Efficient and green method for preparing polyether ether ketone composite material reinforced by nano-modified polyether arone sized fiber cloth

Abstract

The present invention relates to the technical field of composite materials and forming thereof, and specifically relates to an efficient and green method for preparing a polyether ether ketone composite material reinforced by nano-modified polyether arone sized fiber cloth. The method comprises: first, preparing a nano-modified polyether arone water-based sizing agent; sizing fiber cloth by using the sizing agent; and finally, preparing a polyether ether ketone composite material reinforced by the nano-modified polyether arone sized fiber cloth by means of a slurry method. The sizing agent is free of decomposition and failure with heat in a high-temperature forming process of the composite material; moreover, a polyether arone component in the sizing agent is similar to polyether ether ketone in structure and has good compatibility with same; anchor points with a mechanical locking effect are provided by means of the introduction of nanoparticles, such that fibers and a resin are connected together by means of the mechanical locking effect; in addition, a polyether ether ketone powder is dispersed into a cosolvent / water mixed solvent and then brushed onto the fiber cloth, and polyether ether ketone more easily infiltrates fiber bundles by means of a solution, such that an infiltration path of the melt resin is shortened, and the interface performance of the composite material is also improved to a certain extent.

Description

An efficient and green preparation method for nano-modified polyether aryl ketone sizing fiber cloth reinforced polyether ether ketone composite material Technical Field

[0001] The present invention relates to the technical field of composite materials and molding thereof, and in particular to a high-efficiency and green preparation method of a nano-modified polyether aromatic ketone sizing fiber cloth reinforced polyether ether ketone composite material. Background Art

[0002] In recent years, with the rapid development of fields such as aerospace, aviation, automotive, and biomedical engineering, the demand for high-performance materials has increased. The emergence of high-performance fiber-reinforced thermoplastic composites, in particular, has filled the urgent need for high-performance materials in cutting-edge fields. Among the many high-performance thermoplastic resins, polyetheretherketone (PEEK) offers excellent properties such as high-temperature resistance, corrosion resistance, and wear resistance, as well as high strength and toughness. Therefore, fiber-reinforced PEEK composites, as the most representative of high-performance fiber-reinforced thermoplastic composites, have become an indispensable key material in major projects such as aerospace, energy, and petrochemicals.

[0003] In fiber-reinforced polyetheretherketone (PEEK) composites, the interfacial region plays a role in stress transfer when the composite is subjected to stress, directly determining the overall performance of the composite. However, due to defects such as low surface activity and surface energy of the fibers, and the high viscosity of the molten PEEK resin matrix, which is not conducive to good fiber impregnation, the interfacial bond strength between the fiber and the resin is weak, resulting in a decrease in the efficiency of interfacial stress transfer and a deterioration in the overall performance of the composite, which has limited its application.

[0004] Fiber sizing, as a relatively simple and mature interface modification method, can effectively increase the fiber surface energy and improve the interfacial bonding strength of composite materials. Currently, most commercial sizing agents are thermosetting sizing agents with epoxy resin as the main component. For example, the Chinese patent "Anti-aging modified epoxy resin sizing agent for carbon fiber and preparation method thereof, authorization publication number: CN 111139640 B" discloses a preparation method for a carbon fiber sizing agent modified with nanorod-shaped palygorskite and lamellar mica, which is used to solve the problem of sizing agent aging in a hot and humid environment caused by chemical degradation of the resin and cracking of the fiber / resin interface in the prior art; the Chinese patent "Preparation method of a lignin-based sizing agent for composite carbon nanotubes and its application in polyolefins, authorization publication number: CN 113445323 B" proposes first dissolving epoxy resin and ozonated lignin in an organic solvent, heating and stirring the reaction to obtain a lignin-based epoxy resin, then adding an olamine and a carboxylic acid, heating and stirring the reaction, and then adding carbon nanotubes and a silane coupling agent to obtain a lignin-based sizing agent for composite carbon nanotubes, which solves the defects of poor adhesion between carbon fiber and polyolefin and improves the mechanical properties of the composite material; the Chinese patent "A method for simultaneously improving the interface strength and toughness of carbon fiber epoxy composite materials, authorization publication number: CN To improve the interfacial strength and toughness of carbon fiber epoxy composites, zirconium oxide (ZrO2) was surface-modified with a silane coupling agent. The modified ZrO2, epoxy resin, and organic solvent were then uniformly mixed to produce a sizing agent. While this type of sizing agent effectively improves the interfacial strength of fiber / thermosetting resin composites, its application in fiber cloth / polyetheretherketone (PEEK) composites still presents the following key challenges: First, the decomposition temperature of thermosetting sizing agents is generally lower than the molding temperature of PEEK-based composites. This results in the thermosetting sizing agent decomposing at high temperatures during the composite molding process, preventing it from fulfilling its role in enhancing the interfacial bond strength of the composite. Second, the preparation of sizing agents often involves the use of organic solvents, which pose significant risks to operators and equipment. Therefore, it is imperative to develop a green, environmentally friendly, water-based sizing agent suitable for PEEK resin matrices to improve the interfacial properties of fiber cloth / PEEK composites, thereby enhancing the mechanical properties of the composites.

[0005] Furthermore, the high viscosity of the PEEK resin matrix in its molten state makes it difficult to properly impregnate the fiber cloth, which reduces the composite's interfacial properties and is a major challenge facing fiber cloth-reinforced PEEK composites. To ensure adequate resin impregnation of the fibers, a series of composite material preparation methods have been proposed to improve the interfacial bonding between the fibers and the resin. The Chinese patent "A continuous fiber reinforced polyaryletherketone composite material and its preparation method, authorization announcement number: CN 110387119 B" first prepares continuous fibers with a crystalline polyaryletherketone interfacial binder, then uses polyetheretherketone film material to adopt composite winding technology and layer-by-layer stacking technology to prepare a continuous fiber polyaryletherketone composite material precursor, and then obtains the polyaryletherketone continuous fiber composite material by hot pressing; the Chinese patent "A continuous fiber reinforced polyetheraryletherketone composite material and its preparation method, authorization announcement number: CN 110499012 B" first prepares a continuous fiber / phenolphthalein polyaryletherketone prepreg, then electrostatically sprays polyetheretherketone powder onto the surface of the continuous fiber / phenolphthalein polyaryletherketone prepreg, and then melts and rolls to obtain a continuous fiber reinforced polyaryletherketone composite material. Although the above methods have improved the resin impregnation of fibers to a certain extent, the preparation method of such composite materials is complex and has high requirements on equipment. In addition, the resin matrix and fibers are compounded by composite winding, layer-by-layer stacking, and electrostatic spraying. The resin matrix only contacts the surface of the continuous fibers and cannot enter between the fiber bundles. During the composite material molding process, there is still the problem that the resin matrix cannot fully impregnate the fibers.

[0006] Summary of the Invention

[0007] In order to solve the technical problems of low surface activity and low surface energy of fiber cloth and high viscosity of polyetheretherketone in the molten state, which is not conducive to good impregnation of fibers, the present invention provides an efficient and green preparation method for nano-modified polyetheraromatic ketone sizing fiber cloth reinforced with polyetheretherketone composite material. First, a nano-modified polyetheraromatic ketone water-based sizing agent that does not contain any organic solvent is prepared, and then the fiber cloth is sizing treated with the sizing agent, which effectively improves the surface energy of the fiber. In addition, polyetheraromatic ketone has a similar structure to the polyetheretherketone resin matrix and has good compatibility, which is conducive to the sizing fiber cloth and the polyetheretherketone resin matrix having a good interface bonding. Finally, a slurry method is used to prepare a nano-modified polyetheraromatic ketone water-based sizing fiber cloth reinforced with polyetheretherketone composite material. The liquid phase polyetheretherketone slurry can more easily penetrate into the fiber bundles, shortening the impregnation distance of the molten resin. The preparation method of the fiber cloth / polyetheretherketone composite material provided by the present invention effectively improves the interfacial bonding strength of the composite material, and the mechanical properties of the composite material are also improved accordingly.

[0008] To solve the above technical problems, the technical solution adopted by the present invention is: an efficient and green preparation method of a nano-modified polyether aromatic ketone sizing fiber cloth reinforced polyether ether ketone composite material, comprising the following steps:

[0009] (1) Preparation of nano-modified polyether aromatic ketone water-based sizing agent

[0010] The polyether aryl ketone is dried to remove adsorbed water; a dispersant, a wetting agent and a water-based silicone defoamer are added to deionized water and mechanically stirred at room temperature until the mixture is uniform; nanoparticles are then added to the mixture and ultrasonically dispersed at room temperature for a certain time; polyether aryl ketone is then added to the dispersion and mechanically stirred at room temperature for a certain time; the dispersion is then transferred to a high shear homogenizer and stirred at a high speed of 8000 to 12000 r / min at room temperature for 10 to 30 minutes; thus, a uniformly dispersed nano-modified polyether aryl ketone water-based sizing agent is obtained;

[0011] (2) Sizing modification process of nano-modified polyether aromatic ketone water-based sizing agent on fiber cloth surface

[0012] The fiber cloth is completely immersed in the nano-modified polyether aromatic ketone water-based sizing agent of step (1) by an immersion method, ultrasonically immersed for a period of time under room temperature and then dried to obtain the nano-modified polyether aromatic ketone water-based sizing fiber cloth;

[0013] (3) Preparation of nano-modified polyether aryl ketone water-based sizing fiber cloth reinforced polyether ether ketone composite materials by slurry method

[0014] Prepare a cosolvent / water mixed solvent; add the cosolvent / water mixed solvent to polyetheretherketone under the action of 80-100W ultrasound at room temperature, and ultrasonicate for 10-30 minutes to obtain polyetheretherketone slurry; apply the polyetheretherketone slurry to the surface of the nano-modified polyetheraromatic ketone water-based sizing fiber cloth obtained in step (2), dry and remove the solvent to obtain a prepreg; lay the prepregs in a mold coated with a release agent in sequence; place the mold in a hot press, heat and pressurize to cure; maintain pressure and naturally cool to room temperature, then demould to obtain a nano-modified polyetheraromatic ketone water-based sizing fiber cloth reinforced polyetheretherketone composite material.

[0015] Furthermore, the ratio of the components in the nano-modified polyether aromatic ketone aqueous sizing agent described in step (1) is: polyether aromatic ketone 1-8wt%, nanoparticles 0.1-1wt%, dispersant 0.3-0.8wt%, wetting agent 0.1-0.5wt%, aqueous silicone defoamer 0.3-1wt%, deionized water 88.7-98.2wt%.

[0016] Preferably, in step (1), the polyether aromatic ketone is dried at 100-120° C. for 6-10 hours; the mechanical stirring speed after the dispersant, wetting agent and aqueous silicone defoamer are added to deionized water is 200-500 r / min for 10-30 minutes; the ultrasonic dispersion condition after the nanoparticles are added is ultrasonic dispersion at 100-200W for 15-45 minutes; the mechanical stirring speed after the polyether aromatic ketone is added is 200-500 r / min for 50-100 minutes.

[0017] Furthermore, in step (1), the nanoparticles are at least one of graphene oxide, silicon dioxide and carbon nanotubes; the polyether aromatic ketone is at least one of polyether ketone, polyether ether ketone, polyether ketone ketone, polyether ether ketone ketone and polyether ketone ether ketone ketone, which is in powder form with a particle size of 10 to 20 μm.

[0018] Furthermore, in step (1), the dispersant is at least one of anionic polyacrylate sodium salt, polycarboxylic acid sodium salt and tripolyphosphate sodium salt dispersants; the wetting agent is at least one of nonionic alkyl polyoxyethylene ether, nonylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether wetting agents.

[0019] Furthermore, the ultrasonic immersion conditions in step (2) are 0.5 to 2 hours at 80 to 100W; the drying temperature is 60 to 100°C, and the drying time is 12 to 18 hours.

[0020] Furthermore, in step (3), the fiber cloth is any one or more of carbon fiber cloth, basalt fiber cloth and quartz fiber cloth, the polyetheretherketone in step (3) is in powder form with a particle size of 20 to 100 μm, and the cosolvent is at least one of anhydrous ethanol, ethylene glycol and acetone.

[0021] Preferably, in step (3), the proportion of each component of the nano-modified polyether aromatic ketone water-based sizing fiber cloth reinforced polyether ether ketone composite material is 50-70wt% of nano-modified polyether aromatic ketone water-based sizing fiber cloth and 30-50wt% of polyether ether ketone slurry; the mass ratio of polyether ether ketone, cosolvent and water in the polyether ether ketone slurry is 1.0:0.5-2:0.5-2.

[0022] Furthermore, in step (3), the drying and solvent removal conditions are drying at 80-120° C. for 10-16 hours.

[0023] Furthermore, it is characterized in that the heating and pressurizing curing in step (3) includes the following process: heating to 380-400° C., pressurizing to 5-30 MPa, and curing for 1-3 hours.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] (1) The nano-modified polyether aromatic ketone water-based sizing agent prepared by the present invention does not contain any organic solvents during the preparation process and the final product, and does not cause harm to operators and equipment. It is an environmentally friendly sizing agent with a simple preparation method and low production cost.

[0026] (2) Initial decomposition temperature (T 5％) is much higher than the molding temperature of fiber cloth reinforced polyetheretherketone composite materials, so the sizing agent will not decompose and fail due to excessively high temperature during the molding process of the composite materials.

[0027] (3) The nano-modified polyether aryl ketone aqueous sizing agent prepared by the present invention modifies the fiber cloth through Wiener sizing, which can effectively improve the surface energy of the fiber cloth and enable the resin matrix to better impregnate the fiber cloth. In addition, the polyether aryl ketone component in the sizing agent is similar in structure to polyetheretherketone, and the two have good compatibility. In addition, the nanoparticles provide a large number of anchor points for mechanical locking, and the fiber cloth and the resin matrix are connected together by mechanical locking. In summary, the sizing agent effectively solves the problem of weak interfacial interaction of fiber cloth reinforced polyetheretherketone composite materials, and the mechanical properties of the composite materials are also improved accordingly.

[0028] (4) The nano-modified polyether aromatic ketone water-based sizing fiber cloth reinforced polyether ether ketone composite material prepared by the present invention is prepared by a slurry method. The slurry method is to disperse polyether ether ketone in a cosolvent / water mixed solvent to prepare a slurry, then apply it to the surface of the fiber cloth, and then form it into a composite material by hot pressing. With the assistance of the cosolvent / water mixed solvent, the polyether ether ketone matrix is ​​more easily immersed in the fiber bundles, shortening the molten resin impregnation distance, thereby effectively solving the problem that the resin matrix cannot fully impregnate the fiber cloth, and the interface performance and corresponding mechanical properties of the fiber cloth reinforced polyether ether ketone composite material are improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] FIG1 is a schematic diagram of the structure of a prepared nano-modified polyether aromatic ketone water-based sizing fiber cloth reinforced polyether ether ketone composite material.

[0030] Figure 2 is a scanning electron microscope image of the cross-sectional morphology of the prepared composite material after destruction in the mechanical property test. (a), (b) and (c) in Figure 2 are scanning electron microscope images of the transverse cross-sectional views of the composite materials prepared in Comparative Example 1, Comparative Example 2 and Example 1, respectively. (d), (e) and (f) in Figure 2 are scanning electron microscope images of the longitudinal cross-sectional views of the composite materials prepared in Comparative Example 1, Comparative Example 2 and Example 1, respectively.

[0031] Figure 3 is a scanning electron microscope image of the wear scar surface of the prepared composite material after the tribological performance test. (a), (b) and (c) in Figure 3 are scanning electron microscope images of the wear scar surface of the composite materials prepared in Comparative Example 1, Comparative Example 2 and Example 1, respectively.

[0032] The markings in the figure are as follows: 1-polyetheretherketone, 2-nano-modified polyetheraryl ketone water-based sizing agent, 3-fiber cloth. DETAILED DESCRIPTION

[0033] The present invention will be further described below with reference to specific embodiments.

[0034] Comparative Example 1:

[0035] The composition and proportion of each component of the carbon fiber cloth reinforced polyetheretherketone composite material are 60wt% of carbon fiber cloth and 40wt% of polyetheretherketone powder with a particle size of 20μm. The powder impregnation method for preparing the carbon fiber cloth reinforced polyetheretherketone composite material includes the following steps: polyetheretherketone powder is directly and evenly spread on the surface of the carbon fiber cloth; the carbon fiber cloth sprinkled with polyetheretherketone powder is sequentially layered in a mold coated with a release agent; the mold is placed in a hot press, heated and pressurized to cure: the temperature is raised to 390℃, the pressure is increased to 10MPa, and the curing is carried out for 1.5h; the pressure is maintained and naturally cooled to room temperature, and then demolded to obtain the carbon fiber cloth reinforced polyetheretherketone composite material.

[0036] Table 1 summarizes the performance test data of the carbon fiber cloth reinforced polyetheretherketone composite material prepared in Comparative Example 1. Figure 2 (a) and (d) show the transverse cross-sectional morphology and longitudinal cross-sectional morphology of the composite material prepared in Comparative Example 1 after mechanical performance test. The transverse cross-sectional morphology shows that obvious stratification occurs at the cross section, and only a small amount of resin matrix adheres to the surface of the peeled fiber; the longitudinal cross-sectional morphology shows that there are many holes left after the fibers are pulled out at the cross section. The above phenomenon indicates that the interfacial bonding between the fiber and the resin matrix is ​​weak. When the composite material is subjected to external force, the fracture failure form is mainly interfacial debonding, which is a typical adhesion failure mode. The wear scar surface morphology of the composite material prepared in Comparative Example 1 after tribological performance test shown in Figure 3 (a) shows that there are deep pear grooves on the wear scar surface, and some fibers are exposed to the outside, or even peeled off, which is a typical adhesive wear. During the tribological experiment of the composite material, the resin layer on the sliding wear mark is completely removed by friction with the steel ball, and then the first layer of fibers is exposed on the surface of the sample and destroyed. As the friction of the steel ball continues, the wear damage extends to the adjacent layers, and the microcracks formed on the contact surface extend to the internal structure of the composite material. Due to the weak interfacial bonding strength of the composite material, the fibers are separated from the matrix when they reach the interface between the fiber and the matrix, resulting in fiber peeling.

[0037] Table 1 Properties of the prepared composite materials

[0038] Comparative Example 2:

[0039] The composition and proportion of each component of the carbon fiber cloth reinforced polyetheretherketone composite material are as follows: 60wt% carbon fiber cloth, 40wt% polyetheretherketone powder with a particle size of 20μm, and polyetheretherketone: anhydrous ethanol: water = 1:1:1 mass ratio; the slurry method for preparing the carbon fiber cloth reinforced polyetheretherketone composite material includes the following steps: preparing anhydrous ethanol / water mixed solvent; adding the polyetheretherketone powder to the anhydrous ethanol / water mixed solvent under 90W ultrasonic action at room temperature, and ultrasonicating for 30 minutes to obtain polyetheretherketone slurry; applying the polyetheretherketone slurry to the surface of the carbon fiber cloth, drying at 80℃ for 12 hours, drying and removing the solvent to obtain a prepreg; the prepreg is sequentially layered in a mold coated with a release agent; the mold is placed in a hot press, heated and pressurized for curing: heating to 390℃, pressurizing to 10MPa, and curing for 1.5 hours; maintaining the pressure and naturally cooling to room temperature and demolding to obtain the carbon fiber cloth reinforced polyetheretherketone composite material.

[0040] Table 2 summarizes the performance test data of the carbon fiber cloth reinforced polyetheretherketone composite material prepared in Comparative Example 2. Compared with Comparative Example 1, the mechanical properties and tribological properties of the composite material prepared in Comparative Example 2 are improved to varying degrees. (b) and (e) in Figure 2 show the transverse cross-sectional morphology and longitudinal cross-sectional morphology after the mechanical property test of the composite material prepared in Comparative Example 2 is destroyed. Compared with Comparative Example 1, the delamination phenomenon is weakened and the holes are reduced. The wear scar surface morphology after the tribological property test of the composite material prepared in Comparative Example 1 shown in Figure 3 (b) is obtained, and the pear groove becomes shallower and the fiber peeling phenomenon is weakened. The above phenomenon is attributed to the enhanced interfacial bonding strength of the composite material. The reason why the interfacial bonding strength of the composite material is enhanced is mainly because the slurry method is to disperse the powdered resin matrix into an anhydrous ethanol / water mixed solvent, and then apply it to the fiber cloth surface. The resin matrix is ​​more easily immersed in the fiber bundle under the auxiliary effect of the anhydrous ethanol / water mixed solvent, reducing the melt resin infiltration distance, which is conducive to the interface bonding of the fiber and the resin matrix, and the interface performance and mechanical properties of the composite material are enhanced.

[0041] Table 2 Properties of the prepared composite materials

[0042] Example 1

[0043] (1) Preparation of graphene oxide modified polyetherketoneketone water-based sizing agent

[0044] The composition and proportion of each component of the graphene oxide doped polyetherketoneketone water-based sizing agent are as follows: 5wt% of polyetherketoneketone with a particle size of 13μm, 0.5wt% of graphene oxide, 0.8wt% of anionic polyacrylate sodium salt dispersant, 0.4wt% of nonionic alkyl polyoxyethylene ether wetting agent, 0.3wt% of water-based silicone defoamer, and 93wt% of deionized water; the preparation of the graphene oxide doped polyetherketoneketone water-based sizing agent includes the following steps: drying the polyetherketoneketone at 120°C for 6h to remove adsorbed water; dispersant, wetting agent, Add the agent and defoamer to deionized water, and stir mechanically at room temperature and 300 r / min for 15 minutes until the mixture is uniform; add graphene oxide to the above mixture, and ultrasonically disperse it at room temperature and 200W for 15 minutes; add polyetherketoneketone to the above dispersion, and stir mechanically at room temperature and 300 r / min for 50 minutes; then transfer to a high shear homogenizer and stir at high speed at room temperature and 8000 r / min for 30 minutes to obtain a uniformly dispersed graphene oxide modified polyetherketoneketone water-based sizing agent;

[0045] (2) Sizing modification process of graphene oxide modified polyetherketone ketone water-based sizing agent on carbon fiber cloth surface

[0046] The carbon fiber cloth was completely immersed in the graphene oxide-doped polyetherketoneketone water-based sizing agent by the impregnation method, and ultrasonically impregnated at room temperature and 90W for 1 hour; then dried at 60°C for 14 hours to obtain the graphene oxide-modified polyetherketoneketone water-based sizing carbon fiber cloth;

[0047] (3) Preparation of graphene oxide modified polyetherketone ketone water-based sizing carbon fiber cloth reinforced polyetheretherketone composite materials by slurry method

[0048] The composition and distribution ratio of the graphene oxide modified polyetherketone ketone water-based sizing carbon fiber cloth reinforced polyetheretherketone composite material are as follows: 60wt% of graphene oxide modified polyetherketone ketone water-based sizing carbon fiber cloth, 40wt% of polyetheretherketone powder with a particle size of 20μm, and a mass ratio of polyetheretherketone: anhydrous ethanol: deionized water = 1:1:1; the slurry method for preparing the graphene oxide modified polyetherketone ketone water-based sizing carbon fiber cloth reinforced polyetheretherketone composite material includes the following steps: preparing anhydrous ethanol / water mixed solvent; polyetheretherketone powder under room temperature and 90W ultrasonic action; Anhydrous ethanol / deionized water solution was added and ultrasonicated for 30 minutes to obtain a polyetheretherketone slurry; the polyetheretherketone slurry was brushed onto the surface of the fiber cloth, dried at 80°C for 12 hours, and dried and the solvent was removed to obtain a prepreg; the prepregs were sequentially layered in a mold coated with a release agent; the mold was placed in a hot press and heated and pressurized for curing: the temperature was raised to 390°C, the pressure was increased to 10 MPa, and the curing was carried out for 1.5 hours; the pressure was maintained and the polyetherketone ketone water-based sized fiber cloth reinforced polyetheretherketone composite material was obtained after natural cooling to room temperature and demolding.

[0049] Table 3 summarizes the performance test data of the graphene oxide modified polyetherketone ketone water-based sizing carbon fiber cloth reinforced polyetheretherketone composite material prepared in Example 1. The table shows that the initial decomposition temperature of the graphene oxide modified polyetherketone ketone water-based sizing agent is 588°C, which is much higher than the composite material molding temperature, indicating that the sizing agent will not be decomposed and lose its effectiveness due to heat during the composite material molding process. The surface energy of the carbon fiber cloth treated with the sizing agent is 70.18mN / m, which is 60.3% higher than the surface energy of the carbon fiber cloth without sizing modification in Comparative Example 2, which can promote better impregnation of the fiber cloth with the resin matrix. The tensile strength of the carbon fiber cloth sizing agent monofilament is also correspondingly improved compared to the tensile strength of the carbon fiber cloth monofilament in Comparative Example 2, indicating that the sizing agent treatment of the carbon fiber cloth does not damage the properties of the fiber itself. The mechanical and tribological properties of the composite material prepared in Example 1 were significantly improved compared to those in Comparative Example 2. The mechanical properties, including interlaminar shear strength, flexural strength, flexural modulus, and impact strength, increased by 57.4%, 36.4%, 54.6%, and 60.7%, respectively. The tribological properties, including friction coefficient and wear rate, increased by 26.3% and 37.6%, respectively. Figures 2 (c) and (f) show the transverse and longitudinal cross-sectional morphologies of the composite material prepared in Example 1 after mechanical property testing. Compared to Comparative Example 2, after the composite material was modified with a sizing agent interface, the fiber surface was almost completely covered by the resin matrix, the cracks between the fibers and the resin, and the holes caused by the fibers being pulled out almost completely disappeared, and the mixed failure was completely transformed into cohesive failure. This is mainly because the sizing agent sizing treatment of the fiber cloth increases the surface energy, and the structure of the polyetherketone ketone and the polyetheretherketone resin matrix is ​​very similar, which can promote the diffusion and entanglement between the molecular chains of the two, forming π-π interactions. In addition, graphene oxide provides an anchor point for mechanical locking, and the fiber and the resin matrix are tightly connected together by mechanical locking, and the interface performance of the composite material is enhanced. The tribological performance test of the composite material prepared in Example 1 shown in Figure 3 (c) shows the surface morphology of the wear scar after destruction. There is no obvious peeling phenomenon between the fiber and the resin, and the pear groove on the wear surface gradually becomes shallower or even disappears. The appearance of this phenomenon is not only because the introduction of the sizing agent improves the interfacial bonding force of the composite material and suppresses the generation and expansion of cracks on the wear scar surface, but also because graphene oxide, as a solid lubricant, greatly reduces the friction between the composite material sample and the steel ball through its self-lubricating properties.

[0050] Table 3 Properties of the prepared composite materials

[0051] Example 2:

[0052] (1) Preparation of silica-modified polyetherketone water-based sizing agent

[0053] The composition and proportion of each component of the silica-modified polyetherketone water-based sizing agent are as follows: 3wt% of polyetherketone with a particle size of 14μm, 1wt% of silica, 0.55wt% of anionic polycarboxylate sodium salt dispersant, 0.3wt% of nonionic nonylphenol polyoxyethylene ether wetting agent, 0.35wt% of water-based silicone defoamer, and 94.8wt% of deionized water; the preparation of the silica-modified polyetherketone water-based sizing agent includes the following steps: drying the polyetherketone at 100°C for 10h to remove adsorbed water; adding the dispersant, wetting agent and defoamer into deionized water, and mechanically stirring for 13min at room temperature and 260r / min until the mixture is uniform; adding silica into the above-mentioned mixture, and ultrasonically dispersing for 35min at room temperature and 130W; adding the polyetherketone into the above-mentioned dispersion, and stirring at room temperature and 130W for 35min. The mixture was mechanically stirred at 260 r / min for 55 min; then the mixture was transferred to a high shear homogenizer and stirred at 8100 r / min for 20 min at room temperature to obtain a uniformly dispersed silica-modified polyetherketone water-based sizing agent.

[0054] (2) Sizing modification process of silica-modified polyetherketone water-based sizing agent on quartz fiber cloth surface

[0055] The carbon fiber cloth was completely immersed in the silica-doped polyetherketone water-based sizing agent by the impregnation method, and ultrasonically impregnated at room temperature and 95W for 0.8h; then dried at 80℃ for 12h to obtain the silica-modified polyetherketone water-based sizing quartz fiber cloth;

[0056] (3) Preparation of silica-modified polyetherketone water-based sizing quartz fiber cloth reinforced polyetheretherketone composite materials by slurry method

[0057] The composition and distribution ratio of the silica-modified polyetherketone water-based sizing quartz fiber cloth reinforced polyetheretherketone composite material are as follows: 65wt% of silica-modified polyetherketone water-based sizing quartz fiber cloth, 35wt% of polyetheretherketone powder with a particle size of 30μm, and a mass ratio of polyetheretherketone: anhydrous ethanol: water = 1:0.8:0.8; the slurry method for preparing the silica-modified polyetherketone water-based sizing quartz fiber cloth reinforced polyetheretherketone composite material includes the following steps: preparing anhydrous ethanol / water mixed solvent; polyetheretherketone powder under 85W ultrasonic action at room temperature A mixed solvent of anhydrous ethanol / water was added and ultrasonicated for 30 minutes to obtain a polyetheretherketone slurry; the polyetheretherketone slurry was brushed onto the surface of the fiber cloth, dried at 100°C for 10 hours, and dried and the solvent was removed to obtain a prepreg; the prepregs were sequentially layered in a mold coated with a release agent; the mold was placed in a hot press and heated and pressurized for curing: the temperature was raised to 385°C, the pressure was increased to 20 MPa, and the curing was carried out for 1.2 hours; the pressure was maintained and naturally cooled to room temperature, and the mold was demolded to obtain the silica-modified polyetherketone water-based sized fiber cloth reinforced polyetheretherketone composite material of the present invention.

[0058] Example 3:

[0059] (1) Preparation of carbon nanotube-modified polyetheretherketoneketone water-based sizing agent

[0060] The composition and proportion of each component of carbon nanotube modified polyetheretherketoneketone water-based sizing agent are as follows: particle size 15μm 4 wt% of polyetheretherketoneketone, 0.3 wt% of carbon nanotubes, 0.7 wt% of anionic polyacrylic acid sodium salt dispersant, 0.35 wt% of nonionic fatty alcohol polyoxyethylene ether wetting agent, 0.35 wt% of water-based silicone defoamer, and 94.3 wt% of deionized water; the preparation of a carbon nanotube-modified polyetheretherketoneketone water-based sizing agent comprises the following steps: drying the polyetheretherketoneketone at 105° C. for 9.5 h to remove adsorbed water; adding the dispersant, wetting agent, and defoamer into deionized water, and mechanically stirring at room temperature and 350 r / min for 25 min until the mixture is uniform; adding carbon nanotubes into the above-mentioned mixture, and ultrasonically dispersing the mixture at room temperature and 180 W for 25 min; adding polyetheretherketoneketone into the above-mentioned dispersion, and mechanically stirring the mixture at room temperature and 350 r / min for 60 min; and then transferring the mixture into a high-shear homogenizer and stirring at high speed at room temperature and 9000 r / min for 25 min to obtain a uniformly dispersed carbon nanotube-modified polyetheretherketoneketone water-based sizing agent;

[0061] (2) Sizing modification process of carbon fiber cloth surface with carbon nanotube modified polyetheretherketoneketone water-based sizing agent

[0062] The carbon fiber cloth was completely immersed in the carbon nanotube-doped polyetheretherketoneketone water-based sizing agent by the impregnation method, and ultrasonically impregnated at room temperature and 85W for 0.8h; then dried at 70℃ for 13h to obtain the carbon nanotube-modified polyetheretherketoneketone water-based sizing fiber cloth;

[0063] (3) Preparation of carbon nanotube modified polyetheretherketone ketone water-based sizing carbon fiber cloth reinforced polyetheretherketone composite materials by slurry method

[0064] The composition and distribution ratio of the carbon nanotube modified polyetheretherketone ketone water-based sizing fiber cloth reinforced polyetheretherketone composite material are as follows: 50wt% of carbon nanotube modified polyetheretherketone ketone water-based sizing fiber cloth, 50wt% of polyetheretherketone powder with a particle size of 40μm, and a mass ratio of polyetheretherketone: acetone: water = 1:0.95:0.95; the slurry method for preparing the carbon nanotube modified polyetheretherketone ketone water-based sizing fiber cloth reinforced polyetheretherketone composite material includes the following steps: preparing an acetone / water mixed solvent; slurrying the polyetheretherketone powder under 85W ultrasonic action at room temperature; A cosolvent / water mixed solvent is added and ultrasonicated for 25 minutes to obtain a polyetheretherketone slurry; the polyetheretherketone slurry is brushed onto the surface of the fiber cloth, dried at 90°C for 15 hours, and dried and the solvent is removed to obtain a prepreg; the prepregs are sequentially layered in a mold coated with a release agent; the mold is placed in a hot press and heated and pressurized for curing: the temperature is raised to 393°C, the pressure is increased to 15 MPa, and the curing is carried out for 2 hours; the pressure is maintained and naturally cooled to room temperature, and the mold is demolded to obtain the carbon nanotube-modified polyetheretherketone ketone water-based sized fiber cloth reinforced polyetheretherketone composite material of the present invention.

[0065] Example 4:

[0066] (1) Preparation of graphene oxide modified polyetherketone etherketone ketone water-based sizing agent

[0067] The composition and proportion of each component of the graphene oxide modified polyetherketone etherketone ketone water-based sizing agent are as follows: 7 wt% of polyetherketone etherketone ketone with a particle size of 17 μm, 0.2 wt% of graphene oxide, 0.75 wt% of anionic sodium tripolyphosphate dispersant, 0.5 wt% of nonionic alkyl polyoxyethylene ether wetting agent, 0.45 wt% of water-based silicone defoamer, and 91.1 wt% of deionized water; the preparation of the graphene oxide modified polyetherketone etherketone ketone water-based sizing agent comprises the following steps: drying the polyetherketone etherketone ketone at 110° C. for 8.5 h to remove adsorbed water; separating The powder, wetting agent and defoaming agent are added to deionized water and mechanically stirred at room temperature and 400 r / min for 10 minutes until the mixture is uniformly mixed; graphene oxide is added to the above mixture and ultrasonically dispersed at room temperature and 150W for 20 minutes; polyetherketoneetherketoneketone is added to the above dispersion and mechanically stirred at room temperature and 400 r / min for 90 minutes; then the mixture is transferred to a high shear homogenizer and stirred at high speed at room temperature and 9500 r / min for 23 minutes to obtain a uniformly dispersed graphene oxide modified polyetherketoneetherketoneketone water-based sizing agent;

[0068] (2) Sizing modification process of graphene oxide modified polyetherketone etherketone ketone water-based sizing agent on the surface of basalt fiber cloth

[0069] The basalt fiber cloth was completely immersed in the graphene oxide-doped polyether ketone ether ketone ketone water-based sizing agent by the impregnation method, and ultrasonically impregnated at room temperature and 100W for 1.5 hours; then dried at 70°C for 10 hours to obtain the graphene oxide-modified polyether ketone ether ketone ketone water-based sizing fiber cloth;

[0070] (3) Preparation of graphene oxide modified polyether ether ketone ketone water-based sizing basalt fiber cloth reinforced polyether ether ketone composite materials by slurry method

[0071] The composition and distribution ratio of the graphene oxide modified polyether ketone ether ketone ketone water-based sizing basalt fiber cloth reinforced polyether ether ketone composite material are as follows: 75wt% of graphene oxide modified polyether ketone ether ketone ketone water-based sizing basalt fiber cloth, 25wt% of polyether ether ketone powder with a particle size of 50μm, and a mass ratio of polyether ether ketone: ethylene glycol: water = 1:1.5:1.5; the slurry method for preparing the carbon nanotube modified polyether ether ketone ketone water-based sizing fiber cloth reinforced polyether ether ketone composite material includes the following steps: preparing an ethylene glycol / water mixed solvent; at room temperature and under 95W ultrasonic action, polyether Ether ketone powder is added to an ethylene glycol / water mixed solvent and ultrasonicated for 22 minutes to obtain a polyether ether ketone slurry; the polyether ether ketone slurry is brushed onto the surface of a fiber cloth, dried at 105°C for 13 hours, and dried and the solvent is removed to obtain a prepreg; the prepregs are sequentially layered in a mold coated with a release agent; the mold is placed in a hot press and heated and pressurized for curing: the temperature is raised to 400°C, the pressure is increased to 30 MPa, and the curing is performed for 1.3 hours; the pressure is maintained and naturally cooled to room temperature, and then demolded to obtain the carbon nanotube-modified polyether ether ketone ketone water-based sized fiber cloth reinforced polyether ether ketone composite material of the present invention.

[0072] Example 5:

[0073] (1) Preparation of silica-modified polyetherketoneketone water-based sizing agent

[0074] The composition and proportion of each component of the silica-modified polyetherketoneketone water-based sizing agent are as follows: 6 wt% of polyetherketoneketone with a particle size of 15 μm, 0.6 wt% of silica, 0.78 wt% of anionic sodium tripolyphosphate dispersant, 0.5 wt% of nonionic nonylphenol polyoxyethylene ether wetting agent, 0.6 wt% of water-based silicone defoamer, and 91.52 wt% of deionized water. The preparation of the silica-modified polyetherketoneketone water-based sizing agent includes the following steps: drying the polyetherketoneketone at 115° C. for 9.5 h to remove adsorbed water; dispersant , a wetting agent and a defoaming agent are added to deionized water, and mechanically stirred at room temperature and 500r / min for 12 minutes until the mixture is uniform; silicon dioxide is added to the above mixture, and ultrasonically dispersed at room temperature and 185W for 40 minutes; polyetherketoneketone is added to the above dispersion, and mechanically stirred at room temperature and 500r / min for 90 minutes; then transferred to a high shear homogenizer and stirred at high speed at room temperature and 11000r / min for 28 minutes; a uniformly dispersed silicon dioxide modified polyetherketoneketone water-based sizing agent is obtained;

[0075] (2) Sizing modification process of silica-modified polyetherketoneketone water-based sizing agent on quartz fiber cloth surface

[0076] The quartz fiber cloth was completely immersed in the silica-modified polyetherketoneketone water-based sizing agent by an impregnation method, and ultrasonically impregnated for 0.6 h at room temperature and 100 W; and then dried at 95 ° C for 13 h to obtain the silica-modified polyetherketoneketone water-based sizing quartz fiber cloth.

[0077] (3) Preparation of silica-modified polyetherketone ketone water-based sizing quartz fiber cloth reinforced polyetheretherketone composite materials by slurry method

[0078] The composition and distribution ratio of the silica-modified polyetherketone ketone water-based sizing fiber cloth reinforced polyetheretherketone composite material are as follows: 53wt% of silica-modified polyetherketone ketone water-based sizing fiber cloth, 47wt% of polyetheretherketone powder with a particle size of 50μm, and a mass ratio of polyetheretherketone: acetone: water = 1:1.2:1.2; the slurry method for preparing the silica-modified polyetherketone ketone water-based sizing fiber cloth reinforced polyetheretherketone composite material includes the following steps: preparing acetone / deionized water solution; adding polyetheretherketone powder to acetone under 100W ultrasonic action at room temperature; The polyetheretherketone slurry is prepared by applying a ketone / water mixed solvent and ultrasonicating for 24 minutes to obtain a polyetheretherketone slurry; the polyetheretherketone slurry is applied to the surface of the fiber cloth, dried at 120°C for 10 hours, and the solvent is removed by drying to obtain a prepreg; the prepregs are sequentially layered in a mold coated with a release agent; the mold is placed in a hot press and heated and pressurized for curing: the temperature is raised to 397°C, the pressure is increased to 25 MPa, and the curing is performed for 2.5 hours; the pressure is maintained and naturally cooled to room temperature, and the mold is demolded to obtain the silica-modified polyetherketone ketone water-based sized quartz fiber cloth reinforced polyetheretherketone composite material of the present invention.

[0079] The upper and lower limit values ​​of each raw material process parameter listed in the present invention and the interval values ​​thereof can all realize the present invention, and the embodiments are not listed one by one here.

Claims

1. An efficient and green preparation method for a nano-modified polyether aryl ketone sizing fiber cloth reinforced polyether ether ketone composite material, characterized in that: The following steps are involved: (1) Preparation of nano-modified polyether aromatic ketone water-based sizing agent The polyether aryl ketone is dried to remove adsorbed water; a dispersant, a wetting agent and a water-based silicone defoamer are added to water, and mechanically stirred at room temperature until the mixture is uniform; nanoparticles are added to the mixed solution, and ultrasonic dispersion is performed at room temperature for a certain time; polyether aryl ketone is added to the dispersion, and mechanical stirring is performed at room temperature for a certain time; the dispersion is transferred to a high shear homogenizing emulsifier and stirred at high speed for 10 to 30 minutes at room temperature and 8000 to 12000 r / min; a uniformly dispersed nano-modified polyether aryl ketone water-based sizing agent can be obtained; (2) Sizing modification process of nano-modified polyether aromatic ketone water-based sizing agent on fiber cloth surface The fiber cloth is completely immersed in the nano-modified polyether aromatic ketone water-based sizing agent of step (1) by an immersion method, and then ultrasonically immersed for a period of time at room temperature and dried to obtain the nano-modified polyether aromatic ketone water-based sizing fiber cloth; (3) Preparation of nano-modified polyether aryl ketone water-based sizing fiber cloth reinforced polyether ether ketone composite materials by slurry method Prepare a cosolvent / water mixed solvent; add the cosolvent / water mixed solvent to polyetheretherketone under the action of ultrasound at room temperature and 80-100W, and perform ultrasound for 10-30 minutes to obtain polyetheretherketone slurry; apply the polyetheretherketone slurry to the surface of the nano-modified polyetheraromatic ketone water-based sizing fiber cloth obtained in step (2), dry and remove the solvent to obtain a prepreg; lay the prepreg in a mold coated with a release agent in sequence; place the mold in a hot press, heat and pressurize to cure; maintain pressure and naturally cool to room temperature, then demold to obtain a nano-modified polyetheraromatic ketone water-based sizing fiber cloth reinforced polyetheretherketone composite material.

2. The efficient and green preparation method of a nano-modified polyether aryl ketone sizing fiber cloth reinforced polyether ether ketone composite material according to claim 1, characterized in that: The proportions of the components in the nano-modified polyether aromatic ketone aqueous sizing agent described in step (1) are: 1-8wt% polyether aromatic ketone, 0.1-1wt% nanoparticles, 0.3-0.8wt% dispersant, 0.1-0.5wt% wetting agent, 0.3-1wt% aqueous silicone defoamer, and 88.7-98.2wt% deionized water.

3. The efficient and green preparation method of a nano-modified polyether aryl ketone sizing fiber cloth reinforced polyether ether ketone composite material according to claim 1, characterized in that: In step (1), the polyether aromatic ketone is dried at 100-120° C. for 6-10 hours; the mechanical stirring speed after the dispersant, wetting agent and aqueous silicone defoamer are added to deionized water is 200-500 r / min for 10-30 minutes; the ultrasonic dispersion condition after the nanoparticles are added is ultrasonic dispersion at 100-200W for 15-45 minutes; the mechanical stirring speed after the polyether aromatic ketone is added is 200-500 r / min for 50-100 minutes.

4. The efficient and green preparation method of a nano-modified polyether aryl ketone sizing fiber cloth reinforced polyether ether ketone composite material according to claim 1, characterized in that: In step (1), the nanoparticles are at least one of graphene oxide, silicon dioxide and carbon nanotubes; the polyether aromatic ketone is at least one of polyether ketone, polyether ether ketone, polyether ketone ketone, polyether ether ketone ketone and polyether ketone ether ketone ketone, which is in powder form with a particle size of 10 to 20 μm.

5. The efficient and green preparation method of a nano-modified polyether aryl ketone sizing fiber cloth reinforced polyether ether ketone composite material according to claim 1, characterized in that: In step (1), the dispersant is at least one of anionic polyacrylic acid sodium salt, polycarboxylic acid sodium salt and tripolyphosphate sodium salt dispersants; the wetting agent is at least one of nonionic alkyl polyoxyethylene ether, nonylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether wetting agents.

6. The efficient and green preparation method of a nano-modified polyether aryl ketone sizing fiber cloth reinforced polyether ether ketone composite material according to claim 1, characterized in that: The ultrasonic immersion conditions in step (2) are 0.5 to 2 hours at 80 to 100W; the drying temperature is 60 to 100°C and the time is 12 to 18 hours.

7. The efficient and green preparation method of a nano-modified polyether aryl ketone sizing fiber cloth reinforced polyether ether ketone composite material according to claim 1, characterized in that: In step (3), the fiber cloth is any one or more of carbon fiber cloth, basalt fiber cloth and quartz fiber cloth, the polyetheretherketone in step (3) is in powder form with a particle size of 20 to 100 μm, and the co-solvent is at least one of anhydrous ethanol, ethylene glycol and acetone.

8. The efficient and green preparation method of a nano-modified polyether aryl ketone sizing fiber cloth reinforced polyether ether ketone composite material according to claim 1, characterized in that: In step (3), the proportion of each component of the nano-modified polyether aromatic ketone water-based sizing fiber cloth reinforced polyether ether ketone composite material is 50-70wt% of nano-modified polyether aromatic ketone water-based sizing fiber cloth and 30-50wt% of polyether ether ketone slurry; the mass ratio of polyether ether ketone, co-solvent and water in the polyether ether ketone slurry is 1:0.5-2:0.5-2.

9. The efficient and green preparation method of a nano-modified polyether aryl ketone sizing fiber cloth reinforced polyether ether ketone composite material according to claim 1, characterized in that: In step (3), the drying and solvent removal conditions are drying at 80-120° C. for 10-16 hours.

10. The efficient and green preparation method of a nano-modified polyether aryl ketone sizing fiber cloth reinforced polyether ether ketone composite material according to claim 1, characterized in that: Step (3) heating and pressurizing for curing The process includes: heating to 380-400° C., pressurizing to 5-30 MPa, and curing for 1-3 hours.

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