CN111187438A - Preparation method of carbon fiber/toughened epoxy resin prepreg for vacuum bag forming process - Google Patents
Preparation method of carbon fiber/toughened epoxy resin prepreg for vacuum bag forming process Download PDFInfo
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Abstract
The invention discloses a preparation method of a carbon fiber/toughened epoxy resin prepreg for a non-autoclave vacuum bag forming process. The method controls the dissolution degree and the particle size of the curing agent and the toughening agent in the epoxy resin by controlling the resin formula, the particle size of the curing agent and the toughening agent and the process conditions of the resin system configuration, and simultaneously has two modification effects: firstly, toughening a resin system; and secondly, the requirements of the non-autoclave process on the viscosity and the room-temperature storage period of the resin in the prepreg are met. Preparing the prepared epoxy resin system into an adhesive film, further preparing a carbon fiber/epoxy resin prepreg by adopting an adhesive film calendering method, and controlling the pressure and the temperature when the adhesive film is compounded with the carbon fiber to obtain a semi-impregnated prepreg (unsaturated impregnated prepreg).
Description
Technical Field
The invention relates to a preparation method of a carbon fiber/toughened epoxy resin prepreg, in particular to a preparation method of the carbon fiber/toughened epoxy resin prepreg suitable for a non-autoclave vacuum bag forming process, which comprises the preparation of toughened epoxy resin and the preparation of unsaturated impregnated prepreg.
Background
The carbon fiber reinforced epoxy resin-based composite material is widely applied in the fields of aerospace and civil use due to the reasons of light weight, high strength, good molding and curing manufacturability, excellent comprehensive performance and the like, and is one of the most common advanced composite material types. In the field of aerospace, a high-quality composite material product is prepared by using a carbon fiber/epoxy resin prepreg as an intermediate material and using an autoclave process as a forming and curing method.
Compared with the traditional autoclave forming process, the non-autoclave forming process (OoA) is a process method for manufacturing a composite material part with the same or similar performance and quality as the autoclave process without using an autoclave. The non-autoclave vacuum bag forming process takes the prepreg as a raw material, discharges air and volatile matters mixed in the prepreg and resin by means of vacuum pressure, and has great advantages in the aspects of reducing cost and improving manufacturability of large-sized products by only using an oven or a curing oven for heating and curing. However, in order to achieve the same molding quality as that of the autoclave molding process, the OoA process has higher requirements on the prepreg and the resin system thereof, and particularly has severe requirements on the curing and rheological properties of the resin and the impregnation state of the resin in the prepreg to fibers.
In order to better exhaust air inclusion and volatile components, OoA prepreg contains dry fibers which are not impregnated by resin as air guide paths, and the air in the prepreg is exhausted by vacuumizing before curing so as to reduce the void content in the final product and ensure a sufficiently high degree of fiber compactness. The resin from which OoA prepreg is made should be of high viscosity at room temperature to maintain the unobstructed air paths created by the dry fibers during the vacuum draw, and low viscosity at elevated temperatures to achieve sufficient flow to fully impregnate the fibers. On the other hand, the OoA process requires a long vacuum pre-compaction operation at room temperature for the prepreg blank to sufficiently exhaust the gas, and requires a longer storage period at room temperature, i.e., the curing reaction of the resin is low enough to ensure that the change of the rheological property of the resin is within an acceptable range in the molding process. In addition, OoA is also required to have low volatile content in the prepreg, be capable of curing at a lower temperature and the like, so that the manufacturing quality of the composite material is further guaranteed, and the manufacturing cost is reduced.
Generally, epoxy resin has high brittleness and low toughness, and a toughening agent needs to be added into a resin formula to improve the toughness of a composite material. For carbon fiber/epoxy resin prepreg for aerospace, high-performance thermoplastic resin is the most commonly used toughening agent, and the thermoplastic resin can be directly added into the epoxy resin or distributed on the surface of the prepreg, so that a toughening layer is formed between layers of a composite material, namely interlayer toughening. The OoA prepreg related patents which are published at home and abroad at present generally use a thermoplastic toughening agent for interlayer toughening. Patent CN103429371 and patent CN104023979 both disclose methods of adding thermoplastic resin particles or fibers to the surface of partially impregnated prepreg to improve the toughness of the composite material. For OoA prepregs, if an interlaminar toughening process is used, the toughening particles are present between the prepreg layers and may obstruct the air conducting pathways of OoA prepregs. However, if the toughening agent is dissolved in the epoxy resin for toughening, the viscosity of the resin is too high, which may hinder the resin from flowing and impregnating the fiber at high temperature, and the porosity of the cured product is too high, which may affect the molding quality of the product. In addition, the epoxy resin system added with the thermoplastic resin has high viscosity, and the components are often required to be mixed and configured at a high temperature, so that the curing agent and the epoxy resin have obvious curing reaction, the fluidity and the room-temperature storage property of the resin are influenced, and the preparation of the semi-impregnated prepreg is also influenced. Patent CN105109068 discloses a method for adjusting the viscosity of a resin system to meet the requirement of preparing OoA prepreg, but does not provide requirements for the resin raw material and the preparation process of the resin.
In the production process, a preparation method of the carbon fiber/toughened epoxy resin prepreg suitable for the OoA vacuum bag forming process needs to be designed, and the configuration process of a resin system is controlled, so that the resin system can meet the technological requirements of toughening and preparation of OoA prepreg.
The invention aims to provide a preparation method of a carbon fiber/toughened epoxy resin prepreg suitable for a non-autoclave vacuum bag forming process, which comprises the preparation of toughened epoxy resin and a preparation method of unsaturated impregnated prepreg.
Disclosure of Invention
The invention provides a preparation method of a carbon fiber/toughened epoxy resin prepreg for a non-autoclave vacuum bag forming process, aiming at the requirements of high-performance carbon fiber/epoxy resin matrix composite materials on the toughness and manufacturability of OoA prepregs.
The invention aims at a prepreg which takes carbon fiber as a reinforcement and takes an epoxy resin system as a matrix.
The technical scheme adopted by the invention is as follows:
a preparation method of a carbon fiber/toughened epoxy resin prepreg comprises the following steps:
the method comprises the following steps: weighing 60-100 parts of epoxy resin, 5-25 parts of toughening agent and 30-55 parts of epoxy resin curing agent according to the mass ratio;
step two: sequentially adding the raw materials weighed in the step one into a charging barrel according to the sequence of epoxy resin, a toughening agent and an epoxy resin curing agent, and stirring at a certain temperature;
step three: weighing 0.5-3 parts by mass of an accelerator, adding the accelerator into the mixture obtained in the step two, and stirring at a certain temperature;
step four: and compounding the epoxy resin system prepared in the step three with carbon fibers to realize partial impregnation of the carbon fibers by the resin, so as to obtain the semi-impregnated prepreg.
Preferably, the carbon fibers are polyacrylonitrile-based carbon fibers, which are in the form of carbon fiber tows or carbon fiber fabrics. The carbon fiber fabric comprises one or more of carbon fiber unidirectional cloth, carbon fiber plain weave, carbon fiber twill cloth, carbon fiber satin cloth and carbon fiber wrinkle-free fabric.
The invention provides components of an epoxy resin system, which comprise 60-100 parts of epoxy resin or epoxy resin mixture, 5-25 parts of thermoplastic resin toughening agent, 30-55 parts of epoxy resin curing agent and 0.5-3 parts of accelerator in mass ratio.
The epoxy resin is one or a combination of more of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, linear aliphatic type epoxy resin, alicyclic type epoxy resin and phenolic aldehyde type epoxy resin.
The thermoplastic resin toughening agent is thermoplastic resin particles, preferably one or more of polyether ketone, polyether ether ketone, polyether ketone, polyamide, polyimide, polyether sulfone, polyphenylene sulfide and modifications thereof. The particle size (D90) of the toughening agent is preferably 10 to 100. mu.m, more preferably 20 to 70 μm, most preferably 20 to 65 μm.
The epoxy resin curing agent is one or more of polyamine epoxy resin curing agent, ionic epoxy resin curing agent and dicyandiamide epoxy resin curing agent. The particle size (D90) of the curing agent is preferably 10 to 200. mu.m, more preferably 20 to 100. mu.m, most preferably 20 to 30 μm.
The accelerant is one or more of boron trifluoride monoethylamine, dicyandiamide and imidazole.
The epoxy resin system as described above can be prepared by the resin matrix preparation method known to the person skilled in the art, preferably by mixing with a planetary mixer, by the following steps:
the method comprises the following steps: weighing 60-100 parts of epoxy resin, 5-25 parts of toughening agent and 30-55 parts of amine epoxy resin curing agent according to the mass ratio; the concrete proportion is based on the requirement that the toughness, the fluidity and the curing property of the epoxy resin meet the requirement.
Step two: and (3) adding the raw materials weighed in the step one into the charging barrel in sequence according to the sequence of the epoxy resin, the toughening agent and the curing agent, and stirring for a period of time at a certain temperature. The preferred stirring temperature in this step is 70-120 deg.C, and the preferred stirring time is 10-40 min. The specific stirring temperature and stirring time are based on incomplete dissolution of the thermoplastic resin particles and the curing agent. The degree of dissolution can be judged by the particle size of the thermoplastic resin and the curing agent in the epoxy resin after mixing, and the preferred particle size is not less than 50% of the average particle size before mixing.
Step three: and (3) weighing 0.5-3 parts of accelerator by mass, adding into the mixture obtained in the step (II), and stirring for a period of time at a certain temperature. The preferred stirring temperature in this step is 80-110 deg.C, and the preferred stirring time is 3-10 min. The specific stirring temperature and stirring time are based on the degree of cure of the epoxy resin not exceeding a prescribed value, with a prescribed value of the degree of cure of not more than 10% being preferred.
Step four: the compounding of the epoxy resin system and the carbon fiber prepared in the invention generally adopts an adhesive film calendering method (adhesive film hot-melt one-step method or adhesive film hot-melt two-step method), the carbon fiber and a single-sided or double-sided resin adhesive film are compounded at a certain temperature and pressure, the partial impregnation of the carbon fiber by resin is realized, a semi-impregnated prepreg is obtained, and the proportion of the carbon fiber impregnated by the resin is preferably 20-60% (fiber impregnation degree).
The carbon fiber surface density range of the prepreg is 50-700g/m2。
The resin mass fraction range of the prepreg is 30-45%.
The temperature and pressure for preparing the prepreg are determined by the rheological characteristics of the epoxy resin system and the required degree of fiber impregnation, the resin viscosity at the temperature is preferably 10-300 Pa.s, and the pressure is preferably 0.1-0.6 MPa.
The curing agents, tougheners, are generally used in powder form, and their particle size and degree of dissolution of the powder in the epoxy resin system configuration will largely determine the performance and manufacturability of the resin. If the particle size of the curing agent is smaller or the curing agent is completely dissolved, the reaction speed of a resin system is increased, and the room-temperature storage property of the prepreg is reduced; if the toughening agent powder is small in particle size or completely dissolved, the viscosity of a resin system is increased sharply, and the control of the impregnation degree of the prepreg and the flowability of a low-viscosity platform of the resin at high temperature are affected. If the particle size of the curing agent or toughening agent powder is larger, the agglomeration and uneven dispersion of the components in local areas are easily caused, and the particles may become defects after curing to influence the performance of a finished piece. Therefore, the particle size of the curing agent and the toughening agent and the dissolution degree in the epoxy resin need to be controlled within a reasonable range so as to meet the requirements of OoA vacuum bag forming process on various aspects of the carbon fiber/epoxy resin prepreg.
In the invention, the content and the grain diameter of the toughening agent and the curing agent powder are optimized, the stirring temperature and the stirring time in the process of preparing the epoxy resin system are controlled, the powder is partially dissolved in the epoxy resin, and the grain diameter distribution of the curing agent and the toughening agent in the mixed epoxy resin system is in a reasonable range, so that the toughness, the flowability and the curing characteristic of the epoxy resin are adjusted. And further, by controlling the temperature and the pressure in the process of compounding the carbon fibers and the resin in the adhesive film calendering method, the semi-impregnated prepreg with moderate impregnation degree is obtained, the gas permeability of the prepreg is high enough, the requirement of OoA vacuum bag forming process on the gas guide capacity of the prepreg is met, and the carbon fibers can be completely impregnated by the resin at high temperature.
The invention has the advantages that: (1) has wide application range, can be used for various carbon fibers and epoxy resin, and can also be used for other fibers and resin. (2) The preparation method is simple, the controllability of the process is strong, the preparation of large-batch and small-batch resin and prepreg can be realized, and the popularization is easy. (3) The prepared prepreg can meet the requirements of OoA vacuum bag forming technology on various aspects of prepreg storage property at room temperature, air guide capacity at room temperature, high resin fluidity at high temperature, high resin toughness after curing and the like. In addition, the prepreg prepared by adopting the adhesive film calendering method has low volatile content, accurate control of resin content and fiber surface density, high preparation efficiency and environment-friendly manufacturing process. (4) The prepreg prepared by the invention can be used for preparing a composite material product with high performance and good process quality by adopting an OoA vacuum bag forming process, and has obvious advantages in the aspects of low cost and high quality.
Detailed Description
The prepreg system is mainly a prepreg taking carbon fibers as a reinforcement and an epoxy resin system as a matrix.
Preferably, the carbon fibers are polyacrylonitrile-based carbon fibers, which are in the form of carbon fiber tows or carbon fiber fabrics. The carbon fiber fabric comprises one or more of carbon fiber unidirectional cloth, carbon fiber plain weave, carbon fiber twill cloth, carbon fiber satin cloth and carbon fiber wrinkle-free fabric.
The invention provides components of an epoxy resin system, which comprise 60-100 parts of epoxy resin or epoxy resin mixture, 5-25 parts of thermoplastic resin toughening agent, 30-55 parts of epoxy resin curing agent and 0.5-3 parts of accelerator in mass ratio.
The epoxy resin is one or a combination of more of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, linear aliphatic type epoxy resin, alicyclic type epoxy resin and phenolic aldehyde type epoxy resin. Preferably, the epoxy resin is glycidyl amine type epoxy resin with a benzene ring structure in a main chain and a mixture of the glycidyl amine type epoxy resin and other epoxy resins to ensure the mechanical properties of a resin system, and specifically, the glycidyl amine type epoxy resin can be 4, 4' -diaminodiphenylmethane epoxy resin (AG80) and/or p-aminophenol epoxy resin (AFG90), and meanwhile, the low-viscosity epoxy resin can be added to adjust the viscosity of the resin system. The low-viscosity epoxy resin is preferably bisphenol A epoxy resin, and specifically can be one or two of bisphenol A diglycidyl ester products E51 and E44.
The thermoplastic resin toughening agent is thermoplastic resin particles, preferably one or more of polyether ketone, polyether ether ketone, polyether ketone, polyamide, polyimide, polyether sulfone, polyphenylene sulfide and modifications thereof. The particle size (D90) of the toughening agent is preferably 10 to 100. mu.m, more preferably 20 to 70 μm, most preferably 20 to 65 μm.
The epoxy resin curing agent is one or more of polyamine epoxy resin curing agent, ionic epoxy resin curing agent and dicyandiamide epoxy resin curing agent. The particle size (D90) of the curing agent is preferably 10 to 200. mu.m, more preferably 20 to 100. mu.m, most preferably 20 to 30 μm.
The accelerant is one or more of boron trifluoride monoethylamine, dicyandiamide and imidazole.
The sources of the carbon fibers, the epoxy resin, the thermoplastic resin toughening agent, the epoxy resin curing agent and the accelerator are not particularly limited, and the raw materials from which the sources are known to those skilled in the art can be adopted, and specifically, the raw materials can be commercial products of the raw materials.
The epoxy resin system as described above can be prepared by the resin matrix preparation method known to the person skilled in the art, preferably by mixing with a planetary mixer, by the following steps:
the method comprises the following steps: weighing 60-100 parts of epoxy resin and a composition thereof, 5-25 parts of a toughening agent and 30-55 parts of an amine epoxy resin curing agent according to the mass ratio; the concrete proportion is based on the requirement that the toughness, the fluidity and the curing property of the epoxy resin meet the requirement.
Step two: and (3) adding the raw materials weighed in the step (I) into the charging barrel in sequence according to the sequence of the epoxy resin and the composition thereof, the toughening agent and the curing agent, and stirring for a period of time at a certain temperature. The preferred stirring temperature in this step is 70-120 deg.C, and the preferred stirring time is 10-40 min. The specific stirring temperature and stirring time are based on incomplete dissolution of the thermoplastic resin particles and the curing agent. The degree of dissolution can be judged by the particle size of the thermoplastic resin and the curing agent in the epoxy resin after mixing, and the preferred particle size is not less than 50% of the average particle size before mixing.
Step three: and (3) weighing 0.5-3 parts of accelerator by mass, adding into the mixture obtained in the step (II), and stirring for a period of time at a certain temperature. The preferred stirring temperature in this step is 80-110 deg.C, and the preferred stirring time is 3-10 min. The specific stirring temperature and stirring time are based on the degree of cure of the epoxy resin not exceeding a prescribed value, with a prescribed value of the degree of cure of not more than 10% being preferred.
Step four: the compounding of the epoxy resin system and the carbon fiber configured in the invention generally adopts an adhesive film calendering method (adhesive film hot-melting one-step method or adhesive film hot-melting two-step method), the carbon fiber and a single-sided or double-sided resin adhesive film are compounded at a certain temperature and pressure, the partial impregnation of the carbon fiber by resin is realized, a semi-impregnated prepreg is obtained, and the proportion of the carbon fiber impregnated by the resin is preferably 20-60%.
The carbon fiber surface density range of the prepreg is 50-700g/m2。
The resin mass fraction range of the prepreg is 30-45%.
The temperature and pressure for preparing the prepreg are determined by the rheological characteristics of the epoxy resin system and the required degree of fiber impregnation, the resin viscosity at the temperature is preferably 10-300 Pa.s, and the pressure is preferably 0.1-0.6 MPa.
The following will describe the preparation method of the carbon fiber/toughened epoxy resin prepreg for the non-autoclave vacuum bag forming process in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
In the following examples, the starting materials are all commercially available products.
Example one
Preparation of a fiber areal Density of 150g/m Using T700SC carbon fiber tow2OoA prepreg according to (1). An epoxy resin was prepared in a compounding ratio of 80 parts by mass of AG80 resin, 20 parts by mass of E44 resin, 25 parts by mass of polyethersulfone (PES, D90: 50 μm), 47 parts by mass of 4, 4' -DDS (D90: 30 μm), and 0.5 parts by mass of boron trifluoride monoethylamine.
And (3) resin mixing: adding AG80 resin and E44 resin into a charging barrel of a planetary mixer, and mixing for about 10min at 100 ℃; adding PES, and mixing at 100 ℃ for about 30 min; adding 4, 4' -DDS, and mixing at 100 deg.C for about 30 min; boron trifluoride monoethylamine was added and mixed at 100 ℃ for about 5 min.
A prepreg preparation step: coating the resin mixture obtained in the above step on release paper at 70 deg.C, and controlling the thickness of the resin film to make the surface density of the resin film be 40g/m2. The carbon fiber tows and the resin films on the two sides are compounded at 65 ℃ and under the pressure of 0.3MPa, so that the fibers are partially impregnated by the resin, and the toughened non-autoclave carbon fiber/epoxy resin prepreg is obtained.
Example two
Preparation of a fiber areal Density of 125g/m Using T800H carbon fiber tow2OoA prepreg according to (1). Epoxy resin was prepared in a compounding ratio of 80 parts by mass of AFG90 resin, 10 parts by mass of E51 resin, 15 parts by mass of polyether ketone (PEK, D90: 60 μm), 53 parts by mass of 4, 4' -DDS (D90: 25 μm), and 0.5 parts by mass of boron trifluoride monoethylamine.
And (3) resin mixing: adding AFG90 resin and E51 resin into a charging barrel of a planetary mixer, and mixing for about 10min at 90 ℃; adding PEK, and mixing at 90 deg.C for about 30 min; adding 4, 4' -DDS, and mixing at 90 deg.C for about 30 min; boron trifluoride monoethylamine was added and mixed at 90 ℃ for about 5 min.
A prepreg preparation step: coating the resin mixture obtained in the above step on release paper at 60 deg.C, and controlling the thickness of the resin film to make the surface density of the resin film be 34g/m2. The carbon fiber tows and the resin films on the two sides are compounded at the temperature of 55 ℃ and the pressure of 0.6MPa, so that the resin is used for partially impregnating the fibers, and the toughened non-autoclave carbon fiber/epoxy resin prepreg is obtained.
EXAMPLE III
Preparation of a fiber areal Density of 150g/m Using T700SC carbon fiber tow2OoA prepreg according to (1). An epoxy resin was prepared in a compounding ratio of 100 parts by mass of AG80 resin, 25 parts by mass of polyethersulfone (PES, D90: 50 μm), 51 parts by mass of 4, 4' -DDS (D90: 30 μm), and 0.5 parts by mass of boron trifluoride monoethylamine.
And (3) resin mixing: adding AG80 resin into a charging barrel of a planetary mixer, and mixing for about 10min at 100 ℃; adding PES, and mixing at 100 ℃ for about 30 min; adding 4, 4' -DDS, and mixing at 100 deg.C for about 30 min; boron trifluoride monoethylamine was added and mixed at 100 ℃ for about 5 min.
A prepreg preparation step: coating the resin mixture obtained in the above step on release paper at 70 deg.C, and controlling the thickness of the resin film to make the surface density of the resin film be 40g/m2. The carbon fiber tows and the resin films on the two sides are compounded at 65 ℃ and under the pressure of 0.3MPa, so that the fibers are partially impregnated by the resin, and the toughened non-autoclave carbon fiber/epoxy resin prepreg is obtained.
Comparative example 1
Preparation of a fiber areal Density of 150g/m Using T700SC carbon fiber tow2OoA prepreg according to (1). An epoxy resin was prepared in a compounding ratio of 80 parts by mass of AG80 resin, 20 parts by mass of E44 resin, 25 parts by mass of polyethersulfone (PES, D90: 210 μm), 47 parts by mass of 4, 4' -DDS (D90: 30 μm), and 0.5 parts by mass of boron trifluoride monoethylamine.
And (3) resin mixing: adding AG80 resin and E44 resin into a charging barrel of a planetary mixer, and mixing for about 10min at 100 ℃; adding PES, and mixing at 100 ℃ for about 30 min; adding 4, 4' -DDS, and mixing at 100 deg.C for about 30 min; boron trifluoride monoethylamine was added and mixed at 100 ℃ for about 5 min.
A prepreg preparation step: coating the resin mixture obtained in the above step on release paper at 70 deg.C, and controlling the thickness of the resin film to make the surface density of the resin film be 40g/m2. The carbon fiber tows and the resin films on the two sides are compounded at 65 ℃ and under the pressure of 0.3MPa, so that the fibers are partially impregnated by the resin, and the toughened non-autoclave carbon fiber/epoxy resin prepreg is obtained.
Comparative example No. two
Preparation of a fiber areal Density of 150g/m Using T700SC carbon fiber tow2OoA prepreg according to (1). An epoxy resin was prepared in a compounding ratio of 80 parts by mass of AG80 resin, 20 parts by mass of E44 resin, 25 parts by mass of polyethersulfone (PES, D90: 50 μm), 47 parts by mass of 4, 4' -DDS (D90: 5 μm), and 0.5 parts by mass of boron trifluoride monoethylamine.
And (3) resin mixing: adding AG80 resin and E44 resin into a charging barrel of a planetary mixer, and mixing for about 10min at 100 ℃; adding PES, and mixing at 100 ℃ for about 30 min; adding 4, 4' -DDS, and mixing at 100 deg.C for about 30 min; boron trifluoride monoethylamine was added and mixed at 100 ℃ for about 5 min.
A prepreg preparation step: coating the resin mixture obtained in the above step on release paper at 70 deg.C, and controlling the thickness of the resin film to make the surface density of the resin film be 40g/m2. The carbon fiber tows and the resin films on the two sides are compounded at 65 ℃ and under the pressure of 0.3MPa, so that the fibers are partially impregnated by the resin, and the toughened non-autoclave carbon fiber/epoxy resin prepreg is obtained.
The gas permeability of the OoA prepreg obtained in the above example was as follows.
The prepreg obtained in the embodiment is laminated according to the thickness of a required sample, degassing is carried out for 8 hours under the vacuum degree of less than about 10kPa, the vacuum degree is maintained to be less than about 10kPa, the temperature is raised to 120 ℃ at 1 ℃/min, the temperature is kept for 30 minutes, the temperature is raised to 180 ℃ at 1 ℃/min, the temperature is kept for 2 hours, the temperature is raised to 200 ℃ at 1 ℃/min, and the curing system with the constant temperature for 2 hours is used for curing in an oven, so that the porosity and the mechanical property of the obtained product are as follows, and the porosity is low and the mechanical property is.
Claims (10)
1. A preparation method of a carbon fiber/toughened epoxy resin prepreg comprises the following steps:
the method comprises the following steps: weighing 60-100 parts of epoxy resin, 5-25 parts of toughening agent and 30-55 parts of epoxy resin curing agent according to the mass ratio;
step two: sequentially adding the raw materials weighed in the step one into a charging barrel according to the sequence of epoxy resin, a toughening agent and an epoxy resin curing agent, and stirring at a certain temperature;
step three: weighing 0.5-3 parts by mass of an accelerator, adding the accelerator into the mixture obtained in the step two, and stirring at a certain temperature;
step four: and compounding the epoxy resin system prepared in the step three with carbon fibers to realize partial impregnation of the carbon fibers by the resin, so as to obtain the semi-impregnated prepreg.
2. The method as set forth in claim 1, wherein the epoxy resin is one or more of a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a linear aliphatic type epoxy resin, an alicyclic type epoxy resin, and a phenol type epoxy resin.
3. The method of claim 1, wherein the carbon fibers are polyacrylonitrile-based carbon fibers in the form of a carbon fiber tow or a carbon fiber fabric; the carbon fiber fabric comprises one or more of carbon fiber unidirectional cloth, carbon fiber plain weave, carbon fiber twill cloth, carbon fiber satin cloth and carbon fiber wrinkle-free fabric.
4. The method as claimed in claim 1, wherein the toughening agent is thermoplastic resin particles, preferably one or more of polyetherketone, polyetheretherketone, polyetherketoneketone, polyamide, polyimide, polyethersulfone, polyphenylene sulfide, and modifications thereof.
5. The method according to claim 4, characterized in that the particle size (D90) of the toughening agent is preferably 10-100 μm, more preferably 20-70 μm, most preferably 20-65 μm.
6. The method as set forth in claim 1, wherein the epoxy resin curing agent is one or more of polyamine-based epoxy resin curing agents, ionic-based and dicyandiamide-based epoxy resin curing agents; the accelerant is one or more of boron trifluoride monoethylamine, dicyandiamide and imidazole.
7. The method according to claim 6, characterized in that the particle size (D90) of the curing agent is preferably between 10 and 200 μm, more preferably between 20 and 100 μm, most preferably between 20 and 30 μm.
8. The method as set forth in claim 1, wherein the stirring temperature and the stirring time in the second step are based on the fact that the thermoplastic resin particles and the curing agent are not completely dissolved, and the degree of dissolution can be judged by using the particle diameters of the thermoplastic resin and the curing agent in the epoxy resin after mixing, which are not less than 50% of the average particle diameter before mixing.
9. The method as set forth in claim 1, wherein the stirring temperature and the stirring time in the third step are such that the degree of curing of the epoxy resin does not exceed a predetermined value, which is not more than 10%.
10. A process according to any one of claims 1 to 9, characterised in that the proportion of carbon fibres in the prepreg which are impregnated with resin is from 20% to 60%; the carbon fiber surface density range of the prepreg is 50-700g/m2(ii) a The resin mass fraction range of the prepreg is 30-45%.
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