon fiber cloth after the replacement is finished, and drying to obtain the carbon fiber cloth coated with polyamide acid; the concentration of the polyamic acid solution is 1-30wt%; the carbon fiber cloth comprises any one of plain weave, satin weave and twill weave; the soaking is specifically soaking for 20-24 hours at 25 ℃;
the structural formula of the polyamic acid is as follows:
；
b) Heating and curing the carbon fiber cloth coated with polyamide acid to form polyimide, and carbonizing to obtain modified carbon fiber cloth, so that the reticular carbon layer structure of the graphite hexagonal sheet structure formed by in-situ pyrolysis of the polyimide and the carbon fiber can be combined by covalent bonds to form a stable three-dimensional structure; the carbonization in the step B) is specifically as follows: carbonizing for 1-5 h at 800-1800 ℃ in argon atmosphere; the polyimide is pyrolyzed in two stages, wherein the first stage is that an imide ring is broken at 450-650 ℃ to remove carbonyl groups to form benzene ring type compounds, and the compounds containing conjugated cyano groups and isocyano groups are polymerized in series to finally form a polycyclic aromatic hydrocarbon structure temporarily; the second stage is that after 650 ℃, the aromatic heterocyclic structures are gradually combined, redundant nitrogen atoms and oxygen atoms are further removed to obtain a nitrogen-containing aromatic heterocyclic compound, and then the nitrogen-containing aromatic heterocyclic compound is pyrolyzed for a long time to finally generate a netlike carbon layer structure with a graphite hexagonal lamellar structure;
c) And alternately stacking the modified carbon fiber cloth and the polyamide sheet, and performing hot pressing and cooling to obtain the modified carbon fiber cloth.
2. The preparation method according to claim 1, wherein the solvent replacement temperature in step a) is 25 ℃, and the replacement time is 1-72 h; the drying temperature is 80 ℃ and the drying time is 2 hours.
3. The method according to claim 1, wherein the heat curing in step B) is specifically: curing for 0.5-2 hours at 280-350 ℃.
4. The method of claim 1, wherein the polyamide sheet of step C) has a thickness of 0.02 to 1mm.
5. The method according to claim 1, wherein the hot pressing in step C) is specifically: and hot-pressing for 2-180 min at 200-300 ℃ under the condition of 0.1-2 MPa.
6. The carbon fiber reinforced polyamide composite material for the wind power blade is characterized by being prepared by the preparation method of any one of claims 1-5.
7. A wind power blade, characterized in that the raw material comprises the carbon fiber reinforced polyamide composite material according to claim 6.
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