MMT@NiO hybrid filler, preparation method and application thereof, and hybrid filler reinforced self-lubricating fiber fabric composite material, preparation method and application thereof

Abstract

The present application relates to the technical field of lubricating material, in particular to a kind of MMT@NiO hybrid filler and its preparation method and application, hybrid filler reinforced self-lubricating fiber fabric composite material and its preparation method and application.The present application provides a kind of MMT@NiO hybrid filler, including amino silane montmorillonite and nickel oxide nanosheet loaded on the surface of the amino silane montmorillonite.MMT@NiO hybrid filler is added to resin matrix as the reinforcing agent of self-lubricating backing material, can play the load support effect of layered montmorillonite and the interface protection effect of nickel oxide nanosheet in the process of friction, promote the stable protective film to be formed at friction interface, while reducing the wear of composite material, improve the service stability of composite material under dry sliding condition.

Description

Technical Field

[0001] This invention relates to the field of lubrication materials technology, specifically to an MMT@NiO hybrid filler and its preparation method and application, and a hybrid filler-reinforced self-lubricating fiber fabric composite material and its preparation method and application. Background Technology

[0002] Self-lubricating spherical plain bearings are a type of sliding support component that relies on a liner material to reduce friction and resist wear. They typically consist of a metal inner ring, an outer ring, and a self-lubricating fibrous fabric liner placed at the friction interface. These bearings feature high load-bearing capacity, low frictional resistance, wear resistance, long service life, and maintenance-free operation, and are widely used in aerospace, rail transportation, and mechanical equipment. Their friction and wear performance directly affects the stability and safety of equipment operation. Existing fibrous fabric self-lubricating liners are mostly made of a blend of high-performance fibers and polytetrafluoroethylene (PTFE) fibers, further compounded with a matrix such as phenolic resin. The fibrous fabric provides a certain load-bearing and self-lubricating effect, while the resin matrix acts as a binder, shaper, and load transfer agent. However, under high loads, prolonged oscillating friction, and frictional heat, the resin matrix is ​​prone to softening, peeling, and crack propagation, leading to fiber exposure, interface debonding, and accelerated wear, thus reducing the bearing's frictional torque stability and service life.

[0003] To improve the wear resistance of liner materials, existing technologies typically incorporate micro / nano fillers such as metal particles, ceramic particles, carbon-based materials, or metal sulfides into the resin matrix. These fillers can improve the material's load-bearing capacity and thermal stability to some extent and participate in the formation of a protective film at the friction interface. However, these fillers generally suffer from poor dispersibility, easy agglomeration, and weak bonding with the resin interface. Furthermore, some hard fillers may increase the coefficient of friction, causing fluctuations in bearing oscillation torque. Therefore, developing a filler that is stably dispersed, has good interfacial bonding, and combines load-bearing support with friction interface regulation is of great significance for improving the friction-reducing and wear-resistant properties and service reliability of self-lubricating fiber fabric liner materials. Summary of the Invention

[0004] Therefore, the purpose of this invention is to provide an MMT@NiO hybrid filler, its preparation method and application, and a hybrid filler-reinforced self-lubricating fiber fabric composite material, its preparation method and application. The MMT@NiO hybrid filler provided by this invention exhibits high dispersion stability in a resin matrix, and can significantly improve the interfacial load-bearing capacity, friction-reducing and wear-resistant properties, and service life of the composite material.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution: The present invention provides an MMT@NiO hybrid filler comprising aminosilyl montmorillonite and nickel oxide nanosheets supported on the surface of the aminosilyl montmorillonite.

[0006] Preferably, the mass content of nickel oxide nanosheets in the MMT@NiO hybrid filler is 30-75%; The aminosilanized montmorillonite has a length of 6~10µm and a width of 2~6µm; The nickel oxide nanosheets have a length of 100-200 nm and a width of 50-150 nm.

[0007] The present invention also provides a method for preparing the MMT@NiO hybrid filler described in the above technical solution, comprising the following steps: mixing aminosilyl montmorillonite, a nickel source and a polar solvent, performing a solvothermal reaction and then calcining to obtain the MMT@NiO hybrid filler.

[0008] Preferably, the mass ratio of nickel in the aminosilanized montmorillonite and the nickel source is 1:0.2~0.8; The nickel source includes nickel nitrate and / or nickel sulfate; The polar solvent includes N,N-dimethylformamide and / or dimethylacetamide; The solvothermal reaction is carried out at a temperature of 120~250℃ for a time of 8~16h. The calcination temperature is 200~300℃, the holding time is 1~3h, and the calcination atmosphere is air.

[0009] The present invention also provides the application of the MMT@NiO hybrid filler or the MMT@NiO hybrid filler prepared by the preparation method described above in the preparation of self-lubricating composite materials.

[0010] The present invention also provides a hybrid filler-reinforced self-lubricating fiber fabric composite material, the raw materials for preparation including polytetrafluoroethylene-reinforced fiber hybrid woven fabric, resin solution and reinforcing filler, wherein the reinforcing filler includes the MMT@NiO hybrid filler described in the above technical solution or the MMT@NiO hybrid filler prepared by the preparation method described in the above technical solution.

[0011] Preferably, the mass of the reinforcing filler is 0.5-2% of the mass of the resin in the resin solution; The resin includes one or more of phenolic resin, polyimide resin, epoxy resin, and polyamide-imide.

[0012] Preferably, the mass ratio of polytetrafluoroethylene to reinforcing fiber in the polytetrafluoroethylene-reinforcing fiber blended fabric is 1:0.5~2; The reinforcing fibers include polyarylate fibers and / or aramid fibers; The mass fraction of polytetrafluoroethylene-reinforced fiber hybrid fabric in the hybrid filler-reinforced self-lubricating fiber fabric composite material is 65-75%.

[0013] The present invention also provides a method for preparing the hybrid filler-reinforced self-lubricating fiber fabric composite material described in the above technical solution, comprising the following steps: The resin solution and reinforcing filler are mixed to obtain the impregnation solution; The polytetrafluoroethylene-reinforced fiber blended fabric is immersed in the impregnation solution and then dried to obtain an unconsolidated fiber fabric. The uncured fiber fabric is cured to obtain a hybrid filler-reinforced self-lubricating fiber fabric composite material.

[0014] The present invention also provides the application of the hybrid filler reinforced self-lubricating fiber fabric composite material described in the above technical solution or the hybrid filler reinforced self-lubricating fiber fabric composite material prepared by the preparation method described in the above technical solution in the preparation of friction motion parts.

[0015] This invention provides an MMT@NiO hybrid filler, comprising aminosilylated montmorillonite and nickel oxide nanosheets supported on the surface of the aminosilylated montmorillonite. When added to a resin matrix, the MMT@NiO hybrid filler acts as a reinforcing agent for self-lubricating pad materials. During friction, it synergistically combines the load-bearing and supporting role of the layered montmorillonite with the interfacial protection role of the nickel oxide nanosheets, promoting the formation of a stable protective film at the friction interface. This reduces wear on the composite material while improving its service stability under dry sliding conditions.

[0016] This invention also provides a hybrid filler-reinforced self-lubricating fiber fabric composite material. The raw materials include polytetrafluoroethylene (PTFE)-reinforcing fiber blended fabric, resin solution, and reinforcing filler. The reinforcing filler includes the MMT@NiO hybrid filler described in the above-mentioned technical solution or the MMT@NiO hybrid filler prepared by the above-mentioned preparation method. The MMT@NiO hybrid filler provided by this invention, after being added to the resin matrix and composited with the PTFE-reinforcing fiber blended fabric, can effectively improve the dispersibility and interfacial bonding strength of the filler in the resin matrix. During friction, the MMT@NiO hybrid filler can participate in the formation of a dense composite friction film, improving the interfacial load-bearing capacity of the composite material, reducing the direct contact between the composite material and the mating parts, thereby reducing resin peeling and fiber wear, and significantly improving the wear resistance and service life of the composite material.

[0017] This invention modifies montmorillonite (MMT) surface with amino-containing silanes, introducing amino and silicon-oxygen structures to provide interfacial anchoring sites for the nickel source. Subsequently, nickel oxide (NiO) nanosheets are grown in situ on the surface of the aminosilanized montmorillonite sheets using a solvothermal method, thus preparing the MMT@NiO hybrid filler. The preparation method provided by this invention is simple, easy to operate, low in production cost, environmentally friendly, and suitable for industrial production. Attached Figure Description

[0018] Figure 1 The images shown are SEM images (a~c) and TEM images (d~f) of montmorillonite (a and d), nickel oxide (b and e) and MMT@NiO (c and f) in Example 1, as well as EDS elemental scans of MMT@NiO (f1~f6). Figure 2 The figures show the wear rate (a) and friction coefficient (b) test results of the hybrid filler-reinforced self-lubricating fiber fabric composites prepared in Examples 1-4 and the PAR / PTFE self-lubricating fiber fabric composites prepared in Comparative Example 1. Detailed Implementation

[0019] The present invention provides an MMT@NiO hybrid filler comprising aminosilyl montmorillonite and nickel oxide nanosheets supported on the surface of the aminosilyl montmorillonite.

[0020] In this invention, the mass content of nickel oxide nanosheets in the MMT@NiO hybrid filler can be 30-75%, or 33.3-66.7%, specifically 30%, 33.3%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 66.7%, 70% or 75%.

[0021] In this invention, the length of the aminosilanized montmorillonite can be 6-10 µm, or even 7-9 µm; the width of the aminosilanized montmorillonite can be 2-6 µm, or even 3-5 µm. In this invention, the length of the nickel oxide nanosheets can be 100-200 nm, or even 120-180 nm, or further 140-160 nm; the width of the nickel oxide nanosheets can be 50-150 nm, or even 70-130 nm, or further 80-120 nm.

[0022] In this invention, the silane in the aminosilanized montmorillonite is an amino-containing silane, which may specifically include 3-aminopropyltriethoxysilane (APTES) and / or N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (AEAPTMS).

[0023] The present invention also provides a method for preparing the MMT@NiO hybrid filler described in the above technical solution, comprising the following steps: mixing aminosilyl montmorillonite, a nickel source and a polar solvent (denoted as the first mixture), performing a solvothermal reaction and then calcining to obtain the MMT@NiO hybrid filler.

[0024] Unless otherwise specified, the materials and equipment used in this invention are all commercially available products in the field.

[0025] In this invention, the mass ratio of nickel in the aminosilanized montmorillonite and the nickel source can be 1:0.2~0.8, or 1:0.3~0.7, or even 1:0.4~0.6, specifically 1:0.4 or 1:0.5. In this invention, the nickel source can include nickel nitrate and / or nickel sulfate.

[0026] In this invention, the polar solvent may include N,N-dimethylformamide and / or dimethylacetamide. In this invention, the solid-liquid ratio of the aminosilylated montmorillonite to the polar solvent may be 1g:50-80mL, or 1g:60-70mL, specifically 0.6g:40mL.

[0027] In this invention, the first mixing can be a combination of ultrasonic mixing and stirring. The ultrasonic mixing power can be 200-300W, or 220-280W, or even 240-260W, specifically 250W. The ultrasonic mixing time can be 15-45 min, or 20-40 min, or even 25-35 min, specifically 30 min. The stirring speed can be 150-400 r / min, or 200-350 r / min, specifically 250 r / min or 300 r / min. The stirring time can be 1-4 h, or 1.5-3.5 h, specifically 2 h or 3 h. In this invention, during the first mixing process, aminosilanized montmorillonite tends to chelate and adsorb nickel ions in the solution through coordination and electrostatic attraction.

[0028] In this invention, the temperature of the solvothermal reaction can be 120~250℃, or 160~200℃, specifically 120℃, 140℃, 160℃, 180℃, 200℃, 220℃, 240℃, or 250℃; the time of the solvothermal reaction can be 8~16h, or 10~14h, specifically 12h. In this invention, during the solvothermal reaction, nickel oxide (NiO) nanosheets are grown in situ on the surface of aminosilanized montmorillonite, and the nickel oxide nanosheets are uniformly distributed on the surface of the montmorillonite sheets.

[0029] After completing the solvothermal reaction, the present invention may further include: performing solid-liquid separation on the system after the solvothermal reaction, washing and drying the obtained solid component to obtain the MMT@NiO hybrid filler. In this invention, the solid-liquid separation may include filtration, vacuum filtration, or centrifugation; the centrifugation speed may be 6000~10000 r / min, or 7000~9000 r / min, or even 8000~9000 r / min; the centrifugation time may be 5~20 min, or 5~15 min, or even 5~10 min. In this invention, the washing solvent may sequentially include anhydrous ethanol and deionized water. In this invention, the drying temperature may be 40~80℃, or 50~70℃, specifically 60℃; the present invention does not have a special limitation on the drying time, drying to constant weight is sufficient.

[0030] In this invention, the calcination temperature can be 200~300℃, or 220~280℃, or even 240~260℃, specifically 250℃; the calcination holding time can be 1~3h, or 1.5~2.5h, specifically 2h; the calcination atmosphere can be air; the heating rate from room temperature to the calcination temperature can be 1~5℃ / min, or 2~4℃ / min, or even 2~3℃ / min.

[0031] In this invention, the preparation method of the aminosilanized montmorillonite may include the following steps: mixing montmorillonite, aminosilane and solvent (denoted as the second mixture), and carrying out a modification reaction to obtain aminosilanized montmorillonite.

[0032] In this invention, the amino-containing silane may include 3-aminopropyltriethoxysilane (APTES) and / or N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (AEAPTMS). In this invention, the mass ratio of montmorillonite to silane may be 1:7.5~11, or 1:8~10.5, or further 1:9~10, and specifically 1:9.46.

[0033] In this invention, the solvent may include water and an alcohol solvent, wherein the alcohol solvent may include ethanol and / or methanol. In this invention, the volume ratio of the water to the alcohol solvent may be 1:2~5, or 1:2.5~4.5, or further 1:3~4, specifically 1:3 or 1:3.5. In this invention, the solid-liquid ratio of the montmorillonite to the solvent may be 1g:150~250mL, or 1g:180~220mL, specifically 1g:200mL.

[0034] In this invention, the second mixing may include: dispersing montmorillonite in a solvent and then adding silane.

[0035] In this invention, the temperature of the modification reaction can be 60-90℃, or 65-85℃, or further 70-85℃, specifically 75℃ or 80℃; the time of the modification reaction can be 8-16 hours, or 10-14 hours, specifically 12 hours; the modification reaction can be carried out under reflux conditions. In this invention, during the modification reaction, a silane molecular layer is successfully grafted onto the surface of montmorillonite (MMT).

[0036] After the modification reaction, the present invention may further include: sequentially performing solid-liquid separation on the obtained modified system, washing and drying the obtained solid components to obtain aminosilanized montmorillonite. Performing solid-liquid separation, washing and drying the obtained solid components yields MMT@NiO hybrid filler. In the present invention, the solid-liquid separation may include filtration, vacuum filtration, or centrifugation; the centrifugation speed may be 6000~10000 r / min, or 7000~9000 r / min, or further 8000~9000 r / min; the centrifugation time may be 5~20 min, or 5~15 min, or further 5~10 min. In the present invention, the washing solvent may be the same type as the solvent added in the modification reaction. In the present invention, the drying temperature may be 40~80℃, or 50~70℃, specifically 60℃; the present invention does not have a special limitation on the drying time, drying to constant weight is sufficient.

[0037] This invention also provides the application of the MMT@NiO hybrid filler described in the above-described technical solution or the MMT@NiO hybrid filler prepared by the above-described technical solution in the preparation of self-lubricating composite materials. After being added to the resin matrix, the MMT@NiO hybrid filler acts as a reinforcing agent for the self-lubricating liner material. During friction, it can synergistically exert the load-bearing and supporting role of layered montmorillonite and the interfacial protection role of nickel oxide nanosheets, promoting the formation of a stable protective film at the friction interface. This reduces the wear of the composite material while improving its service stability under dry sliding conditions.

[0038] The present invention also provides a hybrid filler-reinforced self-lubricating fiber fabric composite material, the raw materials for preparation including polytetrafluoroethylene-reinforced fiber hybrid woven fabric, resin solution and reinforcing filler, wherein the reinforcing filler includes the MMT@NiO hybrid filler described in the above technical solution or the MMT@NiO hybrid filler prepared by the preparation method described in the above technical solution.

[0039] In this invention, the resin may include one or more of phenolic resin, polyimide resin, epoxy resin, and polyamide-imide. In this invention, the mass of the reinforcing filler is 0.5-2% of the resin mass in the resin solution, and may also be 0.8-1.8%, or further 1-1.5%. In this invention, excessive addition of reinforcing filler may cause filler agglomeration, leading to a decrease in the wear resistance of the composite material; when the amount of reinforcing filler added is too small, effective interfacial reinforcement cannot be achieved, resulting in a weak bond between the fiber and the resin matrix, and the mechanical and tribological properties of the composite material cannot be substantially improved, with the overall performance approaching that of the unmodified state.

[0040] In this invention, the mass ratio of polytetrafluoroethylene (PTFE) to reinforcing fibers in the PTFE-reinforcing fiber blended fabric can be 1:0.5~2, or 1:0.8~1.5, and specifically 1:1. In this invention, the reinforcing fibers may include polyaryl ester (PAR) fibers and / or aramid fibers.

[0041] In this invention, the mass fraction of polytetrafluoroethylene-reinforced fiber hybrid fabric in the hybrid filler-reinforced self-lubricating fiber fabric composite material can be 65-75%, or 68-72%, or specifically 70%.

[0042] The present invention also provides a method for preparing the hybrid filler-reinforced self-lubricating fiber fabric composite material described in the above technical solution, comprising the following steps: The resin solution and reinforcing filler are mixed to obtain the impregnation solution; The polytetrafluoroethylene-reinforced fiber blended fabric is immersed in the impregnation solution and then dried to obtain an unconsolidated fiber fabric. The uncured fiber fabric is cured to obtain a hybrid filler-reinforced self-lubricating fiber fabric composite material.

[0043] This invention mixes a resin solution and reinforcing filler (referred to as the third mixture) to obtain an impregnation solution. This invention does not have specific limitations on the third mixture, as long as it can uniformly disperse the reinforcing filler in the resin solution. In this invention, the solvent in the resin solution may include anhydrous ethanol, acetone, and ethyl acetate. The volume ratio of the anhydrous ethanol, acetone, and ethyl acetate may be 1:0.5~2:0.5~2, or 1:0.8~1.5:1:0.8~1.5, or even more specifically 1:1~1.2:1:1~1.2. The solid content of the resin solution may be 10~20%, or 12~18%, or even more specifically 14~16%, or specifically 14%.

[0044] After obtaining the impregnation solution, the present invention impregnates the polytetrafluoroethylene-reinforced fiber hybrid fabric in the impregnation solution and then dries it to obtain an unconsolidated fiber fabric. In this invention, the impregnation and drying are cyclical. The present invention does not have a specific limitation on the number of impregnation and drying cycles, as long as a hybrid filler-reinforced self-lubricating fiber fabric composite material with a polytetrafluoroethylene-reinforced fiber hybrid fabric mass fraction of 65-75% is obtained. In this invention, the drying temperature can be 40-90℃, or 40-80℃, specifically 40℃, 50℃, 60℃, or 70℃; the present invention does not have a specific limitation on the drying time, as long as drying to constant weight is achieved.

[0045] After obtaining the uncured fiber fabric, the present invention cures the uncured fiber fabric to obtain a hybrid filler-reinforced self-lubricating fiber fabric composite material. In the present invention, the curing temperature can be 150~200℃, or 160~195℃, or further 170~190℃, specifically 150℃, 155℃, 160℃, 165℃, 170℃, 175℃, 180℃, 184℃, 190℃, 195℃, or 200℃; the curing pressure can be 0.1~1MPa, or 0.2~0.8MPa, or further 0.2~0.5MPa, specifically 0.1MPa, 0.2MPa, or 0.3MPa. The pressure is 0.4 MPa, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, or 1 MPa; the curing time can be 100-200 min, 120-180 min, or 130-150 min, specifically 100 min, 110 min, 120 min, 130 min, 140 min, 150 min, 160 min, 170 min, 180 min, 190 min, or 200 min.

[0046] The MMT@NiO hybrid filler provided by this invention, when added to a resin matrix and then composited with a polytetrafluoroethylene-reinforced fiber woven fabric, can effectively improve the dispersibility and interfacial bonding strength of the filler in the resin matrix. During friction, the MMT@NiO hybrid filler can participate in the formation of a dense composite friction film, improving the interfacial load-bearing capacity of the composite material, reducing the direct contact between the composite material and the mating parts, thereby reducing resin peeling and fiber wear, and significantly improving the wear resistance and service life of the composite material.

[0047] This invention also provides the application of the hybrid filler-reinforced self-lubricating fiber fabric composite material described in the above-described technical solutions, or the hybrid filler-reinforced self-lubricating fiber fabric composite material prepared by the above-described technical solutions, in the preparation of friction motion components. In this invention, the friction motion component may include at least one of self-lubricating spherical bearings, sliding bearings, bushings, gaskets, guide rails, or sliding plates. In this invention, the friction motion component can be a friction motion component in the field of high-end equipment; the high-end equipment field may include the aviation, aerospace, shipbuilding, or nuclear industry fields. The hybrid filler-reinforced self-lubricating fiber fabric composite material provided by this invention can be used in high-end equipment fields such as aviation, aerospace, shipbuilding, and nuclear industry, specifically as key motion components such as self-lubricating spherical bearings, sliding bearings, bushings, gaskets, guide rails, and sliding plates, to solve technical problems such as high load-bearing capacity, self-lubrication, and wear resistance under harsh operating conditions such as aircraft landing gear, flaps, and rotor systems.

[0048] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0049] Example 1 (1) Disperse 1g of montmorillonite in 200mL of a mixed solvent of deionized water and ethanol with a volume ratio of 1:3. After stirring evenly, add 10mL of 3-aminopropyltriethoxysilane (APTES). Reflux at 80℃ for 12h, centrifuge at 8000r / min for 5min, wash the obtained solid component with a mixed solvent of deionized water and ethanol with a volume ratio of 1:3, and dry at 60℃ to constant weight to obtain aminosilanized montmorillonite (MMT-APTES).

[0050] (2) 0.6 g of aminosilyl montmorillonite and 1.16 g of nickel nitrate hexahydrate were added to 40 mL of N,N-dimethylformyl. The mixture was sonicated at 250 W for 30 min and then stirred at 250 r / min for 3 h. The mixture was transferred to a stainless steel reactor, sealed, and placed in a constant temperature oven. The reactor was kept at 180 °C for 12 h and centrifuged at 8000 r / min for 5 min. The resulting solid component was washed with anhydrous ethanol and deionized water, dried at 60 °C to constant weight, and then calcined in air at a rate of 3 °C / min to 250 °C for 2 h to obtain the MMT@NiO hybrid filler.

[0051] (3) The MMT@NiO hybrid filler was dispersed in a phenolic resin solution to obtain an impregnation solution. The PAR / PTFE fiber blended fabric was impregnated in the impregnation solution and dried in a cycle until the mass fraction of the uncured PAR / PTFE fiber fabric was 70-75%. The uncured PAR / PTFE fiber fabric was then bonded to the friction and wear test specimens using a phenolic resin adhesive. The specimens were cured at 0.2 MPa and 184 °C for 140 min to obtain the friction test specimens (hybrid filler-reinforced self-lubricating fiber fabric composite material). The solvent in the phenolic resin solution was a mixture of anhydrous ethanol, acetone, and ethyl acetate in a volume ratio of 1:1:1, with a solid content of 14%. The mass of the MMT@NiO hybrid filler was 0.5% of the mass of the phenolic resin. The drying temperature was 40 °C. The mass content of PAR in the PAR / PTFE fiber fabric was 50%.

[0052] (4) The friction and wear performance of the friction test specimens was evaluated using a pin-disc friction and wear testing machine. The load was 74.87 MPa, the speed was 0.26 m / s, the test time was 120 min, and the average wear rate of the friction test specimens was 2.83 × 10⁻⁶. -14 m 3 / N·m, with an average friction coefficient of 0.078.

[0053] Figure 1 The SEM images (a~c) and TEM images (d~f) of montmorillonite (a and d), nickel oxide (b and e) and MMT@NiO (c and f) in Example 1, as well as the EDS elemental scan images (f1~f6) of MMT@NiO, show that nickel oxide in MMT@NiO is uniformly distributed on the surface of the montmorillonite sheets.

[0054] Example 2 The only difference from Example 1 is that the mass of the MMT@NiO hybrid filler is 1% of the mass of the phenolic resin; the average wear rate of the friction test specimen is 1.31 × 10⁻⁶. -14 m 3 / N·m, with an average friction coefficient of 0.081.

[0055] Example 3 The only difference from Example 1 is that the mass of the MMT@NiO hybrid filler is 1.5% of the mass of the phenolic resin; the average wear rate of the friction test specimen is 2.81 × 10⁻⁶. -14 m 3 / N·m, with an average friction coefficient of 0.079.

[0056] Example 4 The only difference from Example 1 is that the mass of the MMT@NiO hybrid filler is 2% of the mass of the phenolic resin; the average wear rate of the friction test specimen is 2.83 × 10⁻⁶. -14 m 3 / N·m, with an average friction coefficient of 0.081.

[0057] Comparative Example 1 Friction test specimens (PAR / PTFE self-lubricating fiber fabric composite material) were prepared according to step (3) of Example 1, the only difference from Example 1 being the absence of MMT@NiO hybrid filler; and tested according to step (4) of Example 1, the average wear rate of the friction test specimens was 3.33 × 10⁻⁶. -14 m 3 / N·m, with an average friction coefficient of 0.081.

[0058] Comparative Example 2 The only difference from Example 1 is that the mass of the MMT@NiO hybrid filler is 3% of the mass of the phenolic resin; the average wear rate of the friction test specimen is 3.16 × 10⁻⁶. -14 m 3 / N·m, with an average friction coefficient of 0.082.

[0059] Figure 2 The figures show the wear rate (a) and friction coefficient (b) test results of the hybrid filler-reinforced self-lubricating fiber fabric composites prepared in Examples 1-4 and the PAR / PTFE self-lubricating fiber fabric composite prepared in Comparative Example 1. It can be seen that when the addition amount of MMT@NiO heterocyclic filler is 0.5wt%, the wear rate of the fabric composite increases from 3.33×10⁻⁶. -14 m 3 / N·m decreased to 2.83×10 -14 m 3 The wear rate was reduced by 15% compared to the composite material without MMT@NiO heterocyclic filler, with an addition of 1 wt% of MMT@NiO heterocyclic filler. When the MMT@NiO heterocyclic filler content was 1 wt%, the wear rate of the composite material decreased to 1.31 × 10⁻⁶ N·m. -14 m 3 / N·m, a decrease of 61%; when the addition amount of MMT@NiO heterocyclic filler was further increased to 1.5wt%, the wear rate of the composite material was 2.81×10 -14 m 3 / N·m, the wear rate increased compared to the 1wt% addition amount; when the addition amount of MMT@NiO heterocyclic filler was further increased to 2wt%, the wear rate of the composite material was 2.83×10. -14 m 3The wear rate was similar to that at 1.5 wt% addition, with a wear rate of / N·m. Comparative Example 2 shows that when the addition amount of MMT@NiO heterocyclic filler reached 3 wt%, the wear rate of the composite material was 3.16 × 10⁻⁶ N·m. -14 m 3 The coefficient of friction is approximately 0.078 N·m, possibly because excessive addition of MMT@NiO hybrid filler can easily lead to filler agglomeration, thus deteriorating the wear resistance of the composite material. Due to the excellent lubrication properties of PTFE fiber itself, the addition of MMT@NiO hybrid filler has little effect on the coefficient of friction, and the average coefficient of friction of all composite materials is between 0.078 and 0.081.

[0060] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. An MMT@NiO hybrid filler comprising aminosilanized montmorillonite and nickel oxide nanosheets supported on the surface of the aminosilanized montmorillonite.

2. The MMT@NiO hybrid filler according to claim 1, characterized in that, The mass content of nickel oxide nanosheets in the MMT@NiO hybrid filler is 30-75%; The aminosilanized montmorillonite has a length of 6~10µm and a width of 2~6µm; The nickel oxide nanosheets have a length of 100-200 nm and a width of 50-150 nm.

3. The method for preparing the MMT@NiO hybrid filler according to claim 1 or 2, comprising the following steps: Aminosilane-modified montmorillonite, a nickel source, and a polar solvent were mixed, subjected to a solvothermal reaction, and then calcined to obtain MMT@NiO hybrid filler.

4. The preparation method according to claim 3, characterized in that, The mass ratio of nickel in the aminosilanized montmorillonite and the nickel source is 1:0.2~0.8; The nickel source includes nickel nitrate and / or nickel sulfate; The polar solvent includes N,N-dimethylformamide and / or dimethylacetamide; The solvothermal reaction is carried out at a temperature of 120~250℃ for a time of 8~16h. The calcination temperature is 200~300℃, the holding time is 1~3h, and the calcination atmosphere is air.

5. The application of the MMT@NiO hybrid filler according to claim 1 or 2 or the MMT@NiO hybrid filler prepared by the preparation method according to claim 3 or 4 in the preparation of self-lubricating composite materials.

6. A hybrid filler-reinforced self-lubricating fiber fabric composite material, the raw materials for preparation include polytetrafluoroethylene-reinforced fiber blended fabric, resin solution and reinforcing filler, wherein the reinforcing filler includes the MMT@NiO hybrid filler according to any one of claims 1 to 2 or the MMT@NiO hybrid filler prepared by the preparation method according to any one of claims 3 to 4.

7. The hybrid filler-reinforced self-lubricating fiber fabric composite material according to claim 6, characterized in that, The mass of the reinforcing filler is 0.5-2% of the mass of the resin in the resin solution; The resin includes one or more of phenolic resin, polyimide resin, epoxy resin, and polyamide-imide.

8. The hybrid filler-reinforced self-lubricating fiber fabric composite material prepared according to claim 6, characterized in that, The mass ratio of polytetrafluoroethylene to reinforcing fiber in the polytetrafluoroethylene-reinforced fiber hybrid fabric is 1:0.5~2; The reinforcing fibers include polyarylate fibers and / or aramid fibers; The mass fraction of polytetrafluoroethylene-reinforced fiber hybrid fabric in the hybrid filler-reinforced self-lubricating fiber fabric composite material is 65-75%.

9. A method for preparing the hybrid filler-reinforced self-lubricating fiber fabric composite material according to any one of claims 6 to 8, comprising the following steps: The resin solution and reinforcing filler are mixed to obtain the impregnation solution; The polytetrafluoroethylene-reinforced fiber blended fabric is immersed in the impregnation solution and then dried to obtain an unconsolidated fiber fabric. The uncured fiber fabric is cured to obtain a hybrid filler-reinforced self-lubricating fiber fabric composite material.

10. The application of the hybrid filler-reinforced self-lubricating fiber fabric composite material according to any one of claims 6 to 8 or the hybrid filler-reinforced self-lubricating fiber fabric composite material prepared by the preparation method according to claim 9 in the preparation of friction motion components.

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