A CMC / UiO66-NH2 / MnO2 synergistic non-destructive modified carbon cloth reinforced resin friction material and method and application

Abstract

The present invention discloses a CMC / UiO66-NH2 / MnO2 synergistic non-destructive modified carbon cloth reinforced resin friction material, method and application, belonging to the technical field of wet friction materials. First, the carbon fiber is immersed in a carboxymethyl cellulose solution, and a layer of highly adhesive CMC film is coated on its surface to form a protective layer; then, a solvent thermal method is used to in-situ grow dense and uniform octahedral UiO66-NH2 grains on the carbon fiber; further, a solvent thermal method is used to in-situ grow needle-shaped nano-MnO2 on the carbon fiber cloth grafted with the UiO66-NH2 grains. A CMC / UiO66-NH2 / MnO2 multi-level structure is constructed, which improves the interface performance of the carbon fiber cloth / resin and significantly enhances the mechanical and friction and wear properties of the friction material. The tensile strength is 463.73-585.07MPa, and the tensile strength increases from 305.33MPa to 585.07MPa, with a tensile strength increase of 91.6%. The friction coefficient is 0.124-0.134; the friction coefficient increases from 0.097 to 0.134, an increase of 38.1%. The wear rate is 3.69×10 ‑12 ‑7.24×10 ‑ 12 m 3 / (N·m), the wear rate is from 10.83×10 ‑12 m 3 / (N·m) decreased to 3.69×10 ‑12 m 3 / (N·m), the wear rate decreased by 65.9%.

Description

Technical Field

[0001] The present invention belongs to the technical field of wet friction materials, and specifically relates to a CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material, a method and an application thereof. Background Art

[0002] In modern industry and transportation, friction materials are key components in mechanical clutch and braking systems, and their performance is directly related to the safety, reliability, and durability of these devices. With technological advancements and the rapid development of high-end equipment manufacturing, the performance requirements for friction materials are becoming increasingly stringent. Friction materials are not only required to possess a stable coefficient of friction, good wear resistance, high strength, and toughness, but also to possess excellent elastic recovery, thermal stability, low thermal expansion coefficient, and superior chemical stability. The combined improvement of these properties is crucial for ensuring the stable operation of various transportation vehicles, such as automobiles, locomotives, and aircraft, under complex operating conditions. Fiber-reinforced resin-based friction materials, with their unique performance advantages, have become a research hotspot and development direction in the friction materials field. To further enhance the performance of fiber-reinforced resin-based friction materials, researchers are continuously exploring new reinforcement materials and modification technologies. Among them, carbon fiber, due to its excellent properties such as high strength, high modulus, high temperature resistance, corrosion resistance, and wear resistance, is widely used as a reinforcement in resin-based friction materials. However, interfacial bonding issues between carbon fiber and the resin matrix have long been a key factor hindering the performance improvement of composite materials. Due to the smooth surface and strong chemical inertness of carbon fibers, it is difficult for them to form an effective bond with the resin matrix, which makes fiber debonding and matrix peeling prone to occur under actual working conditions, thus limiting the widespread application of carbon cloth reinforced resin-based friction materials. Therefore, surface modification of carbon fibers to reduce the modulus difference between the fiber and resin phases and increase the fiber roughness, thereby improving the interfacial bonding between the fiber and resin, is the key to improving the various properties of carbon cloth reinforced resin-based friction materials.

[0003] The Chinese patent publication number CN116903895A, "A method for preparing electron beam irradiated carbon fiber reinforced modified polyaryletherketone", first acidifies the carbon fiber, and then grafts a mixed modifier of an olefin coupling agent, a cross-linking aid, and a polyoxyethylene ether surfactant onto the carbon fiber surface through physical blending. However, acidification treatment can cause problems such as reduced fiber strength, poor stability, and environmental pollution, while physical blending has disadvantages such as poor dispersibility, weak interfacial bonding ability, and limited performance improvement, all of which limit the improvement of composite material performance. The Chinese patent publication number CN114575158A, "A method for preparing a COF grafted modified carbon cloth / resin-based friction material", uses concentrated nitric acid to pretreat the carbon fiber, and then uses a hydrothermal reaction to in-situ grow COF material on the carbon fiber. The COF-loaded carbon fiber cloth is used as a reinforcement for application in the field of wet friction materials.

[0004] While the aforementioned modification methods have improved the interfacial bonding strength between carbon fibers and the resin matrix to a certain extent, numerous challenges and issues remain. First, while acidification can increase the surface activity of the carbon fibers, it can damage the fiber's bulk strength and reduce its mechanical properties. Furthermore, the wastewater generated during the acidification process can also pollute the environment. Second, physical blending methods suffer from poor dispersibility and weak interfacial bonding, resulting in limited modification effectiveness and difficulty in significantly improving the overall performance of the composite material. Furthermore, while single-component modification can improve the wettability of the fiber with the resin to a certain extent, synergistic modification using multiple components is more effective. Synergistic modification of carbon fibers with multiple components, through the dual effects of mechanical meshing and chemical coupling, can significantly strengthen the interfacial bonding between the carbon fibers and the resin matrix, thereby more effectively improving the tribological properties of the material. However, achieving uniform distribution and strong bonding of the multiple components on the carbon fiber surface, as well as further strengthening the interfacial bonding through the dual effects of mechanical meshing and chemical coupling, remain both challenging and hot topics in current research. Therefore, exploring more efficient, environmentally friendly modification methods that effectively enhance the interfacial bonding strength between carbon fibers and the resin matrix is ​​of great significance for promoting the development of fiber-reinforced resin-based friction materials. Summary of the Invention

[0005] In order to overcome the shortcomings of the above-mentioned prior art, the purpose of the present invention is to provide a CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material and method and application, so as to solve the technical problem of how to efficiently and environmentally friendly modify the carbon fiber surface to strengthen the interface bonding between the carbon fiber and the resin matrix, thereby improving the comprehensive performance of the carbon cloth reinforced resin-based friction material.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] The present invention discloses a preparation method of a CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material, comprising the following steps:

[0008] 1) First, the carbon fiber cloth is soaked in acetone and washed, then soaked in a carboxymethyl cellulose solution, washed, and dried to obtain a pretreated carbon fiber cloth;

[0009] 2) dissolving diaminoterephthalic acid in N,N-dimethylformamide, adding zirconium chloride and ultrasonically treating, adding acetic acid dropwise, mixing and stirring uniformly to obtain a mixed solution;

[0010] 3) placing the carbon fibers pretreated in step 1) in the mixed solution of step 2) to undergo a solvothermal reaction, washing them with N,N-dimethylformamide and anhydrous ethanol multiple times after the reaction, and freeze-drying them once to obtain a CMC / UiO66-NH2 synergistically modified carbon fiber cloth;

[0011] 4) placing the CMC / UiO66-NH2 synergistically modified carbon fiber obtained in step 3) in a MnO2 solution for a secondary solvothermal reaction, and after the reaction is completed, washing and secondary freeze-drying are performed to obtain a CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth;

[0012] 5) The CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth obtained in step 4) is vacuum impregnated in a phenolic resin ethanol solution, dried, and then hot-pressed to obtain a CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material.

[0013] Preferably, in step 1), the carbon fiber cloth is soaked in acetone for 30-60 hours; the carboxymethyl cellulose solution is prepared by adding 0.6-1.2g of carboxymethyl cellulose to every 600g of deionized water; and the soaking conditions in the carboxymethyl cellulose solution are: soaking at 75-95°C for 2-4 hours.

[0014] Preferably, the ratio of the pretreated carbon fiber cloth, diaminoterephthalic acid, N,N-dimethylformamide, zirconium chloride and acetic acid is (4-8) g: (0.108-0.216) g: (50-100) ml: (0.14-0.28) g: (2-10) ml;

[0015] In step 2), the mixing and stirring speed is 600-1500 r / min.

[0016] Preferably, in step 3), the temperature of the first solvent thermal reaction is 100-140° C., and the time is 20-30 h.

[0017] Preferably, in step 4), the MnO2 solution is prepared by adding 0.0316-0.0632 g MnO2 to every 50-100 ml of deionized water.

[0018] Preferably, in step 4), the temperature of the secondary solvent thermal reaction is 100-140° C., and the time is 10-24 h.

[0019] Preferably, in step 5), the mass fraction of the phenolic resin ethanol solution is 20%-25%; the immersion pressure is 0.07-0.1 MPa, and the immersion time is 24-26 hours.

[0020] Preferably, in step 5), the temperature of hot pressing curing is 160-180° C., the pressure is 3-8 MPa, and the curing time is 6-12 min.

[0021] The present invention also discloses a CMC / UiO66-NH2 / MnO2 synergistic non-destructive modified carbon cloth reinforced resin friction material, which is prepared by the above-mentioned preparation method of the CMC / UiO66-NH2 / MnO2 synergistic non-destructive modified carbon cloth reinforced resin friction material. The CMC / UiO66-NH2 / MnO2 synergistic non-destructive modified carbon cloth reinforced resin friction material has a tensile strength of 463.73-585.07 MPa; a friction coefficient of 0.124-0.134; and a wear rate of 3.69×10 -12 -7.24×10 -12 m 3 / (N·m).

[0022] The present invention also discloses the application of the CMC / UiO66-NH2 / MnO2 synergistic non-destructive modified carbon cloth reinforced resin friction material prepared by the preparation method of the above-mentioned CMC / UiO66-NH2 / MnO2 synergistic non-destructive modified carbon cloth reinforced resin friction material in vehicle braking.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] The present invention discloses a preparation method of a CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material, constructs a CMC / UiO66-NH2 / MnO2 multi-level structure synergistically modified carbon fiber cloth and constructs a rigid-flexible interface reinforcement structure with a resin matrix, thereby improving the interface performance and significantly enhancing the mechanical properties and friction and wear performance of the friction material. A CMC / UiO66-NH2 / MnO2 multi-level structure was constructed on the carbon fiber surface. First, a film-like CMC was coated on the surface of the carbon fiber without damaging the strength of the carbon fiber itself. Oxygen-containing functional groups such as carboxyl and hydroxyl groups were introduced on the surface of the carbon fiber to provide nucleation sites for the next in-situ growth of UiO66-NH2 crystals. Next, the UiO66-NH2 layer was constructed by a solvent thermal method. The dense and uniform octahedral UiO66-NH2 crystal surface contained a large number of amino and hydroxyl groups to improve the wettability. Secondly, the MnO2 layer was constructed. A large number of MnO2 nucleation sites appeared in the defects of the UiO66-NH2 crystals, and MnO2 then grew from the inside of the defects, eventually forming a CMC / UiO66-NH2 / MnO2 multi-level structure. On the one hand, the needle-shaped MnO2 is embedded within the first two coating layers, forming a mechanical bond with the carbon fibers and also facilitating the mechanical bond between the carbon fibers and the resin. On the other hand, the MnO2 surface contains a large number of oxygen-containing functional groups, such as hydroxyl groups, which chemically bond the carbon fibers and the resin during the hot pressing process, improving interfacial properties and significantly enhancing the mechanical properties and friction and wear resistance of the friction material. The preparation method of the present invention offers the advantages of simple process, low cost, and excellent performance. The CMC / UiO66-NH2 / MnO2 synergistically non-destructively modified carbon cloth-reinforced resin friction material showed an increase in tensile strength of 51.9%-91.6% and a reduction in wear rate of 33.1%-65.9%.

[0025] Furthermore, in step 1), the carbon fiber cloth is soaked in acetone for 30-60 hours. This acetone soaking effectively removes oil and impurities from the carbon fiber cloth's surface, improving its purity and surface activity, and creating optimal conditions for subsequent coating with carboxymethyl cellulose (CMC). Controlling the soaking time to 30-60 hours ensures effective cleaning while preventing damage to the carbon fiber's strength caused by prolonged soaking. The carboxymethyl cellulose solution is prepared by adding 0.6-1.2g of carboxymethyl cellulose to every 600g of deionized water. The precise CMC solution ratio ensures uniformity and thickness of the coating layer, avoiding uneven coating or excessively thick or thin coating layers caused by excessively high or low concentrations. This helps form a stable CMC layer, providing a good foundation for subsequent steps. The soaking temperature in the carboxymethyl cellulose solution is 75-95°C for 2-4 hours. The optimal soaking temperature and time ensure that the CMC is fully adsorbed onto the carbon fiber surface, forming a uniform and dense coating layer. This helps to introduce sufficient oxygen-containing functional groups such as carboxyl and hydroxyl groups, providing sufficient nucleation sites for the in situ growth of UiO66-NH2 crystals.

[0026] Furthermore, the dosage ratio of the pretreated carbon fiber cloth, diaminoterephthalic acid, N,N-dimethylformamide, zirconium chloride and acetic acid is (4-8) g: (0.108-0.216) g: (50-100) ml: (0.14-0.28) g: (2-10) ml; acetic acid controls the morphology of different UiO66-NH2 and then grows MnO2 with different densities; by optimizing the dosage ratio of each raw material, the uniform growth and density of UiO66-NH2 crystals can be ensured, while avoiding raw material waste and unnecessary side reactions.

[0027] Furthermore, in step 2), the mixing speed is 600-1500 rpm. An appropriate stirring speed promotes thorough mixing and uniform dispersion of the raw materials, improving the growth rate and uniformity of the UiO66-NH2 crystals. At the same time, excessively high stirring speeds should be avoided, as they may damage the fibers or cause solution splashing.

[0028] Furthermore, in step 3), the temperature of a solvent thermal reaction is 100-140°C and the time is 20-30h; the appropriate temperature and time conditions can promote the in situ growth of UiO66-NH2 crystals while avoiding excessively high temperatures that may cause destruction of the crystal structure or degradation of carbon fiber performance.

[0029] Furthermore, in step 4), the MnO2 solution is prepared by adding 0.0316-0.0632 g of MnO2 to every 50-100 ml of deionized water. The precise proportion of the MnO2 solution ensures the uniformity and thickness of the MnO2 layer, preventing an excessively thick or thin MnO2 layer from adversely affecting material properties.

[0030] Furthermore, in step 4), the secondary solvothermal reaction temperature is 100-140°C and the reaction time is 10-24 hours. Suitable secondary solvothermal reaction conditions can promote the growth of MnO2 at UiO66-NH2 crystal defects, forming a stable MnO2 layer. At the same time, excessively high temperatures or prolonged reaction times should be avoided, which can lead to degradation of material properties.

[0031] Furthermore, in step 5), the mass fraction of the phenolic resin ethanol solution is 20%-25%, the impregnation pressure is 0.07-0.1 MPa, and the impregnation time is 24-26 hours. A suitable phenolic resin concentration ensures good wetting and bonding between the resin matrix and the carbon fiber cloth, while avoiding excessive concentration that may lead to excessive resin, incomplete curing, or decreased material properties.

[0032] Furthermore, in step 5), the hot press curing temperature is 160-180°C, the pressure is 3-8 MPa, and the curing time is 6-12 minutes. Reasonable hot press curing conditions can promote the complete curing of the resin matrix, improving the overall strength and heat resistance of the material. At the same time, appropriate pressure and curing time ensure a tight bond between the resin and the carbon fiber cloth, forming a stable interface structure.

[0033] The present invention also discloses a CMC / UiO66-NH2 / MnO2 synergistically non-destructively modified carbon cloth reinforced resin friction material, whose tensile strength is 463.73-585.07MPa; compared with traditional carbon cloth reinforced resin friction materials, it is increased by 51.9%-91.6%, a significant improvement; this is mainly due to the synergistic modification effect of the CMC / UiO66-NH2 / MnO2 multi-level structure, which not only enhances the interfacial bonding between the carbon fiber and the resin matrix, but also further enhances the overall strength of the material through the mechanical meshing effect of the needle-shaped MnO2. The friction coefficient is 0.124-0.134, which is ideal for vehicle braking systems, ensuring sufficient braking force while avoiding excessive friction that causes increased wear. The wear rate is 3.69×10 -12 -7.24×10 -12 m 3 / (N·m), which is reduced by 33.1%-65.9% compared with traditional materials, significantly improving the service life and reliability of the material.

[0034] The present invention also discloses the application of the above-mentioned CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material in vehicle braking. Since the friction material has a stable friction coefficient and a low wear rate, it can respond quickly and generate a stable braking force when the vehicle brakes, thereby shortening the braking distance and improving braking efficiency. At the same time, the stable friction performance reduces the vibration and noise during braking, improving driving safety and comfort. The low wear rate means that the brake material can maintain a longer effective thickness during use, reducing the replacement frequency, thereby extending the service life of the entire brake system. This not only reduces the vehicle maintenance cost, but also reduces the safety hazards caused by brake system failures. The friction material prepared by the present invention has good thermal stability and wear resistance, and can adapt to high-speed, high-frequency braking and braking requirements in harsh environments, such as high temperature, humidity, etc. This makes the material have broad application prospects in the braking systems of various types of vehicles. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 These are SEM photos of the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth prepared in the present invention, where (a) is the original carbon fiber cloth, (b), (c) and (d) are the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloths prepared in Example 1, Example 2 and Example 3, respectively.

[0036] Figure 2 This is a comparison chart of the tensile strength of the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction materials prepared in the present invention, wherein C1 is an unmodified carbon cloth reinforced resin-based friction material, C2, C3 and C4 are CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction materials prepared in Example 1, Example 2 and Example 3, respectively.

[0037] Figure 3 This is a comparison chart of the continuous friction coefficients of the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction materials prepared in the present invention, wherein C1 is an unmodified carbon cloth reinforced resin-based friction material, and C2, C3 and C4 are CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction materials prepared in Example 1, Example 2 and Example 3, respectively.

[0038] Figure 4This is a comparison chart of the wear rates of the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction materials prepared in the present invention, wherein C1 is an unmodified carbon cloth reinforced resin-based friction material, and C2, C3 and C4 are CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction materials prepared in Example 1, Example 2 and Example 3, respectively. DETAILED DESCRIPTION

[0039] The technical solution of the present invention will be described clearly and completely below. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0040] In the present invention, unless otherwise specified, all the embodiments and preferred implementation methods mentioned herein can be combined with each other to form a new technical solution.

[0041] In the present invention, unless otherwise specified, all technical features and preferred features mentioned herein can be combined with each other to form a new technical solution.

[0042] In the present invention, unless otherwise specified, percentages (%) or parts refer to percentages by weight or parts by weight relative to the composition.

[0043] In the present invention, unless otherwise specified, the components involved or their preferred components can be combined with each other to form a new technical solution.

[0044] In this disclosure, unless otherwise specified, the numerical range "a-b" is an abbreviation for any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "6-22" indicates that all real numbers between "6-22" are listed herein, and "6-22" is merely an abbreviation for these numerical combinations.

[0045] The "range" disclosed in the present invention is in the form of lower limit and upper limit, which can be one or more lower limits, and one or more upper limits respectively.

[0046] In the present invention, the term "and / or" used herein refers to any combination and all possible combinations of one or more of the associated listed items, and includes these combinations.

[0047] In the present invention, unless otherwise specified, each reaction or operation step can be carried out sequentially or in a sequential manner. Preferably, the reaction method herein is carried out sequentially.

[0048] Unless otherwise indicated, the professional and scientific terms used herein are the same as those familiar to those skilled in the art. In addition, any method or material similar or equivalent to the described content can also be applied to the present invention.

[0049] The present invention provides a preparation method of a CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material, the steps of which are as follows:

[0050] Step 1: Pre-treat the carbon fiber cloth by soaking and washing with acetone and deionized water at room temperature to remove surface sizing agents and impurities;

[0051] Step 2: Soak the carbon fiber cloth obtained in step 1 in a carboxymethyl cellulose solution, wash it two to three times with deionized water, and then dry it for later use;

[0052] Step 3: First, dissolve diaminoterephthalic acid in N, N-dimethylformamide to obtain a mixed solution A. Then, zirconium chloride is added to the mixed solution A and ultrasonically treated to obtain a mixed solution B. Then, acetic acid is added dropwise to form a mixed solution C. Subsequently, the carbon fiber cloth obtained in step 2 is rolled up and placed vertically in a polytetrafluoroethylene reactor containing mixed solution C for a solvent thermal reaction. After the reaction is completed, it is repeatedly filtered and washed with N, N-dimethylformamide and anhydrous ethanol, and finally freeze-dried once to obtain CMC / UiO66-NH2 synergistically modified carbon fiber cloth;

[0053] Step 4: First, MnO2 is dissolved in deionized water and ultrasonically mixed to obtain a MnO2 solution. The CMC / UiO66-NH2 synergistically modified carbon fiber cloth obtained in Step 3 is sewn into a column with thread and then vertically placed into a polytetrafluoroethylene liner filled with MnO2 solution for a secondary solvothermal reaction. After the reaction is completed, the carbon fiber cloth is washed with deionized water multiple times and freeze-dried twice to obtain a CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth.

[0054] Step 5: Vacuum impregnate the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth obtained in step 4 into a phenolic resin ethanol solution, dry it, and then hot-press and cure it using a vulcanizer to obtain a CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material.

[0055] Furthermore, in step 1, the method for pre-treating and removing the surface sizing agent and impurities is: soaking the carbon fiber cloth in an acetone solution at room temperature for 30-60 hours.

[0056] Furthermore, in step 2, 0.6-1.2 g of carboxymethyl cellulose is added to every 600 g of deionized water, and the soaking condition in the carboxymethyl cellulose solution is: soaking at 75-95° C. for 2-4 hours.

[0057] Furthermore, in step three, 4-8 g of carbon fiber cloth, 0.108-0.216 g of diaminoterephthalic acid and 0.14-0.28 g of zirconium chloride are added to every 50-100 ml of N,N-dimethylformamide.

[0058] Furthermore, in step 3, the magnetic stirring of the mixed liquid C is controlled at a rotation speed of 600-1500 r / min, and 2-10 ml of acetic acid is added dropwise to the mixed liquid using a syringe.

[0059] Furthermore, in step three, the temperature of the first solvent thermal reaction is 100-140° C., and the time is 20-30 h.

[0060] Furthermore, in step 4, the MnO2 solution is prepared by adding 0.0316-0.0632 g MnO2 to every 50-100 ml of deionized water.

[0061] Furthermore, in step 4, the temperature of the secondary solvent thermal reaction is 100-140° C., and the time is 10-24 hours.

[0062] Furthermore, in step five, the mass fraction of the phenolic resin ethanol solution is 20%-25%; the immersion pressure is 0.07-0.1 MPa, and the immersion time is 24-26 hours.

[0063] Furthermore, in step five, the process parameters of hot pressing curing in a vulcanizing machine are: temperature of 160-180° C., pressure of 3-8 MPa, and curing time of 6-12 min.

[0064] The CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material disclosed in the present invention has a tensile strength of 463.73-585.07 MPa, showing extremely strong load-bearing capacity and tensile resistance; a friction coefficient of 0.124-0.134, ensuring stability and reliability during braking; and a wear rate of 3.69×10 -12 -7.24×10 -12 m 3 / (N·m), showing excellent wear resistance and long service life. These excellent performance indicators make this material have broad application prospects and huge market potential in the field of high-performance friction materials.

[0065] The disclosed CMC / UiO66-NH2 / MnO2 synergistic, non-destructive modified carbon cloth-reinforced resin friction material is used in vehicle braking. Its stable friction coefficient and extremely low wear rate ensure rapid braking response and reliability over extended periods of use, providing strong material support for improving vehicle braking efficiency and safety.

[0066] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Generally, the components of the embodiments of the present invention described and shown in the drawings herein can be arranged and designed in various different configurations. Therefore, the following detailed description of the embodiments of the present invention provided in the drawings is not intended to limit the scope of the claimed invention, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0067] Example 1

[0068] A method for preparing a CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material comprises the following steps:

[0069] Step 1: Put 6g of carbon fiber cloth into acetone, seal it and soak it at room temperature for 45 hours, then wash the carbon fiber cloth with deionized water two to three times and dry it to obtain the pretreated carbon fiber cloth;

[0070] Step 2: Soak the pretreated carbon fiber cloth obtained in step 1 in a 0.15% carboxymethyl cellulose solution at 80° C. for 3 hours, then wash it two to three times with deionized water and dry it for later use;

[0071] Step 3: Dissolve 0.108 g of diaminoterephthalic acid in 50 mL of N,N-dimethylformamide at room temperature to obtain a mixed solution A, and perform ultrasonic treatment on the mixed solution to uniformly disperse the diaminoterephthalic acid in the mixed solution A;

[0072] Step 4: adding 0.14 g of zirconium chloride to the mixed solution A and performing ultrasonic treatment to obtain a mixed solution B;

[0073] Step 5: Add 2 mL of acetic acid dropwise to the mixed solution B, stir magnetically at a speed of 900 r / min, and mix well to obtain a mixed solution C;

[0074] Step 6: Pour the mixed solution C and carbon fiber cloth into a 100 mL polytetrafluoroethylene liner, and then fix the liner in a matching stainless steel reactor;

[0075] Step 7: The stainless steel reactor containing the mixed solution C and the carbon fiber cloth was fixed in a homogeneous reactor and reacted at 120° C. and a rotation speed of 60 r / min for 24 h to obtain a grafted UiO66-NH2 carbon fiber cloth;

[0076] Step 8: The grafted UiO66-NH2 carbon fiber cloth obtained in step 7 is washed with N,N-dimethylformamide and anhydrous ethanol several times to remove unreacted monomers and UiO66-NH2 not grafted on the carbon fiber cloth, and then placed in an oven for drying;

[0077] Step 9: Dissolve 0.0316g of MnO2 in 50ml of deionized water and mix ultrasonically to obtain solution D. Sew the washed and dried grafted UiO66-NH2 carbon fiber cloth obtained in step 8 into a column and vertically place it into a polytetrafluoroethylene liner. Then, fix the liner into a matching stainless steel reactor.

[0078] Step 10: Fix the stainless steel reactor containing solution D and carbon fiber cloth in a homogeneous reactor and react at 100°C and a rotation speed of 50 r / min for 12 hours to obtain carbon fiber cloth grafted with MnO2;

[0079] Step 11: The carbon fiber cloth grafted with MnO2 obtained in step 10 is washed with deionized water several times to remove unreacted monomers and MnO2 not grafted on the carbon fiber cloth, and freeze-dried to obtain CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth; the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth is vacuum impregnated in a phenolic resin ethanol solution with a mass fraction of 25%, and the impregnation conditions are: pressure of 0.08 MPa at room temperature, and impregnation time of 24 hours; the impregnated preform is placed in an oven and allowed to stand and dry, and hot-pressed and cured with a vulcanizer, and the hot-pressing curing conditions are: temperature 175°C, pressure 4 MPa, and curing time 12 minutes to obtain CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material.

[0080] The tensile strength of the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material prepared in Example 1 is 491.73 MPa; the friction coefficient is 0.124; and the wear rate is 5.4×10 -12 m 3 / (N·m).

[0081] Example 2

[0082] A method for preparing a CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material comprises the following steps:

[0083] Step 1: Put 6g of carbon fiber cloth into acetone, seal it and soak it at room temperature for 45 hours, then wash the carbon fiber cloth with deionized water two to three times and dry it to obtain the pretreated carbon fiber cloth;

[0084] Step 2: Soak the pretreated carbon fiber cloth obtained in step 1 in a 0.15% carboxymethyl cellulose solution at 80° C. for 3 hours, then wash it two to three times with deionized water and dry it for later use;

[0085] Step 3: Dissolve 0.108 g of diaminoterephthalic acid in 50 mL of N,N-dimethylformamide at room temperature to obtain a mixed solution A, and perform ultrasonic treatment on the mixed solution to uniformly disperse the diaminoterephthalic acid in the mixed solution A;

[0086] Step 4: adding 0.14 g of zirconium chloride to the mixed solution A and performing ultrasonic treatment to obtain a mixed solution B;

[0087] Step 5: Add 6 mL of acetic acid dropwise to the mixed solution B, stir magnetically at a speed of 900 r / min, and mix well to obtain a mixed solution C;

[0088] Step 6: Pour the mixed solution C and carbon fiber cloth into a 100 mL polytetrafluoroethylene liner, and then fix the liner in a matching stainless steel reactor;

[0089] Step 7: The stainless steel reactor containing the mixed solution C and the carbon fiber cloth was fixed in a homogeneous reactor and reacted at 120° C. and a rotation speed of 60 r / min for 24 h to obtain a grafted UiO66-NH2 carbon fiber cloth;

[0090] Step 8: The grafted UiO66-NH2 carbon fiber cloth obtained in step 7 is washed with N,N-dimethylformamide and anhydrous ethanol several times to remove unreacted monomers and UiO66-NH2 not grafted on the carbon fiber cloth, and then placed in an oven for drying;

[0091] Step 9: Dissolve 0.0316g of MnO2 in 50ml of deionized water and mix ultrasonically to obtain solution D. Sew the washed and dried UiO66-NH2 grafted carbon fiber cloth obtained in step 8 into a columnar shape and vertically place it into a polytetrafluoroethylene liner. Then, fix the liner into a matching stainless steel reactor.

[0092] Step 10: Fix the stainless steel reactor containing solution D and carbon fiber cloth in a homogeneous reactor and react at 100°C and a rotation speed of 50 r / min for 12 hours to obtain carbon fiber cloth grafted with MnO2;

[0093] Step 11: The carbon fiber cloth grafted with MnO2 obtained in step 10 is washed with deionized water several times to remove unreacted monomers and MnO2 not grafted on the carbon fiber cloth, and freeze-dried to obtain CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth; the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth is vacuum impregnated in a phenolic resin ethanol solution with a mass fraction of 25%, and the impregnation conditions are: pressure of 0.08 MPa at room temperature, and impregnation time of 24 hours; the impregnated preform is placed in an oven and allowed to stand and dry, and hot-pressed and cured with a vulcanizer, and the hot-pressing curing conditions are: temperature 175°C, pressure 4 MPa, and curing time 12 minutes to obtain CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material.

[0094] The tensile strength of the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material prepared in Example 2 is 585.07 MPa; the friction coefficient is 0.134; and the wear rate is 3.69×10 -12 m 3 / (N·m).

[0095] Example 3

[0096] A method for preparing a CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material comprises the following steps:

[0097] Step 1: Put 6g of carbon fiber cloth into acetone, seal it and soak it at room temperature for 45 hours, then wash the carbon fiber cloth with deionized water two to three times and dry it to obtain the pretreated carbon fiber cloth;

[0098] Step 2: Soak the pretreated carbon fiber cloth obtained in step 1 in a 0.15% carboxymethyl cellulose solution at 80° C. for 3 hours, then wash it two to three times with deionized water and dry it for later use;

[0099] Step 3: Dissolve 0.108 g of diaminoterephthalic acid in 50 mL of N,N-dimethylformamide at room temperature to obtain a mixed solution A, and perform ultrasonic treatment on the mixed solution to uniformly disperse the diaminoterephthalic acid in the mixed solution A;

[0100] Step 4: adding 0.14 g of zirconium chloride to the mixed solution A and performing ultrasonic treatment to obtain a mixed solution B;

[0101] Step 5: Add 10 mL of acetic acid dropwise to the mixed solution B, stir magnetically at a speed of 900 r / min, and mix well to obtain a mixed solution C;

[0102] Step 6: Pour the mixed solution C and carbon fiber cloth into a 100 mL polytetrafluoroethylene liner, and then fix the liner in a matching stainless steel reactor;

[0103] Step 7: The stainless steel reactor containing the mixed solution C and the carbon fiber cloth was fixed in a homogeneous reactor and reacted at 120° C. and a rotation speed of 60 r / min for 24 h to obtain a grafted UiO66-NH2 carbon fiber cloth;

[0104] Step 8: The grafted UiO66-NH2 carbon fiber cloth obtained in step 7 is washed with N,N-dimethylformamide and anhydrous ethanol several times to remove unreacted monomers and UiO66-NH2 not grafted on the carbon fiber cloth, and then placed in an oven for drying;

[0105] Step 9: Dissolve 0.0316g of MnO2 in 50ml of deionized water and mix ultrasonically to obtain solution D. Sew the washed and dried grafted UiO66-NH2 carbon fiber cloth obtained in step 8 into a column and vertically place it into a polytetrafluoroethylene liner. Then, fix the liner into a matching stainless steel reactor.

[0106] Step 10: Fix the stainless steel reactor containing solution D and carbon fiber cloth in a homogeneous reactor and react at 100°C and a rotation speed of 50 r / min for 12 hours to obtain carbon fiber cloth grafted with MnO2;

[0107] Step 11: The carbon fiber cloth grafted with MnO2 obtained in step 10 is washed with deionized water several times to remove unreacted monomers and MnO2 not grafted on the carbon fiber cloth, and freeze-dried to obtain CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth; the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth is vacuum impregnated in a phenolic resin ethanol solution with a mass fraction of 25%, and the impregnation conditions are: pressure of 0.08 MPa at room temperature, and impregnation time of 24 hours; the impregnated preform is placed in an oven and allowed to stand and dry, and hot-pressed and cured with a vulcanizer, and the hot-pressing curing conditions are: temperature 175°C, pressure 4 MPa, and curing time 12 minutes to obtain CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material.

[0108] The tensile strength of the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material prepared in Example 3 is 463.73 MPa; the friction coefficient is 0.126; and the wear rate is 7.24×10 -12 m3 / (N·m).

[0109] Example 4

[0110] A method for preparing a CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material comprises the following steps:

[0111] Step 1: Put 4g of carbon fiber cloth into acetone, seal it and soak it at room temperature for 30 hours, then wash the carbon fiber cloth with deionized water two to three times and dry it to obtain the pretreated carbon fiber cloth;

[0112] Step 2: Soak the pretreated carbon fiber cloth obtained in step 1 in a 0.1% carboxymethyl cellulose solution at 75° C. for 2 hours, then wash it two to three times with deionized water and dry it for later use;

[0113] Step 3: Dissolve 0.216 g of diaminoterephthalic acid in 100 mL of N,N-dimethylformamide at room temperature to obtain a mixed solution A, and perform ultrasonic treatment on the mixed solution to uniformly disperse the diaminoterephthalic acid in the mixed solution A;

[0114] Step 4: adding 0.28 g of zirconium chloride to the mixed solution A and performing ultrasonic treatment to obtain a mixed solution B;

[0115] Step 5: 8 mL of acetic acid was added dropwise to the mixed solution B with magnetic stirring at a speed of 600 r / min, and mixed evenly to obtain a mixed solution C;

[0116] Step 6: Pour the mixed solution C and carbon fiber cloth into a 100 mL polytetrafluoroethylene liner, and then fix the liner in a matching stainless steel reactor;

[0117] Step 7: Fix the stainless steel reactor containing the mixed solution C and the carbon fiber cloth in a homogeneous reactor and react at 100° C. and a rotation speed of 60 r / min for 20 hours to obtain a grafted UiO66-NH2 carbon fiber cloth;

[0118] Step 8: The grafted UiO66-NH2 carbon fiber cloth obtained in step 7 is washed with N,N-dimethylformamide and anhydrous ethanol several times to remove unreacted monomers and UiO66-NH2 not grafted on the carbon fiber cloth, and then placed in an oven for drying;

[0119] Step 9: Dissolve 0.0632g of MnO2 in 100ml of deionized water and mix ultrasonically to obtain solution D. Sew the washed and dried grafted UiO66-NH2 carbon fiber cloth obtained in step 8 into a column with thread and place it vertically into a polytetrafluoroethylene liner. Then, fix the liner into a matching stainless steel reactor.

[0120] Step 10: Fix the stainless steel reactor containing solution D and carbon fiber cloth in a homogeneous reactor and react at 120°C and a rotation speed of 50 r / min for 10 hours to obtain carbon fiber cloth grafted with MnO2;

[0121] Step 11: The carbon fiber cloth grafted with MnO2 obtained in step 10 is washed with deionized water several times to remove unreacted monomers and MnO2 not grafted on the carbon fiber cloth, and freeze-dried to obtain CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth; the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth is vacuum impregnated in a phenolic resin ethanol solution with a mass fraction of 20%, and the impregnation conditions are: pressure of 0.07MPa at room temperature, and impregnation time of 24h; the impregnated preform is placed in an oven and allowed to stand and dry, and hot-pressed and cured with a vulcanizer, and the hot-pressing curing conditions are: temperature of 160°C, pressure of 4MPa, and curing time of 6min, to obtain CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material.

[0122] The tensile strength of the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material prepared in Example 4 is 555.34 MPa; the friction coefficient is 0.125; and the wear rate is 4.26×10 -12 m 3 / (N·m).

[0123] Example 5

[0124] A method for preparing a CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material comprises the following steps:

[0125] Step 1: Put 8g of carbon fiber cloth into acetone, seal it and soak it at room temperature for 48 hours, then wash the carbon fiber cloth with deionized water two to three times and dry it to obtain the pretreated carbon fiber cloth;

[0126] Step 2: Soak the pretreated carbon fiber cloth obtained in step 1 in a 0.15% by mass carboxymethyl cellulose solution, treat it at 95° C. for 4 hours, wash it two to three times with deionized water, and then dry it for later use;

[0127] Step 3: Dissolve 0.216 g of diaminoterephthalic acid in 100 mL of N,N-dimethylformamide at room temperature to obtain a mixed solution A, and perform ultrasonic treatment on the mixed solution to uniformly disperse the diaminoterephthalic acid in the mixed solution A;

[0128] Step 4: adding 0.28 g of zirconium chloride to the mixed solution A and performing ultrasonic treatment to obtain a mixed solution B;

[0129] Step 5: Add 2 mL of acetic acid dropwise to the mixed solution B, stir magnetically at a speed of 700 r / min, and mix well to obtain a mixed solution C;

[0130] Step 6: Pour the mixed solution C and carbon fiber cloth into a 100 mL polytetrafluoroethylene liner, and then fix the liner in a matching stainless steel reactor;

[0131] Step 7: Fix the stainless steel reactor containing the mixed solution C and the carbon fiber cloth in a homogeneous reactor and react for 20 minutes at 140° C. and a rotation speed of 60 r / min to obtain a grafted UiO66-NH2 carbon fiber cloth;

[0132] Step 8: The grafted UiO66-NH2 carbon fiber cloth obtained in step 7 is washed with N,N-dimethylformamide and anhydrous ethanol several times to remove unreacted monomers and UiO66-NH2 not grafted on the carbon fiber cloth, and then placed in an oven for drying;

[0133] Step 9: Dissolve 0.0632g of MnO2 in 100ml of deionized water and mix ultrasonically to obtain solution D. Sew the washed and dried grafted UiO66-NH2 carbon fiber cloth obtained in step 8 into a column with thread and place it vertically into a polytetrafluoroethylene liner. Then, fix the liner into a matching stainless steel reactor.

[0134] Step 10: Fix the stainless steel reactor containing solution D and carbon fiber cloth in a homogeneous reactor and react at 120°C and a rotation speed of 50 r / min for 10 hours to obtain carbon fiber cloth grafted with MnO2;

[0135] Step 11: The carbon fiber cloth grafted with MnO2 obtained in step 10 is washed with deionized water several times to remove unreacted monomers and MnO2 not grafted on the carbon fiber cloth, and freeze-dried to obtain CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth; the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth is vacuum impregnated in a phenolic resin ethanol solution with a mass fraction of 22%, and the impregnation conditions are: pressure of 0.09 MPa at room temperature, and impregnation time of 25 hours; the impregnated preform is placed in an oven and allowed to stand and dry, and hot-pressed and cured with a vulcanizer, and the hot-pressing curing conditions are: temperature 180°C, pressure 3 MPa, and curing time 8 minutes to obtain CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material.

[0136] The tensile strength of the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material prepared in Example 5 is 482.54 MPa; the friction coefficient is 0.132; and the wear rate is 4.31×10 -12 m3 / (N·m).

[0137] Example 6

[0138] A method for preparing a CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material comprises the following steps:

[0139] Step 1: Place 7g of carbon fiber cloth in acetone, seal it, and soak it at room temperature for 60 hours. Then, wash the carbon fiber cloth with deionized water two to three times and dry it to obtain the pretreated carbon fiber cloth.

[0140] Step 2: Soak the pretreated carbon fiber cloth obtained in step 1 in a 0.2% carboxymethyl cellulose solution at 95° C. for 4 hours, then wash it two to three times with deionized water and dry it for later use;

[0141] Step 3: Dissolve 0.111 g of diaminoterephthalic acid in 80 mL of N,N-dimethylformamide at room temperature to obtain a mixed solution A, and perform ultrasonic treatment on the mixed solution to uniformly disperse the diaminoterephthalic acid in the mixed solution A;

[0142] Step 4: adding 0.14 g of zirconium chloride to the mixed solution A and performing ultrasonic treatment to obtain a mixed solution B;

[0143] Step 5: Add 10 mL of acetic acid dropwise to the mixed solution B, stir magnetically at a speed of 1500 r / min, and mix well to obtain a mixed solution C;

[0144] Step 6: Pour the mixed solution C and carbon fiber cloth into a 100 mL polytetrafluoroethylene liner, and then fix the liner in a matching stainless steel reactor;

[0145] Step 7: Fix the stainless steel reactor containing the mixed solution C and the carbon fiber cloth in a homogeneous reactor and react at 120° C. and a rotation speed of 60 r / min for 30 hours to obtain a grafted UiO66-NH2 carbon fiber cloth;

[0146] Step 8: The grafted UiO66-NH2 carbon fiber cloth obtained in step 7 is washed with N,N-dimethylformamide and anhydrous ethanol several times to remove unreacted monomers and UiO66-NH2 not grafted on the carbon fiber cloth, and then placed in an oven for drying;

[0147] Step 9: Dissolve 0.0542g of MnO2 in 50ml of deionized water and mix ultrasonically to obtain solution D. Sew the washed and dried grafted UiO66-NH2 carbon fiber cloth obtained in step 8 into a columnar shape and vertically place it into a polytetrafluoroethylene liner. Then, fix the liner into a matching stainless steel reactor.

[0148] Step 10: Fix the stainless steel reactor containing solution D and carbon fiber cloth in a homogeneous reactor and react at 140°C and a rotation speed of 50 r / min for 24 hours to obtain carbon fiber cloth grafted with MnO2;

[0149] Step 11: The carbon fiber cloth grafted with MnO2 obtained in step 10 is washed with deionized water several times to remove unreacted monomers and MnO2 not grafted on the carbon fiber cloth, and freeze-dried to obtain CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth; the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth is vacuum impregnated in a phenolic resin ethanol solution with a mass fraction of 25%, and the impregnation conditions are: pressure of 0.1 MPa at room temperature, and impregnation time of 26 hours; the impregnated preform is placed in an oven and allowed to stand and dry, and hot-pressed and cured with a vulcanizer, and the hot-pressing curing conditions are: temperature 180°C, pressure 8 MPa, and curing time 12 minutes to obtain CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material.

[0150] The tensile strength of the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material prepared in Example 6 is 495.51 MPa; the friction coefficient is 0.127; and the wear rate is 6.85×10 -12 m 3 / (N·m).

[0151] Comparative Example 1

[0152] A method for preparing an unmodified carbon cloth reinforced resin-based friction material comprises the following steps:

[0153] Step 1: Soak 6g of carbon fiber cloth in acetone at room temperature for 45 hours to remove surface sizing and impurities, wash it repeatedly with deionized water three to four times, and then dry it for later use;

[0154] Step 2: Vacuum impregnate the carbon fiber cloth obtained in step 1 into a phenolic resin ethanol solution with a mass fraction of 25%. The impregnation conditions are: pressure of 0.08 MPa at room temperature and impregnation time of 24 h;

[0155] Step 3: The impregnated preform is placed in an oven and allowed to dry, and then hot-pressed and cured in a vulcanizer to obtain an unmodified carbon cloth reinforced resin-based friction material. The hot-pressing curing conditions are: temperature 175° C., pressure 4 MPa, and curing time 12 min.

[0156] The tensile strength of the unmodified carbon cloth reinforced resin-based friction material prepared in this comparative example 1 is 305.33 MPa; the friction coefficient is 0.097; the wear rate is 10.83×10 -12 m 3 / (N·m).

[0157] See also Figure 1 The SEM photos of the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth prepared by the present invention, wherein (a) is the original carbon fiber cloth, (b), (c) and (d) are the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth prepared in Example 1, Example 2 and Example 3, respectively; it can be seen from the figure that the surface of the original carbon fiber is smooth, and narrow and shallow grooves can be seen along the axial direction of the fiber. After modification, it can be seen that the surface of the carbon fiber is covered with needle-shaped MnO2.

[0158] Figure 2 This is a comparison chart of the tensile strength of the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction materials prepared by the present invention, wherein C1 is an unmodified carbon cloth reinforced resin-based friction material, C2, C3 and C4 are CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction materials prepared in Example 1, Example 2 and Example 3, respectively; it can be seen from the figure that the tensile strength of the modified composite material is improved.

[0159] Figure 3 This is a comparison chart of the continuous friction coefficients of the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction materials prepared by the present invention, wherein C1 is an unmodified carbon cloth reinforced resin-based friction material, C2, C3 and C4 are the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction materials prepared in Example 1, Example 2 and Example 3, respectively; it can be seen from the figure that the friction coefficient of the modified composite material is improved.

[0160] Figure 4 This is a comparison chart of the wear rates of the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction materials prepared in the present invention, wherein C1 is an unmodified carbon cloth reinforced resin-based friction material, C2, C3 and C4 are CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction materials prepared in Example 1, Example 2 and Example 3, respectively; it can be seen from the figure that the wear rate of the modified composite material is reduced.

[0161] In summary, the present invention discloses a method for preparing a CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material. First, the carbon fiber is immersed in a carboxymethyl cellulose solution and coated with a highly adhesive CMC film on its surface to form a protective layer. Next, a solvent thermal method is used to in-situ grow dense and uniform octahedral UiO66-NH2 grains on the carbon fiber. Furthermore, a solvent thermal method is used to in-situ grow needle-shaped nano-MnO2 on the carbon fiber cloth grafted with UiO66-NH2 grains. A CMC / UiO66-NH2 / MnO2 multi-level structure is constructed, which improves the interface performance of the carbon fiber cloth / resin and significantly improves the mechanical and friction and wear properties of the friction material. The friction coefficient is increased from 0.097 to 0.134, an increase of 38.1%, and the wear rate is increased from 10.83×10 -12 m 3 / (N·m) decreased to 3.69×10 -12 m 3 / (N·m), the wear rate decreased by 65.9%, and the tensile strength increased from 305.33MPa to 585.07MPa, a 91.6% increase in tensile strength. This is expected to bring new breakthroughs and progress to the development of vehicle braking systems.

[0162] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material, characterized in that: The following steps are involved: 1) First, the carbon fiber cloth is soaked in acetone and washed, then soaked in a carboxymethyl cellulose solution, washed, and dried to obtain a pretreated carbon fiber cloth; 2) dissolving diaminoterephthalic acid in N,N-dimethylformamide, adding zirconium chloride and ultrasonically treating, adding acetic acid dropwise, mixing and stirring uniformly to obtain a mixed solution; 3) placing the carbon fibers pretreated in step 1) in the mixed solution of step 2) to undergo a solvothermal reaction, washing them with N,N-dimethylformamide and anhydrous ethanol multiple times after the reaction, and freeze-drying them once to obtain a CMC / UiO66-NH2 synergistically modified carbon fiber cloth; 4) placing the CMC / UiO66-NH2 synergistically modified carbon fiber obtained in step 3) in a MnO2 solution for a secondary solvothermal reaction, and after the reaction is completed, washing and secondary freeze-drying are performed to obtain a CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth; 5) The CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon fiber cloth obtained in step 4) is vacuum impregnated in a phenolic resin ethanol solution, dried, and then hot-pressed to obtain a CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material.

2. The method for preparing the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material according to claim 1, characterized in that: In step 1), the carbon fiber cloth is soaked in acetone for 30-60 hours; the carboxymethyl cellulose solution is prepared by adding 0.6-1.2g of carboxymethyl cellulose to every 600g of deionized water; and the soaking conditions in the carboxymethyl cellulose solution are: soaking at 75-95°C for 2-4 hours.

3. The method for preparing the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material according to claim 1, characterized in that: The amount ratio of the pretreated carbon fiber cloth, diaminoterephthalic acid, N,N-dimethylformamide, zirconium chloride and acetic acid is (4-8) g: (0.108-0.216) g: (50-100) ml: (0.14-0.28) g: (2-10) ml; In step 2), the mixing and stirring speed is 600-1500 r / min.

4. The method for preparing the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material according to claim 1, characterized in that: In step 3), the temperature of the first solvent thermal reaction is 100-140° C., and the time is 20-30 hours.

5. The method for preparing the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material according to claim 1, characterized in that: In step 4), the MnO2 solution is prepared by adding 0.0316-0.0632 g of MnO2 to every 50-100 ml of deionized water.

6. The method for preparing the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material according to claim 1, characterized in that: In step 4), the temperature of the secondary solvent thermal reaction is 100-140° C., and the time is 10-24 hours.

7. The method for preparing the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material according to claim 1, characterized in that: In step 5), the mass fraction of the phenolic resin ethanol solution is 20%-25%; the immersion pressure is 0.07-0.1 MPa, and the immersion time is 24-26 hours.

8. The method for preparing the CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material according to claim 1, characterized in that: In step 5), the temperature of the hot pressing curing is 160-180° C., the pressure is 3-8 MPa, and the curing time is 6-12 minutes.

9. A CMC / UiO66-NH2 / MnO2 synergistically non-destructive modified carbon cloth reinforced resin friction material, characterized in that: The CMC / UiO66-NH2 / MnO2 synergistic non-destructive modified carbon cloth reinforced resin friction material is prepared by the preparation method of any one of claims 1 to 8. The CMC / UiO66-NH2 / MnO2 synergistic non-destructive modified carbon cloth reinforced resin friction material has a tensile strength of 463.73-585.07 MPa; a friction coefficient of 0.124-0.134; and a wear rate of 3.69×10 -12 -7.24×10 -12 m 3 / (N·m).

10. Use of the CMC / UiO66-NH2 / MnO2 synergistic non-destructive modified carbon cloth reinforced resin friction material prepared by the preparation method of the CMC / UiO66-NH2 / MnO2 synergistic non-destructive modified carbon cloth reinforced resin friction material according to any one of claims 1 to 8 in vehicle braking.

Images