Carbon fiber resin matrix composite material for ski and method for manufacturing the same

Abstract

The application provides a carbon fiber resin matrix composite material for skis and a preparation method thereof. The composite material has the advantages of high toughness at low temperature by using the composition and the preparation method. When the composite material is used in skis, the negative influence of low temperature on interlayer mechanical properties is reduced, the response sensitivity of the skis to the action of skiers is improved, and the feedback efficiency of the snow surface to the action of skiers is improved, so that the matching degree of the skiers and the skis is higher.

Description

Technical Field

[0001] This invention relates to the field of composite material preparation technology, specifically to a carbon fiber resin-based composite material for skis and its preparation method. Background Technology

[0002] As the core equipment of skiing, skis directly affect the user's athletic performance and safety. With the popularization of skiing and the improvement of competitive levels, the performance requirements for ski materials are becoming increasingly stringent.

[0003] Carbon fiber composite materials have advantages such as being lightweight, high-strength, and high-modulus, making them an ideal material for making skis. Current carbon fiber composite skis use advanced high-performance materials such as carbon fiber and resin matrix, and through precise lamination processes and mold forming technology, the advantages of lightweight, high strength, and corrosion resistance of the materials are perfectly combined.

[0004] However, skis are typically stored at room temperature, while the actual operating temperature is much lower, such as -20°C or even lower. This temperature difference causes the resin matrix of carbon fiber composite materials to become less tough and more brittle, which can lead to excessive torsional rigidity, reduced energy transfer, and decreased stability when used on skis. These changes in performance make it difficult for skis to accurately respond to changes in the skier's movements, thus affecting the skier's actions.

[0005] Therefore, providing a composite material that can reduce the response delay of skis is of great significance to the industry. Summary of the Invention

[0006] To address the aforementioned shortcomings of existing technologies, this invention provides a carbon fiber resin matrix composite material for skis and its preparation method. The composite material obtained using the composition and preparation method provided by this invention exhibits the advantage of high low-temperature toughness. When used in skis, this composite material reduces the impact of low temperatures on the toughness, brittleness, and interlaminar mechanical properties of the carbon fiber composite resin matrix, ensuring the torsional rigidity of the skis, reducing the impact on energy conduction, improving the skis' responsiveness to skier movements, and enhancing the snow's feedback efficiency to skiers' movements, thereby achieving a higher degree of coordination between the skier and the skis.

[0007] The technical solution of the present invention is as follows: A carbon fiber resin-based composite material for skis, comprising the following components in parts by weight: 40-60 parts carbon fiber, 25-40 parts modified epoxy resin matrix, 5-10 parts curing agent, 3-8 parts toughening agent, 2-6 parts wear-resistant filler, 1-3 parts coupling agent, and 0.5-2 parts antioxidant; The modified epoxy resin matrix includes bisphenol A type epoxy resin and silicone modified epoxy resin; the mass ratio of bisphenol A type epoxy resin to silicone modified epoxy resin is 3-5:1; the introduction of silicone modified epoxy resin can significantly improve the low-temperature toughness of the modified epoxy resin matrix, making the composite material more adaptable to the low-temperature environment of -40℃ and reducing the embrittlement of the modified epoxy resin matrix.

[0008] Preferably, the organosilicon-modified epoxy resin is prepared by the following method: S1, Material Preparation By weight, take 60-80 parts of bisphenol A type epoxy resin, 20-40 parts of silane coupling agent KH560, 10-20 parts of anhydrous ethanol, and 0.5-1.5 parts of dibutyltin dilaurate; S2, premixed reaction Add bisphenol A epoxy resin to a reactor equipped with a stirrer and a reflux condenser, heat to 80-90℃, stir at 300-500r / min, add anhydrous ethanol and dibutyltin dilaurate, and stir for 10-15min. S3, grafting reaction Add the silane coupling agent KH560 dropwise to the reactor. After the addition is complete, raise the temperature to 100-110℃ and keep the temperature for 2-3 hours. S4, Post-processing After the reaction was completed, the reaction product was cooled to 60-70℃ and distilled under reduced pressure to obtain a light yellow transparent organosilicon-modified epoxy resin.

[0009] Preferably, in step S4, the conditions for vacuum distillation are: distillation pressure 0.06-0.08 MPa, distillation time 1-1.5 h.

[0010] Preferably, the carbon fiber is T700 or T800 grade carbon fiber. Using this grade of carbon fiber as a reinforcement can provide excellent mechanical support for the composite material.

[0011] Preferably, the curing agent is methyltetrahydrophthalic anhydride, which has excellent low-temperature curing properties and can fully react with epoxy resin at lower temperatures to form a dense cross-linked structure, thereby improving the mechanical properties and low-temperature stability of the composite material.

[0012] Preferably, the toughening agent is a core-shell structured acrylate elastomer, with a core layer of polybutadiene and a shell layer of polymethyl methacrylate, and a particle size of 50-200 nm. The core-shell structured toughening agent can effectively improve the toughness of the epoxy resin matrix through a particle toughening mechanism, while not affecting the rigidity of the matrix, thereby further optimizing the low-temperature mechanical properties of the composite material.

[0013] Preferably, the core-shell structured acrylate elastomer is prepared by the following method: SS1, Preparation of Seed Solution By mass, add 80-100 parts of deionized water, 0.8-1.5 parts of sodium dodecyl sulfate, 0.3-0.6 parts of ammonium persulfate, and 20-30 parts of butadiene monomer to a reaction vessel. Purge the air in the vessel with nitrogen 3-5 times, raise the temperature to 60-70℃, stir at 200-300 r / min, and keep the reaction at this temperature for 3-4 hours to obtain polybutadiene seed emulsion. SS2, shell polymerization Add 15-25 parts of methyl methacrylate monomer and 2-5 parts of butyl acrylate to the seed emulsion, and continue the reaction at 60-70℃ for 2-3 hours; during this period, add 0.1-0.2 parts of ammonium persulfate to maintain stable polymerization of the system; SS3, Post-processing After the reaction was completed, the emulsion was cooled to room temperature and the pH was adjusted to 6.5-7.5 with a 5% sodium hydroxide solution. Then, it was concentrated by vacuum distillation and spray-dried to obtain a powdered core-shell structured acrylate elastomer.

[0014] Preferably, in step SS2, ammonium persulfate is added in two parts: the first part is added after 1 hour of heat preservation reaction, and the second part is added 1 hour after the first addition.

[0015] Preferably, in step SS3, the conditions for vacuum distillation are a distillation pressure of 0.07-0.09 MPa and a temperature of 50-60°C; the inlet air temperature for spray drying is 120-130°C and the outlet air temperature is 60-70°C.

[0016] Preferably, the wear-resistant filler is a mixture of nano-alumina and nano-silica in a mass ratio of 2:1-3:1, with a particle size of 50-100nm. Both nano-alumina and nano-silica have high hardness and excellent wear resistance. When combined, they can be uniformly dispersed in the modified epoxy resin matrix, significantly improving the surface wear resistance of the composite material and reducing friction damage during skiing.

[0017] Preferably, the coupling agent is a silane coupling agent KH-550; the coupling agent can improve the interfacial bonding force between carbon fiber, wear-resistant filler and resin matrix, enhance the interlaminar shear strength of composite material and avoid interlaminar delamination.

[0018] Preferably, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1; the antioxidant can inhibit the oxidative aging of the composite material during processing and use, and extend the service life of the composite material.

[0019] A method for preparing carbon fiber resin-based composite material for skis, the process is as follows: Step 1: Carbon fiber pretreatment The carbon fiber was placed in a plasma treatment device under an argon atmosphere. The plasma power was 80-120W and the treatment time was 10-20 minutes. After treatment, immerse it in a coupling agent solution, which is prepared by mixing coupling agent and ethanol at a mass ratio of 1:50-80, and soak for 2-4 hours. Then, it is taken out and dried at 80-100℃ for 2-3 hours to obtain pretreated carbon fiber; Plasma treatment and coupling agent modification can enhance the activity and roughness of carbon fiber surfaces, thereby strengthening their interfacial bonding with the modified epoxy resin matrix. Step 2, Preparation of composite matrix According to the mass fraction, add the modified epoxy resin matrix, toughening agent, wear-resistant filler and antioxidant into a high-speed mixer and mix for 30-40 minutes at a speed of 1500-2000 r / min and a temperature of 60-80℃. Then add the curing agent and continue mixing for 15-20 minutes to obtain a uniform composite matrix; This mixing process ensures that the components are fully dispersed and avoids localized aggregation. Step 3, composite molding, using resin transfer molding process for composite molding. The pretreated carbon fiber from step one is laid in the mold according to the preset layup method. The mold is then closed and sealed. The composite matrix prepared in step two is injected into the mold at an injection pressure of 0.3-0.5 MPa and an injection temperature of 70-80℃. After injection, a curing process is performed. The curing process is as follows: first, keep the temperature at 80℃ for 2-3 hours, then raise the temperature to 120℃ and keep it at 3-3.5 hours, and finally raise the temperature to 150℃ and keep it at 1-1.5 hours. After curing, cool to room temperature and demold to obtain the composite material preform; This process ensures that the composite matrix and carbon fiber are fully impregnated to form a dense composite material structure. At the same time, the layup method can be designed according to the performance requirements of the skis to ensure that the mechanical properties of the composite material are evenly distributed. Step 4, Post-processing The composite material preform is machined to remove burrs and excess edges, followed by surface grinding and polishing to obtain the final carbon fiber resin-based composite material for skis.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. In this invention, by introducing organosilicon-modified epoxy resin and core-shell structure acrylate elastomer toughening agent, the low-temperature toughness of the composite matrix is ​​significantly improved, avoiding torsional stiffness fluctuations caused by excessive embrittlement of the composite matrix, maintaining stable torsional performance, and improving the adaptability of skis in extreme low-temperature environments.

[0021] 2. In this invention, a wear-resistant filler composed of nano-alumina and nano-silica is added. By uniformly dispersing the wear-resistant filler in the resin matrix, the surface wear resistance of the composite material is significantly improved, friction damage with the snow and ground during skiing is reduced, and the service life of the skis is extended.

[0022] 3. In this invention, by plasma treatment and coupling agent modification of carbon fiber, the interfacial bonding force between carbon fiber and composite matrix is ​​improved. At the same time, the molding process is optimized, which significantly improves the interlaminar shear strength of composite material, meets the load-bearing requirements of skis under complex working conditions, avoids interlaminar delamination, and ensures energy conduction efficiency at low temperatures, so that the snow surface can better respond to the actions and forces of skiers. Detailed Implementation

[0023] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this invention.

[0024] In this invention, the carbon fiber is T700 grade carbon fiber, the curing agent is methyltetrahydrophthalic anhydride, the wear-resistant filler is a mixture of nano-alumina and nano-silica in a mass ratio of 2.5:1 with a particle size of 50-100nm, the coupling agent is silane coupling agent KH-550, and the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

[0025] Example 1 A carbon fiber resin-based composite material for skis, comprising the following components in parts by weight: 50 parts carbon fiber, 35 parts modified epoxy resin matrix, 7 parts curing agent, 5 parts toughening agent, 4 parts wear-resistant filler, 2 parts coupling agent, and 1 part antioxidant; The modified epoxy resin matrix includes bisphenol A type epoxy resin and silicone modified epoxy resin; the mass ratio of bisphenol A type epoxy resin and silicone modified epoxy resin is 4:1. The preparation method of silicone-modified epoxy resin is as follows: S1, Material Preparation Take 70 parts by weight of bisphenol A epoxy resin, 30 parts of silane coupling agent KH560, 15 parts of anhydrous ethanol, and 1 part of dibutyltin dilaurate. S2, premixed reaction Bisphenol A type epoxy resin was added to a reactor equipped with a stirrer and a reflux condenser. The temperature was raised to 85°C and the stirring speed was 400 r / min. Anhydrous ethanol and dibutyltin dilaurate were added and stirred for 12 min. S3, grafting reaction The silane coupling agent KH560 was added dropwise to the reactor. After the addition was complete, the temperature was raised to 105°C and the reaction was maintained at this temperature for 2.5 hours. S4, Post-processing After the reaction was completed, the reaction product was cooled to 65°C and distilled under reduced pressure to obtain a pale yellow transparent organosilicon-modified epoxy resin. The conditions for vacuum distillation are: distillation pressure 0.07 MPa, distillation time 1.3 h; The toughening agent is a core-shell structured acrylate elastomer, with a core layer of polybutadiene and a shell layer of polymethyl methacrylate, and a particle size of 50-200 nm; the preparation method is as follows: SS1, Preparation of Seed Solution By mass, 90 parts of deionized water, 1.1 parts of sodium dodecyl sulfate, 0.4 parts of ammonium persulfate, and 25 parts of butadiene monomer were added to the reactor. Nitrogen gas was introduced to replace the air in the reactor four times. The temperature was raised to 65°C, the stirring speed was 250 r / min, and the reaction was kept at this temperature for 3.5 h to obtain polybutadiene seed emulsion. SS2, shell polymerization Add 20 parts of methyl methacrylate monomer and 4 parts of butyl acrylate to the seed emulsion, and continue to react at 65℃ for 2.5h; during this period, add 0.16 parts of ammonium persulfate to maintain stable polymerization of the system; Ammonium persulfate was added in two batches, 0.08 parts each time; the first batch was added after 1 hour of incubation, and the second batch was added 1 hour after the first batch. SS3, Post-processing After the reaction was completed, the emulsion was cooled to room temperature, and the pH was adjusted to 7.0 with a 5% sodium hydroxide solution. Then, it was concentrated by vacuum distillation and spray dried to obtain a powdered core-shell structured acrylate elastomer. The conditions for vacuum distillation are: distillation pressure 0.08 MPa and temperature 55℃; the inlet air temperature for spray drying is 125℃ and the outlet air temperature is 65℃. The preparation method of the above-mentioned carbon fiber resin matrix composite material for skis is as follows: Step 1: Carbon fiber pretreatment The carbon fiber was placed in a plasma treatment device under an argon atmosphere, with a plasma power of 100W and a treatment time of 15 minutes. After treatment, it is immersed in a coupling agent solution, which is prepared by mixing coupling agent and ethanol at a mass ratio of 1:70, and the immersion time is 3 hours. The carbon fiber was then removed and dried at 90°C for 2.5 hours to obtain pretreated carbon fiber. Step 2, Preparation of composite matrix According to the mass fractions, the modified epoxy resin matrix, toughening agent, wear-resistant filler and antioxidant are added to a high-speed mixer and mixed for 35 minutes at a speed of 1800 r / min and a temperature of 70℃. Then add the curing agent and continue mixing for 17 minutes to obtain a uniform composite matrix; Step 3, composite molding, using resin transfer molding process for composite molding. The pretreated carbon fiber from step one is laid in the mold according to the preset layup method. The mold is then closed and sealed. The composite matrix prepared in step two is injected into the mold at an injection pressure of 0.4 MPa and an injection temperature of 75°C. After injection, a curing process is performed. The curing process is as follows: first, keep the temperature at 80℃ for 2 hours, then raise the temperature to 120℃ and keep it at 3 hours, and finally raise the temperature to 150℃ and keep it at 1 hour. After curing, cool to room temperature and demold to obtain the composite material preform; This process ensures that the composite matrix and carbon fiber are fully impregnated to form a dense composite material structure. At the same time, the layup method can be designed according to the performance requirements of the skis to ensure that the mechanical properties of the composite material are evenly distributed. Step 4, Post-processing The composite material preform is machined to remove burrs and excess edges, followed by surface grinding and polishing to obtain the final carbon fiber resin-based composite material for skis.

[0026] Comparative Example 1 The difference from Example 1 is that no silicone-modified epoxy resin is added to the modified epoxy resin matrix, and the silicone-modified epoxy resin is replaced with an equal amount of bisphenol A type epoxy resin.

[0027] Comparative Example 2 The difference from Example 1 is that step one in the preparation process of the composite material is different; in this Comparative Example 2, step one is: immersing carbon fibers in a coupling agent solution, which is prepared by mixing coupling agent and ethanol at a mass ratio of 1:60, and soaking for 3 hours; then taking them out and drying them at 90°C for 2.5 hours to obtain pretreated carbon fibers.

[0028] Example 2 The difference from Example 1 lies in the preparation method of the modified epoxy resin matrix; in this example, the preparation method of the modified epoxy resin matrix is ​​as follows: S1, Material Preparation By weight, take 60 parts of bisphenol A epoxy resin, 20 parts of silane coupling agent KH560, 10 parts of anhydrous ethanol, and 0.5 parts of dibutyltin dilaurate; S2, premixed reaction Bisphenol A type epoxy resin was added to a reactor equipped with a stirrer and a reflux condenser. The temperature was raised to 80°C and the stirring speed was 300 r / min. Anhydrous ethanol and dibutyltin dilaurate were added and stirred for 10 min. S3, grafting reaction The silane coupling agent KH560 was added dropwise to the reactor. After the addition was complete, the temperature was raised to 100°C and the reaction was maintained for 2 hours. S4, Post-processing After the reaction was completed, the reaction product was cooled to 60°C and distilled under reduced pressure to obtain a pale yellow transparent organosilicon-modified epoxy resin. The conditions for vacuum distillation are: distillation pressure 0.06 MPa and distillation time 1 h.

[0029] Example 3 The difference from Example 1 lies in the preparation method of the modified epoxy resin matrix; in this example, the preparation method of the modified epoxy resin matrix is ​​as follows: S1, Material Preparation Take 80 parts by weight of bisphenol A epoxy resin, 40 parts of silane coupling agent KH560, 20 parts of anhydrous ethanol, and 1.5 parts of dibutyltin dilaurate; S2, premixed reaction Bisphenol A type epoxy resin was added to a reaction vessel equipped with a stirrer and a reflux condenser, the temperature was raised to 90°C, the stirring speed was 500 r / min, anhydrous ethanol and dibutyltin dilaurate were added, and the mixture was stirred for 15 min. S3, grafting reaction The silane coupling agent KH560 was added dropwise to the reactor. After the addition was complete, the temperature was raised to 110°C and the reaction was maintained for 3 hours. S4, Post-processing After the reaction was completed, the reaction product was cooled to 70°C and distilled under reduced pressure to obtain a pale yellow transparent organosilicon-modified epoxy resin. The conditions for vacuum distillation are: distillation pressure 0.08 MPa and distillation time 1.5 h.

[0030] Example 4 The difference from Example 1 lies in the preparation method of the core-shell structured acrylate elastomer; in this example, the preparation method of the core-shell structured acrylate elastomer is as follows: SS1, Preparation of Seed Solution By mass fraction, 80 parts of deionized water, 0.8 parts of sodium dodecyl sulfate, 0.3 parts of ammonium persulfate, and 20 parts of butadiene monomer were added to the reactor. Nitrogen gas was introduced to replace the air in the reactor three times. The temperature was raised to 60°C, the stirring speed was 200 r / min, and the reaction was kept at this temperature for 4 hours to obtain polybutadiene seed emulsion. SS2, shell polymerization Add 15 parts of methyl methacrylate monomer and 2 parts of butyl acrylate to the seed emulsion, and continue to react at 60℃ for 3 hours; during this period, add 0.1 parts of ammonium persulfate to maintain stable polymerization of the system; Ammonium persulfate was added in two batches, 0.05 parts each time. The first batch was added after 1 hour of incubation, and the second batch was added 1 hour after the first batch. SS3, Post-processing After the reaction was completed, the emulsion was cooled to room temperature, and the pH was adjusted to 6.5 with a 5% sodium hydroxide solution. Then, it was concentrated by vacuum distillation and spray dried to obtain a powdered core-shell structured acrylate elastomer. The conditions for vacuum distillation are a distillation pressure of 0.07 MPa and a temperature of 50°C; the inlet air temperature for spray drying is 120°C and the outlet air temperature is 60°C.

[0031] Example 5 The difference from Example 1 lies in the preparation method of the core-shell structured acrylate elastomer; in this example, the preparation method of the core-shell structured acrylate elastomer is as follows: SS1, Preparation of Seed Solution By mass, 100 parts of deionized water, 1.5 parts of sodium dodecyl sulfate, 0.6 parts of ammonium persulfate, and 30 parts of butadiene monomer were added to the reactor. Nitrogen gas was introduced to replace the air in the reactor four times. The temperature was raised to 70°C, the stirring speed was 300 r / min, and the reaction was kept at this temperature for 3 hours to obtain polybutadiene seed emulsion. SS2, shell polymerization Add 25 parts of methyl methacrylate monomer and 5 parts of butyl acrylate to the seed emulsion, and continue to react at 70°C for 2 hours; during this period, add 0.2 parts of ammonium persulfate to maintain stable polymerization of the system; Ammonium persulfate was added in two batches, 0.1 parts each time. The first batch was added after 1 hour of incubation, and the second batch was added 1 hour after the first batch. SS3, Post-processing After the reaction was completed, the emulsion was cooled to room temperature, and the pH was adjusted to 7.5 with a 5% sodium hydroxide solution. Then, it was concentrated by vacuum distillation and spray dried to obtain a powdered core-shell structured acrylate elastomer. The conditions for vacuum distillation are a distillation pressure of 0.09 MPa and a temperature of 60°C; the inlet air temperature for spray drying is 130°C and the outlet air temperature is 70°C.

[0032] Example 6 A carbon fiber resin-based composite material for skis, comprising the following components in parts by weight: 40 parts carbon fiber, 25 parts modified epoxy resin matrix, 5 parts curing agent, 3 parts toughening agent, 2 parts wear-resistant filler, 1 part coupling agent, and 0.5 parts antioxidant; The modified epoxy resin matrix includes bisphenol A type epoxy resin and silicone modified epoxy resin; the mass ratio of bisphenol A type epoxy resin and silicone modified epoxy resin is 3:1. The preparation method of the organosilicon-modified epoxy resin is the same as in Example 1; The toughening agent was prepared using the same method as in Example 1; The preparation method of the above-mentioned carbon fiber resin matrix composite material for skis is as follows: Step 1: Carbon fiber pretreatment The carbon fiber was placed in a plasma treatment device under an argon atmosphere, with a plasma power of 80W and a treatment time of 20 minutes. After treatment, it is immersed in a coupling agent solution, which is prepared by mixing coupling agent and ethanol at a mass ratio of 1:50, and the immersion time is 4 hours. The carbon fiber was then removed and dried at 80°C for 3 hours to obtain pretreated carbon fiber. Step 2, Preparation of composite matrix According to the mass fractions, the modified epoxy resin matrix, toughening agent, wear-resistant filler, and antioxidant are added to a high-speed mixer and mixed for 40 minutes at a speed of 1500 r / min and a temperature of 60℃. Then add the curing agent and continue mixing for 20 minutes to obtain a uniform composite matrix; Step 3, composite molding, using resin transfer molding process for composite molding. The pretreated carbon fiber from step one is laid in the mold according to the preset layup method. The mold is then closed and sealed. The composite matrix prepared in step two is injected into the mold at an injection pressure of 0.3 MPa and an injection temperature of 70°C. After injection, a curing process is performed. The curing process is as follows: first, keep the temperature at 80℃ for 2.5 hours, then raise the temperature to 120℃ and keep it at 3.5 hours, and finally raise the temperature to 150℃ and keep it at 1.5 hours. After curing, cool to room temperature and demold to obtain the composite material preform; Step 4, Post-processing The composite material preform is machined to remove burrs and excess edges, followed by surface grinding and polishing to obtain the final carbon fiber resin-based composite material for skis.

[0033] Example 7 A carbon fiber resin-based composite material for skis, comprising the following components in parts by weight: 60 parts carbon fiber, 40 parts modified epoxy resin matrix, 10 parts curing agent, 8 parts toughening agent, 6 parts wear-resistant filler, 3 parts coupling agent, and 2 parts antioxidant; The modified epoxy resin matrix includes bisphenol A type epoxy resin and silicone modified epoxy resin; the mass ratio of bisphenol A type epoxy resin and silicone modified epoxy resin is 5:1. The preparation method of the organosilicon-modified epoxy resin is the same as in Example 1; The toughening agent was prepared using the same method as in Example 1; The preparation method of the above-mentioned carbon fiber resin matrix composite material for skis is as follows: Step 1: Carbon fiber pretreatment The carbon fiber was placed in a plasma treatment device under an argon atmosphere. The plasma power was 120W and the treatment time was 10 minutes. After treatment, it is immersed in a coupling agent solution, which is prepared by mixing coupling agent and ethanol at a mass ratio of 1:80, and the immersion time is 2 hours. The carbon fiber was then removed and dried at 100°C for 2 hours to obtain pretreated carbon fiber. Step 2, Preparation of composite matrix According to the mass fractions, the modified epoxy resin matrix, toughening agent, wear-resistant filler, and antioxidant are added to a high-speed mixer and mixed for 30 minutes at a speed of 2000 r / min and a temperature of 80℃. Then add the curing agent and continue mixing for 15 minutes to obtain a uniform composite matrix; Step 3, composite molding, using resin transfer molding process for composite molding. The pretreated carbon fiber from step one is laid in the mold according to the preset layup method. The mold is then closed and sealed. The composite matrix prepared in step two is injected into the mold at an injection pressure of 0.5 MPa and an injection temperature of 80°C. After injection, a curing process is performed. The curing process is as follows: first, keep the temperature at 80℃ for 3 hours, then raise the temperature to 120℃ and keep it at 3.5 hours, and finally raise the temperature to 150℃ and keep it at 1.5 hours. After curing, cool to room temperature and demold to obtain the composite material preform; This process ensures that the composite matrix and carbon fiber are fully impregnated to form a dense composite material structure. At the same time, the layup method can be designed according to the performance requirements of the skis to ensure that the mechanical properties of the composite material are evenly distributed. Step 4, Post-processing The composite material preform is machined to remove burrs and excess edges, followed by surface grinding and polishing to obtain the final carbon fiber resin-based composite material for skis.

[0034] For the testing of composite materials in Examples 1-7 and Comparative Examples 1-2, the testing methods referred to the company's commonly used methods, which have been disclosed in previous patent applications and will not be repeated here. 1. Bending strength test: The corresponding bending strength was tested according to ASTM D790, and the results are shown in Table 1; Table 1 Bending strength test results

[0035] 2. Tensile strength test: The corresponding tensile strength was tested according to ASTM D3039, and the results are shown in Table 2; Table 2 Tensile strength test results

[0036] 3. Low-temperature impact resistance test: The test was conducted according to ASTM D256 (cantilever beam impact test), and the results are shown in Table 3: Table 3 Results of Low-Temperature Impact Resistance Test

[0037] 4. Interlaminar shear strength test: The interlaminar shear strength was tested according to ASTM D2344, and the results are shown in Table 4. Table 4 Results of Interlaminar Shear Strength Test

[0038] 5. Elastic modulus test, according to GB / T 1447-2005, the results are shown in Table 5; Table 5 Results of Elastic Modulus Test

[0039] 6. Abrasion resistance test, refer to GB / T1768 test, the results are shown in Table 6; Table 6 Abrasion resistance test results

[0040] Although the present invention has been described in detail with reference to preferred embodiments, it is not limited thereto. Various equivalent modifications or substitutions can be made to the embodiments of the present invention by those skilled in the art without departing from the spirit and essence of the invention, and such modifications or substitutions should all be within the scope of the present invention. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should also be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the scope of the claims.

Claims

1. A carbon fiber resin-based composite material for skis, characterized in that, The components include the following parts by mass: 40-60 parts carbon fiber, 25-40 parts modified epoxy resin matrix, 5-10 parts curing agent, 3-8 parts toughening agent, 2-6 parts wear-resistant filler, 1-3 parts coupling agent, and 0.5-2 parts antioxidant; The modified epoxy resin matrix includes bisphenol A type epoxy resin and silicone modified epoxy resin; the mass ratio of bisphenol A type epoxy resin to silicone modified epoxy resin is 3-5:

1.

2. The carbon fiber resin-based composite material for skis as described in claim 1, characterized in that, The silicone-modified epoxy resin is prepared by the following method: S1, Material Preparation By weight, take 60-80 parts of bisphenol A type epoxy resin, 20-40 parts of silane coupling agent KH560, 10-20 parts of anhydrous ethanol, and 0.5-1.5 parts of dibutyltin dilaurate; S2, premixed reaction Add bisphenol A epoxy resin to a reactor equipped with a stirrer and a reflux condenser, heat to 80-90℃, stir at 300-500r / min, add anhydrous ethanol and dibutyltin dilaurate, and stir for 10-15min. S3, grafting reaction Add the silane coupling agent KH560 dropwise into the reactor. After the addition is complete, raise the temperature to 100-110℃ and keep the temperature for 2-3 hours. S4, Post-processing After the reaction was completed, the reaction product was cooled to 60-70℃ and distilled under reduced pressure to obtain a pale yellow transparent organosilicon-modified epoxy resin.

3. The carbon fiber resin-based composite material for skis as described in claim 2, characterized in that, In step S4, the conditions for vacuum distillation are: distillation pressure 0.06-0.08 MPa, distillation time 1-1.5 h.

4. The carbon fiber resin-based composite material for skis as described in claim 1, characterized in that, The carbon fiber is T700 or T800 grade carbon fiber.

5. The carbon fiber resin-based composite material for skis as described in claim 1, characterized in that, The curing agent is methyltetrahydrophthalic anhydride.

6. The carbon fiber resin-based composite material for skis as described in claim 1, characterized in that, The toughening agent is a core-shell structured acrylate elastomer, with a core layer of polybutadiene and a shell layer of polymethyl methacrylate, and a particle size of 50-200 nm.

7. The carbon fiber resin-based composite material for skis as described in claim 6, characterized in that, The core-shell structured acrylate elastomer is prepared by the following method: SS1, Preparation of Seed Solution By mass, add 80-100 parts of deionized water, 0.8-1.5 parts of sodium dodecyl sulfate, 0.3-0.6 parts of ammonium persulfate, and 20-30 parts of butadiene monomer to a reaction vessel. Purge the air in the vessel with nitrogen 3-5 times, raise the temperature to 60-70℃, stir at 200-300 r / min, and keep the reaction at this temperature for 3-4 hours to obtain polybutadiene seed emulsion. SS2, shell polymerization Add 15-25 parts of methyl methacrylate monomer and 2-5 parts of butyl acrylate to the seed emulsion, and continue the reaction at 60-70℃ for 2-3 hours; during this period, add 0.1-0.2 parts of ammonium persulfate. SS3, Post-processing After the reaction was completed, the emulsion was cooled to room temperature and the pH was adjusted to 6.5-7.5 with a 5% sodium hydroxide solution. Then, it was concentrated by vacuum distillation and spray-dried to obtain a powdered core-shell structured acrylate elastomer.

8. The carbon fiber resin-based composite material for skis as described in claim 7, characterized in that, In step SS2, ammonium persulfate is added in two parts: the first part is added after the reaction has been kept at the temperature for 1 hour, and the second part is added 1 hour after the first addition. In step SS3, the conditions for vacuum distillation are a distillation pressure of 0.07-0.09 MPa and a temperature of 50-60℃; the inlet air temperature for spray drying is 120-130℃ and the outlet air temperature is 60-70℃.

9. The carbon fiber resin-based composite material for skis as described in claim 1, characterized in that, The wear-resistant filler is a mixture of nano-alumina and nano-silica in a mass ratio of 2:1-3:1, with a particle size of 50-100nm; The coupling agent is silane coupling agent KH-550; The antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:

1.

10. A method for preparing a carbon fiber resin-based composite material for skis as described in claim 1, characterized in that, The process is as follows: Step 1, Carbon fiber pretreatment The carbon fiber was placed in a plasma treatment device under an argon atmosphere. The plasma power was 80-120W and the treatment time was 10-20 minutes. After treatment, immerse it in a coupling agent solution, which is prepared by mixing coupling agent and ethanol at a mass ratio of 1:50-80, and soak for 2-4 hours. Then, it is taken out and dried at 80-100℃ for 2-3 hours to obtain pretreated carbon fiber; Step 2, Preparation of composite matrix According to the mass fraction, add the modified epoxy resin matrix, toughening agent, wear-resistant filler and antioxidant into a high-speed mixer and mix for 30-40 minutes at a speed of 1500-2000 r / min and a temperature of 60-80℃. Then add the curing agent and continue mixing for 15-20 minutes to obtain a uniform composite matrix; Step 3, composite molding, using resin transfer molding process for composite molding. The pretreated carbon fiber from step one is laid in the mold according to the preset layup method. The mold is then closed and sealed. The composite matrix prepared in step two is injected into the mold at an injection pressure of 0.3-0.5 MPa and an injection temperature of 70-80℃. After injection, a curing process is performed. The curing process is as follows: first, keep the temperature at 80℃ for 2-3 hours, then raise the temperature to 120℃ and keep it at 3-3.5 hours, and finally raise the temperature to 150℃ and keep it at 1-1.5 hours. After curing, cool to room temperature and demold to obtain the composite material preform; Step 4, Post-processing The composite material preform is machined to remove burrs and excess edges, followed by surface grinding and polishing to obtain the final carbon fiber resin-based composite material for skis.

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