Wear-resistant prepreg as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of wear-resistant materials, and discloses a wear-resistant prepreg as well as a preparation method and application thereof, the wear-resistant prepreg is prepared from the following raw materials: a resin matrix, carbon fibers and at least two nanoparticles which have different median particle sizes and are modified by a silane coupling agent; the production process of the wear-resistant prepreg is basically consistent with that of a conventional prepreg, and only in the epoxy resin impregnation process, a proper number of nanoparticles which have different median diameters and are modified by a silane coupling agent are uniformly distributed in the prepreg, so that the carbon fiber prepreg with wear resistance is formed.

Description

Technical Field

[0001] The present invention relates to the technical field of wear-resistant materials, and particularly relates to a wear-resistant prepreg, a preparation method thereof, and an application thereof. Background Art

[0002] Prepreg laying is one of the main forming methods of carbon fiber reinforced epoxy resin composites. Due to the relatively high friction coefficient and poor wear resistance of the epoxy resin matrix, its application in the field of wear resistance requirements is limited. When the epoxy resin on the surface of the carbon fiber reinforced epoxy resin composite is worn to a certain extent, the internal carbon fibers are exposed and will be further worn, resulting in the destruction of its mechanical properties, reduction of its service life, and even potential safety hazards in use. Therefore, it is necessary to perform functional wear-resistant treatment on the carbon fiber reinforced epoxy resin composite.

[0003] The prior art improves the wear resistance of carbon fiber reinforced epoxy resin composites by painting or using metal protection sheets. However, these methods have disadvantages. For example, painting is easily worn and requires frequent repainting, and the metal protection sheets increase the weight of the product and affect the appearance.

[0004] Chinese Patent Document CN106832779B discloses a wear-resistant epoxy resin composite and a preparation method thereof. By dispersing 0.05 - 15% of flaky tungsten sulfide / graphene oxide nanocomposite in the resin matrix, its wear resistance is effectively improved. However, this method involves steps such as surface treatment, ultrasonic dispersion, drying, and vacuum pumping, and the overall process is complex and lengthy, which is not suitable for mass production.

[0005] Chinese Patent Document CN114015199B discloses a wear-resistant epoxy resin composite and a preparation method thereof. By adding 1 - 5% of metal-organic framework-derived nickel silicate to the epoxy resin matrix, about 80% reduction in wear is reported. However, the metal-organic framework-derived nickel silicate itself has a high cost, is not easy to disperse in the resin matrix, is prone to agglomeration and precipitation, and is difficult to store.

[0006] Chinese Patent Document CN113088162B discloses a wear-resistant epoxy resin coating and a preparation method thereof. A wear-resistant coating is prepared, the coating matrix is epoxy resin, and the dispersed phase is 3% of nano / micro titanium dioxide treated with KH550 coupling agent. Since the coating already contains both epoxy resin and curing agent, it cannot be stored for a long time.

[0007] In summary, it is very necessary to provide a prepreg with self-wear resistance to improve the wear resistance of carbon fiber reinforced epoxy resin composites. Summary of the Invention

[0008] In view of the above problems, the present invention provides a wear-resistant prepreg, a preparation method and an application thereof. The wear-resistant prepreg itself has wear resistance and can significantly improve the wear resistance of carbon fiber reinforced epoxy resin composites in a low-cost and high-efficiency manner without changing the production process and flow.

[0009] To solve the above technical problems, a first aspect of the present invention provides a wear-resistant prepreg. The raw materials for preparing the wear-resistant prepreg include a resin matrix, carbon fibers and at least two kinds of nanoparticles with different median particle sizes (D50) and modified by a silane coupling agent.

[0010] According to some embodiments of the present invention, in the wear-resistant prepreg, the mass ratio of carbon fiber to resin matrix is 60:40 - 45; and / or,

[0011] The mass of the modified nanoparticles is 8% - 12% of the mass of the resin matrix.

[0012] According to some embodiments of the present invention, the nanoparticles are selected from at least one of alumina, silica or silicon carbide; preferably, the wear-resistant particles are selected from alumina and / or silicon carbide.

[0013] According to some embodiments of the present invention, the nanoparticles include a first nanoparticle and a second nanoparticle; preferably, the D50 of the first nanoparticle is 50nm - 80nm, the D10 is 40nm - 46nm, the D90 is 83nm - 94nm, the D50 of the second nanoparticle is 60nm - 100nm, the D10 is 57nm - 62nm, the D90 is 98nm - 108nm, and the difference between the D50 of the first nanoparticle and the D50 of the second nanoparticle is ≧ 30nm, preferably 30nm - 40nm; further preferably, the mass ratio of the first nanoparticle to the second nanoparticle is 1:2 - 5.

[0014] According to some embodiments of the present invention, the resin matrix includes an epoxy resin, an acid anhydride curing agent and an accelerator; preferably, the mass ratio of the epoxy resin to the acid anhydride curing agent is 100:85 - 90; the mass of the accelerator is 1.5% - 2.0% of the total mass of the epoxy resin and the acid anhydride curing agent.

[0015] According to some embodiments of the present invention, the epoxy resin is selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, bisphenol S epoxy resin; the acid anhydride curing agent is selected from at least one of methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride; the accelerator is selected from at least one of 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole.

[0016] According to some embodiments of the present invention, the steps of modifying the nanoparticles with a silane coupling agent include: placing the nanoparticles in an ethanol aqueous solution with a concentration of 30 vol% to 50 vol%, performing ultrasonic dispersion for 15 min to 30 min and then performing the first drying; then placing the nanoparticles after the first drying in a silane coupling agent aqueous solution with a volume concentration of 1% to 3% and a pH of 4 - 5, performing ultrasonic dispersion for 15 min to 30 min and then performing the second drying to obtain the nanoparticles;

[0017] Preferably, the conditions for the first drying include: a temperature of 80°C to 100°C and a time of 2 h to 4 h;

[0018] and / or, the temperature for the second drying is 120°C to 140°C and the time is 2 h to 4 h.

[0019] In the present invention, there is no particular limitation on the type of the silane coupling agent, and examples thereof may include KH550, KH551, KH560, A - 151, etc.

[0020] In the present invention, during the process of modifying the nanoparticles with a silane coupling agent, there is no particular limitation on the solid - liquid ratio of the nanoparticles to the ethanol aqueous solution and the nanoparticles to the silane coupling agent aqueous solution, and examples thereof may include 1:5 - 10.

[0021] The second aspect of the present invention provides a method for preparing the wear - resistant prepreg provided in the first aspect above, including:

[0022] (1) Preparing a resin impregnating solution: mixing the nanoparticles with a resin matrix to obtain a resin impregnating solution;

[0023] (2) Impregnating: impregnating carbon fibers in the resin impregnating solution obtained in step (1) and pre - curing to obtain the wear - resistant prepreg.

[0024] According to some embodiments of the present invention, in step (1), the mixing is carried out in a vacuum mixer; preferably, the conditions for the mixing include: a rotation speed of 300 rpm to 400 rpm, a vacuum degree of - 0.05 MPa to - 0.1 MPa, and a time of 30 min to 40 min.

[0025] According to some embodiments of the present invention, in step (2), the impregnating is carried out in a resin tank; preferably, the temperature of the resin tank is 40 ± 2°C;

[0026] and / or, the conditions for the impregnating include: a pressure of 0.2 MPa to 0.5 MPa (ensuring that the resin fully penetrates the fiber bundle);

[0027] And / or, the conditions for pre-curing include: temperature of 80°C to 85°C and time of 30s to 40s; the purpose of pre-curing is to preliminarily crosslink the resin (gel degree reaches 60% to 70%), so as to avoid resin adhesion during subsequent lamination with the release film.

[0028] During the preparation process of the wear-resistant prepreg of the present invention, there is no special limitation on the traction rate of carbon fiber and the feeding rate of the resin impregnating solution. For example, the traction rate of carbon fiber is controlled by a frequency conversion of the traction motor to be 1.2 - 1.5 m / min, and the feeding rate of the resin impregnating solution matches the traction rate of carbon fiber to control the resin coating amount at 35 ± 2 g / m 2 .

[0029] The impregnation of the present invention is carried out in a closed resin tank. Among them, the resin tank is equipped with a circulating heating system and an ultrasonic dispersion device. The ultrasonic wave acts continuously to prevent nanoparticle agglomeration. The resin viscosity in the resin tank is monitored in real time and the temperature is feedback-regulated; the carbon fiber roving enters the resin tank through a guiding roller, and the immersion depth is 10 cm. Excess resin is extruded through two sets of opposing rollers (gap 0.5 mm).

[0030] In the present invention, the pre-cured wear-resistant prepreg is laid flat on the release film, and the surface is covered with another layer of release film (sandwich structure: film - prepreg - film); it is pressed by two sets of rubber rollers (temperature 60°C, pressure 0.1 MPa) to ensure no bubbles and the film-to-film adhesion degree > 95%; the tension is maintained at 20 N / cm, the winding speed is synchronized with the impregnation line speed, and the alignment error of the coil edge is ≤ 1 mm.

[0031] The third aspect of the present invention provides a carbon fiber reinforced epoxy resin composite material, including the wear-resistant prepreg provided in the first aspect above or the wear-resistant prepreg prepared by the preparation method provided in the second aspect above.

[0032] According to some embodiments of the present invention, the preparation method of the carbon fiber reinforced epoxy resin composite material includes: covering at least one layer of the above-mentioned wear-resistant prepreg on the surface of the carbon fiber prepreg, and performing vacuum pumping and curing to obtain the carbon fiber reinforced epoxy resin composite material.

[0033] In the present invention, there is no special limitation on the carbon fiber prepreg, which can be a carbon fiber prepreg known to those skilled in the art or obtained through commercial channels; it can also be the prepreg without nanoparticles provided in the first aspect of the present invention or the prepreg without nanoparticles prepared by the preparation method provided in the second aspect.

[0034] In the present invention, there is no special limitation on the conditions for vacuum pumping, and the vacuum pumping can meet the technical requirements in the art.

[0035] According to some embodiments of the present invention, the curing is carried out in a curing furnace; the conditions for the curing include: a temperature of 130°C to 140°C and a time of 12 h to 16 h.

[0036] Beneficial effects:

[0037] The present invention provides a prepreg with wear resistance. The production process of this wear-resistant prepreg is basically the same as that of a conventional prepreg. Only during the epoxy resin impregnation process, an appropriate number of nanoparticles with different median particle sizes (D50) and modified with a silane coupling agent are evenly distributed in the prepreg to form a carbon fiber prepreg with wear resistance.

[0038] In the preparation method of the wear-resistant prepreg of the present invention, the carbon fiber roving will carry away nanoparticles during the impregnation of epoxy resin, which can provide protection for the prepreg after curing and can also serve as the outermost protective layer of the carbon fiber reinforced epoxy resin composite material.

[0039] The method involved in the present invention does not change the laying process, nor does it change the properties of the raw materials. Under the condition of convenient process, it can effectively and economically improve the wear resistance of the carbon fiber reinforced epoxy resin composite material. Specifically, after the prepreg of the carbon fiber reinforced epoxy resin composite material is laid and before it is processed in a bag, an additional layer of the wear-resistant prepreg described in the present invention is laid on its surface. Since the wear-resistant prepreg described in the present invention is essentially no different from the prepreg of the carbon fiber reinforced epoxy resin composite material, it can be co-cured with the prepreg of the carbon fiber reinforced epoxy resin composite material without changing the production process of the carbon fiber reinforced epoxy resin composite material, but the wear of the carbon fiber reinforced epoxy resin composite material can be reduced to 20%.

[0040] The wear-resistant prepreg described in the present invention can be used as an ordinary prepreg. Before the carbon fiber reinforced epoxy resin composite material is cured, the wear-resistant prepreg is laid on the surface of the carbon fiber reinforced epoxy resin composite material that needs to be protected and cured, and the wear of the carbon fiber reinforced epoxy resin composite material can be effectively reduced. Description of the drawings

[0041] Figure 1 It is a schematic diagram of the laying of the wear-resistant prepreg of the present invention;

[0042] Figure 2 It is a schematic diagram of the preparation process of the wear-resistant prepreg of the present invention. Detailed embodiments

[0043] The following further illustrates the present invention with reference to embodiments. However, the present invention is not limited by these embodiments.

[0044] In the following examples and comparative examples of the present invention, without special instructions, all kinds of raw materials used are commercially available.

[0045] In the embodiments and comparative examples of the present invention,

[0046] The carbon fiber is T700 grade carbon fiber roving (purchased from Fucaiyigou, monofilament diameter 7μm, tensile strength 4.9GPa, modulus 230GPa), and the areal density of the carbon fiber is 200g / m 2 ;

[0047] The epoxy resin is bisphenol A type epoxy resin (E-51, epoxy value 0.48 - 0.54);

[0048] The anhydride curing agent is methylhexahydrophthalic anhydride;

[0049] The accelerator is 2-ethyl-4-methylimidazole;

[0050] The release film is a polyester-based silicone-coated film with a thickness of 25μm.

[0051] In the present invention, 4 layers of carbon fiber prepreg are laid.

[0052] In the present invention, during the modification treatment of the wear-resistant particles with silane coupling agent, the solid-liquid ratios of the wear-resistant particles to the ethanol aqueous solution and the wear-resistant particles to the silane coupling agent aqueous solution are not particularly limited, and the solid-liquid ratios in the examples are all 1:5.

[0053] Example 1

[0054] This example is used to illustrate the wear-resistant prepreg and its preparation method described in the present invention.

[0055] The preparation of the nano-particles includes:

[0056] Aluminum oxide (a combination of aluminum oxide with D50 of 60nm, D10 of 40nm, D90 of 91nm and aluminum oxide with D50 of 90nm, D10 of 60nm, D90 of 105nm, with a mass ratio of 1:3.5) is placed in a 50vol% ethanol aqueous solution, ultrasonically dispersed for 15min and then dried at 80°C for 2h; then the dried wear-resistant particles are placed in a 1% volume concentration, pH = 4 aqueous solution of silane coupling agent (KH550), ultrasonically dispersed for 15min and then dried at 120°C for 2h to obtain the nano-particles.

[0057] The preparation of the wear-resistant prepreg includes:

[0058] The epoxy resin, anhydride curing agent, accelerator and the above-mentioned nano-particles are mixed in a vacuum mixer under the mixing conditions of a rotation speed of 300rpm, a vacuum degree of -0.1MPa and a time of 30min to obtain a resin impregnating solution;

[0059] The carbon fiber roving enters the resin tank through the guiding roller (the temperature of the resin tank is 40 °C, and the traction rate of the carbon fiber is 1.2 m / min), with an immersion depth of 10 cm. Excess resin is extruded through two sets of opposing rollers (pressure is 0.3 MPa), and then pre-cured at 80 °C for 30 s and then laminated with the release film. After being pressed by two sets of rubber rollers, the wear-resistant prepreg is obtained by winding;

[0060] In the wear-resistant prepreg, the mass ratio of carbon fiber to resin matrix is 60:40; the mass of the nano-particles is 10% of the mass of the resin matrix; and / or, the mass ratio of the epoxy resin to the anhydride curing agent is 100:85; the mass of the accelerator is 1.5% of the total mass of the epoxy resin and the anhydride curing agent;

[0061] The pressing conditions of the two sets of rubber rollers include: temperature is 60 °C, pressure is 0.1 MPa; the winding conditions include: the tension control is 20 N / cm.

[0062] Example 2

[0063] This example is used to illustrate the wear-resistant prepreg and its preparation method of the present invention.

[0064] The preparation of the nano-particles includes:

[0065] Put silicon carbide (a combination of silicon carbide with D50 of 60 nm, D10 of 40 nm, D90 of 91 nm and silicon carbide with D50 of 90 nm, D10 of 60 nm, D90 of 105 nm, with a mass ratio of 1:3.5) into an aqueous ethanol solution with a volume concentration of 50 vol%, ultrasonically disperse for 15 min, and then dry at 80 °C for 2 h; then put the dried wear-resistant particles into an aqueous solution of silane coupling agent (KH550) with a volume concentration of 1% and pH = 4, ultrasonically disperse for 15 min, and then dry at 120 °C for 2 h to obtain the nano-particles.

[0066] The preparation of the wear-resistant prepreg includes:

[0067] Mix epoxy resin, anhydride curing agent, accelerator and the above-mentioned nano-particles in a vacuum mixer, and the mixing conditions are a rotation speed of 300 rpm, a vacuum degree of -0.1 MPa, and a time of 30 min to obtain a resin impregnating solution;

[0068] The carbon fiber roving enters the resin tank through the guiding roller (the temperature of the resin tank is 40 °C, and the traction rate of the carbon fiber is 1.2 m / min), with an immersion depth of 10 cm. Excess resin is extruded through two sets of opposing rollers (pressure is 0.3 MPa), and then pre-cured at 80 °C for 30 s and then laminated with the release film. After being pressed by two sets of rubber rollers, the wear-resistant prepreg is obtained by winding;

[0069] In the wear-resistant prepreg, the mass ratio of carbon fiber to resin matrix is 60:40; the mass of the nano-particles is 10% of the mass of the resin matrix; and / or, the mass ratio of the epoxy resin to the anhydride curing agent is 100:85; the mass of the accelerator is 1.5% of the total mass of the epoxy resin and the anhydride curing agent.

[0070] The pressing conditions of the two groups of rubber rollers include: the temperature is 60 °C and the pressure is 0.1 MPa; the winding conditions include: the tension control is 20 N / cm.

[0071] Example 3

[0072] This example is used to illustrate the wear-resistant prepreg and its preparation method described in the present invention.

[0073] The preparation of the nano-particles includes:

[0074] Aluminum oxide and silicon carbide (a combination of aluminum oxide with D50 of 60 nm, D10 of 40 nm, and D90 of 91 nm and silicon carbide with D50 of 90 nm, D10 of 60 nm, and D90 of 105 nm, with a mass ratio of 1:3.5) are placed in a 50 vol% ethanol aqueous solution, ultrasonically dispersed for 15 min, and then dried at 80 °C for 2 h; then the dried wear-resistant particles are placed in a 1% volume concentration and pH = 4 aqueous solution of silane coupling agent (KH550), ultrasonically dispersed for 15 min, and then dried at 120 °C for 2 h to obtain the nano-particles.

[0075] The preparation of the wear-resistant prepreg includes:

[0076] Epoxy resin, anhydride curing agent, accelerator, and the above-mentioned nano-particles are mixed in a vacuum mixer, and the mixing conditions are a rotation speed of 300 rpm, a vacuum degree of -0.1 MPa, and a time of 30 min to obtain a resin impregnating solution;

[0077] The carbon fiber roving enters the resin tank through a guide roller (the temperature of the resin tank is 40 °C, and the traction rate of the carbon fiber is 1.2 m / min), the immersion depth is 10 cm, the excess resin is extruded through two groups of opposing rollers (the pressure is 0.3 MPa), then pre-cured at 80 °C for 30 s and then compounded with a release film, and finally wound by two groups of rubber rollers to obtain the wear-resistant prepreg;

[0078] In the wear-resistant prepreg, the mass ratio of carbon fiber to resin matrix is 60:40; the mass of the nano-particles is 10% of the mass of the resin matrix; and / or, the mass ratio of the epoxy resin to the anhydride curing agent is 100:85; the mass of the accelerator is 1.5% of the total mass of the epoxy resin and the anhydride curing agent.

[0079] The pressing conditions of the two groups of rubber rollers include: the temperature is 60°C and the pressure is 0.1 MPa; the winding conditions include: the tension control is 20 N / cm.

[0080] Example 4

[0081] This example is used to illustrate the wear-resistant prepreg and its preparation method of the present invention.

[0082] The preparation of the nano-particles includes:

[0083] Silica (a combination of silica with D50 of 60 nm, D10 of 40 nm, D90 of 91 nm and silica with D50 of 90 nm, D10 of 60 nm, D90 of 105 nm, with a mass ratio of 1:3.5) is placed in a 50 vol% ethanol aqueous solution, ultrasonically dispersed for 15 min and then dried at 80°C for 2 h; then the dried wear-resistant particles are placed in an aqueous solution of silane coupling agent (KH550) with a volume concentration of 1% and pH = 4, ultrasonically dispersed for 15 min and then dried at 120°C for 2 h to obtain the nano-particles.

[0084] The preparation of the wear-resistant prepreg includes:

[0085] Epoxy resin, anhydride curing agent, accelerator and the above nano-particles are mixed in a vacuum mixer, and the mixing conditions are a rotation speed of 300 rpm, a vacuum degree of -0.1 MPa, and a time of 30 min to obtain a resin impregnating solution;

[0086] The carbon fiber roving enters the resin tank through a guide roller (the temperature of the resin tank is 40°C, and the traction rate of the carbon fiber is 1.2 m / min), the immersion depth is 10 cm, the excess resin is extruded through two groups of opposing rollers (the pressure is 0.3 MPa), then pre-cured at 80°C for 30 s and then compounded with a release film, and wound after being pressed by two groups of rubber rollers to obtain the wear-resistant prepreg;

[0087] In the wear-resistant prepreg, the mass ratio of carbon fiber to resin matrix is 60:40; the mass of the nano-particles is 10% of the mass of the resin matrix; and / or, the mass ratio of the epoxy resin to the anhydride curing agent is 100:85; the mass of the accelerator is 1.5% of the total mass of the epoxy resin and the anhydride curing agent;

[0088] The pressing conditions of the two groups of rubber rollers include: the temperature is 60°C and the pressure is 0.1 MPa; the winding conditions include: the tension control is 20 N / cm.

[0089] Example 5

[0090] This example is used to illustrate the wear-resistant prepreg and its preparation method of the present invention.

[0091] The preparation of the nanoparticles includes:

[0092] Aluminum oxide (a combination of aluminum oxide with D50 of 60 nm, D10 of 40 nm, D90 of 91 nm and aluminum oxide with D50 of 100 nm, D10 of 58 nm, D90 of 108 nm, with a mass ratio of 1:3.5) is placed in an aqueous ethanol solution with a volume concentration of 50 vol%, ultrasonically dispersed for 15 min, and then dried at 80 °C for 2 h; then the dried wear-resistant particles are placed in an aqueous solution of a silane coupling agent (KH550) with a volume concentration of 1% and a pH of 4, ultrasonically dispersed for 15 min, and then dried at 120 °C for 2 h to obtain the nanoparticles.

[0093] The preparation of the wear-resistant prepreg includes:

[0094] Epoxy resin, acid anhydride curing agent, accelerator and the above-mentioned nanoparticles are mixed in a vacuum mixer under the mixing conditions of a rotation speed of 300 rpm, a vacuum degree of -0.1 MPa, and a time of 30 min to obtain a resin impregnating solution;

[0095] The carbon fiber roving enters the resin bath through a guide roller (the temperature of the resin bath is 40 °C, and the traction rate of the carbon fiber is 1.2 m / min), with an immersion depth of 10 cm. Excess resin is extruded through two pairs of pressure rollers (with a pressure of 0.3 MPa), and then pre-cured at 80 °C for 30 s and then laminated with a release film, and pressed by two pairs of rubber rollers to obtain the wear-resistant prepreg;

[0096] In the wear-resistant prepreg, the mass ratio of carbon fiber to resin matrix is 60:40; the mass of the nanoparticles is 10% of the mass of the resin matrix; and / or, the mass ratio of the epoxy resin to the acid anhydride curing agent is 100:85; the mass of the accelerator is 1.5% of the total mass of the epoxy resin and the acid anhydride curing agent;

[0097] The pressing conditions of the two pairs of rubber rollers include: a temperature of 60 °C and a pressure of 0.1 MPa; the winding conditions include: the tension control is 20 N / cm.

[0098] Comparative Example 1

[0099] This comparative example is used to illustrate the wear-resistant prepreg and its preparation method of the present invention.

[0100] The preparation of the nanoparticles includes:

[0101] Aluminum oxide (aluminum oxide with D50 of 60 nm, D10 of 40 nm, and D90 of 91 nm) was placed in an aqueous ethanol solution with a volume fraction of 50%, ultrasonically dispersed for 15 min, and then dried at 80 °C for 2 h; then the dried wear-resistant particles were placed in an aqueous solution of silane coupling agent (KH550) with a volume concentration of 1% and pH = 4, ultrasonically dispersed for 15 min, and then dried at 120 °C for 2 h to obtain the nanoparticles.

[0102] The preparation of the wear-resistant prepreg includes:

[0103] Epoxy resin, anhydride curing agent, accelerator, and the above-mentioned nanoparticles were mixed in a vacuum mixer under the mixing conditions of a rotation speed of 300 rpm, a vacuum degree of -0.1 MPa, and a time of 30 min to obtain a resin impregnating solution;

[0104] The carbon fiber roving enters the resin tank through a guide roller (the temperature of the resin tank is 40 °C, and the traction rate of the carbon fiber is 1.2 m / min), with an immersion depth of 10 cm. Excess resin is extruded through two sets of opposed pressure rollers (pressure is 0.3 MPa), and then pre-cured at 80 °C for 30 s and then laminated with a release film, and laminated by two sets of rubber rollers to obtain the wear-resistant prepreg;

[0105] In the wear-resistant prepreg, the mass ratio of carbon fiber to resin matrix is 60:40; the mass of the nanoparticles is 10% of the mass of the resin matrix; and / or, the mass ratio of the epoxy resin to the anhydride curing agent is 100:85; the mass of the accelerator is 1.5% of the total mass of the epoxy resin and the anhydride curing agent;

[0106] The lamination conditions of the two sets of rubber rollers include: temperature is 60 °C, pressure is 0.1 MPa; the winding conditions include: the tension control is 20 N / cm.

[0107] Comparative Example 2

[0108] This comparative example is used to illustrate the wear-resistant prepreg and its preparation method of the present invention.

[0109] The nanoparticles include: aluminum oxide (aluminum oxide with D50 of 60 nm, D10 of 40 nm, and D90 of 91 nm).

[0110] The preparation of the wear-resistant prepreg includes:

[0111] Epoxy resin, anhydride curing agent, accelerator, and the above-mentioned nanoparticles were mixed in a vacuum mixer under the mixing conditions of a rotation speed of 300 rpm, a vacuum degree of -0.1 MPa, and a time of 30 min to obtain a resin impregnating solution;

[0112] The carbon fiber roving enters the resin tank through a guiding roller (the temperature of the resin tank is 40°C, and the traction rate of the carbon fiber is 1.2 m / min), with an immersion depth of 10 cm. Excess resin is extruded through two sets of opposing rollers (pressure is 0.3 MPa), and then pre-cured at 80°C for 30 s and then compounded with a release film, and pressed by two sets of rubber rollers, and wound up to obtain the wear-resistant prepreg;

[0113] In the wear-resistant prepreg, the mass ratio of carbon fiber to resin matrix is 60:40; the mass of the nano-particles is 10% of the mass of the resin matrix; and / or, the mass ratio of the epoxy resin to the anhydride curing agent is 100:85; the mass of the accelerator is 1.5% of the total mass of the epoxy resin and the anhydride curing agent;

[0114] The pressing conditions of the two sets of rubber rollers include: temperature is 60°C, pressure is 0.1 MPa; the winding conditions include: the tension control is 20 N / cm.

[0115] Comparative Example 3

[0116] This comparative example is used to illustrate the wear-resistant prepreg and its preparation method of the present invention.

[0117] The nano-particles include: alumina (a combination of alumina with D50 of 60 nm, D10 of 40 nm, D90 of 91 nm and alumina with D50 of 90 nm, D10 of 60 nm, D90 of 105 nm, and the mass ratio is 1:3.5).

[0118] The preparation of the wear-resistant prepreg includes:

[0119] Mix the epoxy resin, anhydride curing agent, accelerator and the above-mentioned nano-particles in a vacuum mixer, and the mixing conditions are rotation speed of 300 rpm, vacuum degree of -0.1 MPa, and time of 30 min to obtain a resin impregnating solution;

[0120] The carbon fiber roving enters the resin tank through a guiding roller (the temperature of the resin tank is 40°C, and the traction rate of the carbon fiber is 1.2 m / min), with an immersion depth of 10 cm. Excess resin is extruded through two sets of opposing rollers (pressure is 0.3 MPa), and then pre-cured at 80°C for 30 s and then compounded with a release film, and pressed by two sets of rubber rollers, and wound up to obtain the wear-resistant prepreg;

[0121] In the wear-resistant prepreg, the mass ratio of carbon fiber to resin matrix is 60:40; the mass of the nano-particles is 10% of the mass of the resin matrix; and / or, the mass ratio of the epoxy resin to the anhydride curing agent is 100:85; the mass of the accelerator is 1.5% of the total mass of the epoxy resin and the anhydride curing agent;

[0122] The pressing conditions of the two groups of rubber rollers include: temperature of 60 °C and pressure of 0.1 MPa; the winding conditions include: tension control of 20 N / cm.

[0123] Comparative Example 4

[0124] This comparative example is used to illustrate the wear-resistant prepreg and its preparation method described in the present invention.

[0125] The preparation of the nano-particles includes:

[0126] Aluminum oxide (a combination of aluminum oxide with D50 of 60 nm, D10 of 40 nm, D90 of 91 nm and aluminum oxide with D50 of 80 nm, D10 of 62 nm, D90 of 102 nm, with a mass ratio of 1:3.5) is placed in an aqueous ethanol solution of 50 vol%, ultrasonically dispersed for 15 min, and then dried at 80 °C for 2 h; then the dried wear-resistant particles are placed in an aqueous solution of silane coupling agent (KH550) with a volume concentration of 1% and pH = 4, ultrasonically dispersed for 15 min, and then dried at 120 °C for 2 h to obtain the nano-particles.

[0127] The preparation of the wear-resistant prepreg includes:

[0128] Epoxy resin, acid anhydride curing agent, accelerator and the above-mentioned nano-particles are mixed in a vacuum mixer, and the mixing conditions are a rotation speed of 300 rpm, a vacuum degree of -0.1 MPa, and a time of 30 min to obtain a resin impregnating solution;

[0129] The carbon fiber roving enters the resin tank through a guide roller (the temperature of the resin tank is 40 °C, and the traction rate of the carbon fiber is 1.2 m / min), the immersion depth is 10 cm, the excess resin is extruded through two groups of opposing rollers (pressure of 0.3 MPa), then pre-cured at 80 °C for 30 s and then compounded with a release film, and pressed by two groups of rubber rollers and wound to obtain the wear-resistant prepreg;

[0130] In the wear-resistant prepreg, the mass ratio of carbon fiber to resin matrix is 60:40; the mass of the nano-particles is 10% of the mass of the resin matrix; and / or, the mass ratio of the epoxy resin to the acid anhydride curing agent is 100:85; the mass of the accelerator is 1.5% of the total mass of the epoxy resin and the acid anhydride curing agent;

[0131] The pressing conditions of the two groups of rubber rollers include: temperature of 60 °C and pressure of 0.1 MPa; the winding conditions include: tension control of 20 N / cm.

[0132] Comparative Example 5

[0133] This comparative example is used to illustrate the wear-resistant prepreg and its preparation method described in the present invention.

[0134] The preparation of the wear-resistant prepreg includes:

[0135] Mix epoxy resin, anhydride curing agent, and accelerator in a vacuum mixer under the conditions of a rotation speed of 300 rpm, a vacuum degree of -0.1 MPa, and a time of 30 min to obtain a resin impregnating solution;

[0136] The carbon fiber roving enters the resin bath through a guide roller (the temperature of the resin bath is 40°C, and the traction rate of the carbon fiber is 1.2 m / min), with an immersion depth of 10 cm. Excess resin is extruded through two sets of opposing pressure rollers (pressure is 0.3 MPa), and then pre-cured at 80°C for 30 s and then laminated with a release film, and pressed by two sets of rubber rollers and wound to obtain the wear-resistant prepreg;

[0137] In the wear-resistant prepreg, the mass ratio of carbon fiber to resin matrix is 60:40; and / or, the mass ratio of the epoxy resin to the anhydride curing agent is 100:85; the mass of the accelerator is 1.5% of the total mass of the epoxy resin and the anhydride curing agent;

[0138] The pressing conditions of the two sets of rubber rollers include: a temperature of 60°C and a pressure of 0.1 MPa; the winding conditions include: the tension is controlled at 20 N / cm.

[0139] Application Example

[0140] This application example is used to illustrate the application of the wear-resistant prepregs prepared in Examples 1-5 and Comparative Examples 1-5 of the present invention.

[0141] Lay the carbon fiber prepreg prepared in Comparative Example 5 (3 layers) on a mold, and then cover a layer of the wear-resistant prepregs prepared in Examples 1-5 and Comparative Examples 1-5 on the surface of the carbon fiber prepreg prepared in Comparative Example 5 respectively. Then stick a sealing strip and a vacuum bag around the mold on which the carbon fiber prepreg is laid, evacuate, and put it into a curing furnace for curing (temperature 130°C, time 12 h). After demolding, a carbon fiber-reinforced epoxy resin composite material is obtained, and the obtained carbon fiber-reinforced epoxy resin composite material is subjected to a TABER wear test;

[0142] During the TABER test, the thickness of the sample plate is controlled at 4.0 ± 0.2 mm, cut into circular specimens (diameter 100 mm, center hole 6 mm), and placed on a TABER abrasion machine; fix the specimen on the turntable to ensure accurate positioning of the center hole and uniform clamping force (to avoid warping); record the initial mass, and record the mass after the experiment after 3000 R. The mass change is the wear rate; the grinding wheel model is H-18, and the load is 1 kg / wheel), and the wear rates are statistically shown in Table 1.

[0143] Table 1

[0144] sample TABER wear rate (%) Example 1 0.74 Example 2 0.53 Example 3 0.59 Example 4 1.12 Example 5 0.89 Comparative Example 1 1.28 Comparative Example 2 1.92 Comparative Example 3 1.44 Comparative Example 4 1.01 Comparative Example 5 2.77

[0145] As can be seen from the results in Table 1, the wear-resistant prepreg of the present invention has good affinity with the carbon fiber prepreg without nanoparticles, can be firmly combined with it, effectively improves the wear resistance of the prepreg, and enhances the wear resistance of the carbon fiber reinforced epoxy composite material.

[0146] It should be noted that the above-described embodiments are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described by referring to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words rather than limiting words. Modifications can be made to the present invention within the scope of the claims of the present invention as provided, and the present invention can be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein. On the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A wear-resistant prepreg, characterized in that: The raw materials for preparing the wear-resistant prepreg include a resin matrix, carbon fibers and at least two nanoparticles with different median particle sizes and modified by a silane coupling agent.

2. The wear-resistant prepreg according to claim 1, characterized in that: In the wear-resistant prepreg, the mass ratio of carbon fiber to resin matrix is ​​60:40-45; The mass of the nanoparticles is 8% to 12% of the mass of the resin matrix.

3. The wear-resistant prepreg according to claim 1 or 2, characterized in that: The nanoparticles are selected from at least one of aluminum oxide, silicon oxide or silicon carbide; preferably, the wear-resistant particles are selected from aluminum oxide and / or silicon carbide.

4. The wear-resistant prepreg according to any one of claims 1 to 3, characterized in that: The nanoparticles include at least first nanoparticles and second nanoparticles; preferably, the D50 of the first nanoparticles is 50nm-80nm, D10 is 40nm-46nm, and D90 is 83nm-94nm, the D50 of the second nanoparticles is 60nm-100nm, D10 is 57nm-62nm, and D90 is 98nm-108nm, and the difference between the D50 of the first nanoparticles and the D50 of the second nanoparticles is ≧30nm, preferably 30nm-40nm; further preferably, the mass ratio of the first nanoparticles to the second nanoparticles is 1:2-5.

5. The wear-resistant prepreg according to any one of claims 1 to 4, characterized in that: The resin matrix includes epoxy resin, anhydride curing agent and accelerator; Preferably, the mass ratio of the epoxy resin to the acid anhydride curing agent is 100:85-90; the mass of the accelerator is 1.5% to 2.0% of the total mass of the epoxy resin and the acid anhydride curing agent; Further preferably, the epoxy resin is selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD ​​epoxy resin, and bisphenol S epoxy resin; the acid anhydride curing agent is selected from at least one of methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride; and the accelerator is selected from at least one of 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole.

6. The wear-resistant prepreg according to any one of claims 1 to 5, characterized in that: The step of modifying the nanoparticles with a silane coupling agent comprises: placing the nanoparticles in a 30 vol% to 50 vol% ethanol aqueous solution, ultrasonically dispersing for 15 minutes to 30 minutes, and then performing a first drying; then placing the first dried nanoparticles in a 1% to 3% volume concentration, pH=4-5 silane coupling agent aqueous solution, ultrasonically dispersing for 15 minutes to 30 minutes, and then performing a second drying to obtain nanoparticles modified with a silane coupling agent; Preferably, the first drying conditions include: temperature of 80°C to 100°C and time of 2h to 4h; And / or, the temperature of the second drying is 120° C. to 140° C., and the time is 2 h to 4 h.

7. The method for preparing the wear-resistant prepreg according to any one of claims 1 to 6, characterized in that: The preparation method of the wear-resistant prepreg comprises: (1) preparing a resin impregnation solution: mixing the nanoparticles with a resin matrix to obtain a resin impregnation solution; (2) Impregnation: Impregnating the carbon fiber in the resin impregnation solution obtained in step (1), precuring, and obtaining the wear-resistant prepreg.

8. The preparation method according to claim 7, characterized in that: In step (1), the mixing is carried out in a vacuum mixer; preferably, the mixing conditions include: a rotation speed of 300 rpm to 400 rpm, a vacuum degree of -0.05 MPa to -0.1 MPa, and a time of 30 min to 40 min.

9. The preparation method according to claim 7 or 8, characterized in that: In step (2), the immersion is carried out in a resin tank; preferably, the temperature of the resin tank is 40±2°C; And / or, the impregnation conditions include: a pressure of 0.2MPa to 0.5MPa; And / or, the pre-curing conditions include: temperature of 80° C. to 85° C. and time of 30 s to 40 s.

10. A carbon fiber reinforced epoxy resin composite material, characterized in that: The invention comprises the wear-resistant prepreg according to any one of claims 1 to 6 or the wear-resistant prepreg prepared by the preparation method according to any one of claims 7 to 9.

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